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A Review on Thin Film Technology and Nanomaterial Characterization

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DOI: 10.30919/esmm1198

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DOI: https://dx.doi.org/10.30919/esmm1198

A Review on Thin Film Technology and Nanomaterial

Characterization Techniques
Rai Dhirendra Prasad,1, 14 Shivanand B. Teli,2 Rai Surendra Prasad,3 Rai Bishvendra Prasad,4 Saurabh R. Prasad,5 Pramode Sinha,6
Amit Sinha,7 Preety Sinha,6 Mamata Saxena,8 Rai Rajnarayan. Prasad,9 R. S. Pande,10 Naresh Charmode,10 K. G. Deshmukh,11
Prashant D. Sarvalkar,2 U. D. Kadam,12 Chandrasekhar Chiplunkar,13 Nirmala Prasad,15 M.V. Padvi2 and Zhanhu Guo16

Abstract
Over the last 200 years, there has been an increase in the process of depositing thin film materials, which has been
considerably developing. A good understanding of the various deposition methods and processes is necessary to improve the
desired film thickness and characteristics. The purpose of this review paper is to display the critical analysis of existing thin
film deposition methods. The paper discusses some important thin film techniques that are advanced and suitable for the
analysis of thin films. Nanomaterials are invisible and require various advanced characterization to investigate their physical
and chemical properties. Therefore, it becomes essential to determine these properties: there is a need for advanced
scientific tools for the analysis of nanomaterials and thin films. A comprehensive list of fundamentals of thin film technology,
including deposition, structure, film properties, advanced characterization tools and applications are presented together.
Keywords: Nanomaterials; Thin Films; Characterization tools; Deposition techniques; Optical properties, mechanical properties;
Electrical properties; Applications.
Received: 31 March 2024; Revised: 21 June 2024; Accepted: 28 July 2024.
Article type: Review article.

1. Introduction substrate in the form of thin films. Thin film materials are the
The development scenario of an era is accepted by the use of main elements of continued technological advances developed
materials in that particular era e.g. stone, brass, plastic age and in the fields of optoelectronic, photonic and magnetic devices.
now stepped into Nano age. Thus, it becomes essential to study Producing materials into thin films permits easy integration
the properties of materials at Nano regime.[1] Also, it becomes into different kinds of devices. Thin films are enormously
important to deposit nanomaterials on the surface of the solid thermally stable and rationally hard but they are fragile.[2]
Therefore, modern technology needs to study thin films
1 Bihar Veterinary College, Samanpura, Khajpura, Patna 800014, applications in different areas such as gas sensing, super
Bihar, India. capacitors and solar cells, etc. Thus, thin film technology is
2 Shivaji University, Kolhapur 416004, Maharashtra, India. the basis of astonishing development in solid-state electronic
3 Banaras Hindu University Varansi 221005, Uttar Pradesh, India. research area. The usefulness of the optical properties of metal
4 Department of Botany, Birsa Agricultural University, Kanke films and scientific curiosity about the behavior of two-
Ranchi 834006, Jharkhand, India. dimensional solids has been responsible for the immense
5 Department of Electronic and Telecommunication Engineering , interest in the study of science and technology of the thin
DKTE Society’s Textile and Engineering Institute, Ichalkaranji films.[3] Thin film studies have directly or indirectly advanced
416115, Maharashtra State, India. many new areas of research in solid state physics and
6 Department of Zoology, BA Bihar University, Muzaffarpur 842001, chemistry which are based on phenomena uniquely
Bihar, India. characteristic of the thickness, geometry, and structure of the
7 Department of Defense Studies, SP. Pune University, Pune 411007, film.[4]
Maharashtra, India. A thin film is a layer of material whose thickness ranges
8 Regional College of Education, Bhopal 462013, Madhya Pradesh, from 100 nm. The art of creating thin film on any solid
India. substrate is known as thin film deposition. Of course, it is a
9 Department of Civil Engineering, Muzaffarpur Institute of relative layer, but in most cases, thin film deposition
Technology, Muzaffarpur 842003, Bihar State, India. techniques are intended to develop layers that are only 100 nm

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Review article ES Materials & Manufacturing

thick. Material science researchers considered that, thin films (100-10000 Å) and moderately thick film (above 1000 Å).[11,12]
are commonly thought of in connection with semiconductors. In physical deposition technique, mechanical or
Thus, these are significant in a multiplicity of other research electrochemical methods are used to deposit the thin film on
fields where coatings only a 50-100 nm thick. The thin film is the substrate. Materials to be deposited on the substrate is
essential because it amend the surface interactions of newly totally depend upon the temperature, pressure and other
made platform from the bulk substrate properties. Thin films physical conditions.[13] The second process is called as
have a range of properties such as (1) Optical thin films, (2) chemical vapor deposition. It is a chemical process in which,
Electrical or electronic thin films, (3) Magnetic thin films, (4) the gaseous precursor is used. The precursor gases are moved
Chemical thin films, (5) Mechanical thin and (6) Thermal thin into the chamber with the substrate. A chemical reaction takes
films.[5] place between the substrate and precursor. The reaction is
It is possible to deposit materials in the form of thin film continued up to higher temperature till the desired thickness is
by employing number of physical or chemical techniques. obtained.[14,15] The overall thin film deposition technique
These various techniques are classified into different groups contains three major steps viz. (1) The creation of
(see Fig. 1). The synthetic technique is broadly classified into atomic/molecular/ionic species, (2) Transport of these
two groups such as physical method, also known as top-down materials through a suitable medium, and (3) Condensation of
method and chemical method, also known as bottom-up species on a proper substrate.[16]
method. Physical method involves various routes of synthesis
such as thermal evaporation, sputtering, epitaxial growth, 2. Thin Fil deposition techniques
electron beam evaporation and vacuum evaporation.[6] In There are many thin film deposition techniques but some of
physical route of deposition, the material to be deposited was them are briefly discussed below:
converted into gaseous form either by heating or mechanical
impact.[7] Meanwhile, the chemical synthesis of thin films 2.1 Vacuum evaporation method
method involves anodization, chemical vapor deposition, Vacuum evaporation (vapor deposition) is a processing
chemical bath, electrodeposition, electroplating, electrolysis technology that involves heating materials in a high-vacuum
and electroplating, etc.[8,9] On the other hand, the physical space until they turn into vapor and form a thin film (coating)
routes of synthesis are crucial, expensive and require advanced on the substrate. When powerful energy is applied to
instruments for product analyses. The chemical routes of evaporation materials using an electronic beam or lasers in a
synthesis are economical and simple compared to physical vacuum environment, they evaporate and coat a nearby glass
route. Thus, the chemical route of synthesis is widely used for or plastic substrate, forming a thin film. This process is called
the preparation of thin films. The properties of thin film vacuum evaporation, and it is one of the key method for
depend upon numerous factors such as preparation conditions, creating a thin film on the objects (see Fig. 2). The vacuum
film structures, defects existence if any, impurities and film evaporation process contains two steps: i.e. evaporation of the
thickness.[10] The huge usage of nanomaterials in the form of functional material and its condensation on the surface of a
thin film have managed the interest to the researchers to seek suitable substrate. In high vacuum evaporation, electrical
into the appropriate method for synthesis to obtain better heating or electron beam heating is used for melting or
specific properties. A thin film may be define as deposited gasification and evaporation of the coating materials.[17]
solid layer thickness should be few angstrom to 10 microns. The vacuum evaporation method needs following essential
Further depending upon the thickness, the thin films may be requirements:
classified into three groups: Ultra-thin (50-100 Å), Thin film (a) Source: In high evaporation system the electrical or
electron beam heating is used to melt, gasify and evaporate the
10 Nagpur Veterinary College, Nagpur 440006, Maharashtra State, deposited material. The vapor of the deposited material then
India. moves to the surface of the substrate and after cooling a good
11 Veterinary and Animal Husbandry, Osmania University,
quality thin film layer was formed. The vacuum is used to
Hyderabad 500007, Andhra Pradesh, India. arrest the collision of evaporated particles with the
12 Department of Chemistry, Warana Mahavidyalay, Warananagar
background of gas or other unwanted particles.[18]
416114, Kolhapur, Maharashtra, India. (b) Evaporate: The evaporation and deposition of thin film on
13 Department of Textile Engineering, Indian Institute of
the substrate is carried out in vacuum condition is known as
Technology, Delhi 110016, India. evaporate (see Fig. 3). Evaporating the evaporation materials
14 Koshi College, Khagaria 851205, Bihar, India.
under vacuum conditions that are 1 to 100-millionth of
15 Department of Education, CSJM Kanpur University, Kanpur
atmospheric pressure allows more reliable formation of the
298024, Uttar Pradesh, India. thin film on the substrate. The difficulties arise in direct
16Department of Mechanical and Construction Engineering,
evaporation process because of fragmentation of the vaporized
Northumbria University, Newcastle upon Tyne NE1 8ST, UK compounds which are overcome in reactive evaporation where
* Email: [email protected] (R. D. a metal is evaporated and forms the metal species in presence
Prasad) of reactive gas molecules.[19]

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Fig. 1 Thin film deposition techniques. Reproduced with the permission from [8], Copyright 2020 Korean Physical Society.

2.2 Hydrothermal method

In the early days, the hydrothermal technique was popular and
was well developed by geologists. Definition for the word
hydrothermal also known as solvothermal, glycothermal,
alcothermal and ammonothermal. In origin Greek word
meaning of the “hydrous” is water and “thermos” means heat.
The term hydrothermal coined by British geologist, Sir
Roderick Murchison to describe the action of water on
elevated temperature and pressure.[21] Whenever water is used
as a solvent the technique is recognized as hydrothermal and
method is perfect for the synthesis of crystalline oxide and
non-oxide material. The crystalline solids include silicates
with high porosity like zeolite is an oxide and some non-
oxides material.[22] The non-oxide crystalline material
Fig. 2 Vacuum evaporation method. produced by solvothermal process includes carbon nanotubes,
diamonds, carbides, chalcogenides, nitrides, phosphides and
(c) Substrate: Substrate is nothing but the material on which borides.[23] In solvothermal process higher pressure can be
film is to be deposited and should be chemically washable. applied to disperse non oxide, Nano-crystalline materials and
The resistance heated wire should be chosen of materials to stabilize meta stable phase. This method also involves
which have high melting point and low vapor pressure and are reaction like hydrolysis, oxidation and thermolysis and
made up of Tungsten, Molybdenum and Tantalum.[20] possible to synthesize fine powder or thin films.[24]

Fig. 3 Evaporation mechanism for thin film preparation in presence of (a) air and (b) vacuum.

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Now a days this process has become important tool for a) Preparation: The substrate typically made of silicon, glass
advanced material processing because of its advantage in or another suitable material is cleaned carefully to remove any
Nano structured materials for a wide range of technological contaminants that could affect the quality of the film. The
uses such as in optoelectronics, dye degradation, magnetic liquid precursor often referred to as a spin-on material is ready
data storage, biomedical, biophotonics, ceramics, biosensors to keep by dissolving the desired material in a solvent to form
and gas sensors.[25,26] It is believed that the largest single crystal a homogeneous solution or suspension.
formed in nature and some of the large quantity of single b) Dispensing: A small amount of the liquid precursor is
crystal formed in nature and some of the large quantity of dispensed onto the center of the substrate using a syringe,
single crystal created by man in one experimental run is pipette or automated dispensing system. The volume of liquid
hydrothermal origin. Another aspect of hydrothermal dispensed and the viscosity of the solution determine the final
synthesis technique is called as forced hydrolysis. In this case thickness of the thin film.
usually diluted solutions of MTeMoO6 (M=Zn, Mg, Mn) c) Spinning: The substrate is placed on a spin coater, a
inorganic metal salts are hydrolysis for energy storage at specialized instrument equipped with a spinning chuck. The
elevated temperature.[27] Fig. 4 represents the hydrothermal spin coater rapidly spins the substrate at high speeds typically
autoclave system for synthesis of metal salts, with Teflon liner ranging from a 100 to several thousand revolutions per minute.
and stainless steel module. As the substrate spins, centrifugal force causes the liquid
An ideal hydrothermal autoclave should have the following precursor to spread outwards, forming uniform thin film.
characteristics: d) Evaporation: As the liquid film spreads, the solvent begins
1) It should be inert towards the action of acids, bases and to evaporate, leaving behind a thin layer of the desired material
oxidizing agents. on the substrate. The rate of solvent evaporation depends on
2) The apparatus should be such as to easily assemble and factors such as temperature, humidity and the volatility of the
dissemble. solvent.
3) There should be temperature variation system. e) Annealing (optional): In some cases, the thin film may be
4) Leak-proof with unlimited capabilities to the required subjected to annealing or baking to remove residual solvent
temperature and pressure. and enhance the film's properties, such as adhesion, density,
5) Rugged enough to bear high pressure and temperature and crystallinity.
experiments for long duration, so that no treatment is required f) Advantages
after each experimental run. 1) High uniformity: The centrifugal force generated during
spinning helps to spread the liquid precursor evenly across the
2.3 Spin coating method substrate, resulting in thin films with excellent uniformity and
This is a widely used technique for depositing thin films of thickness control.
materials onto a substrate. It is commonly applied in different 2) Versatility: Spin coating can be used with a wide range of
area such as microelectronics, optics, electronics and materials, including polymers, photoresists, nanoparticles, and
nanotechnology. This process contains spread on a liquid organic compounds, making it suitable for diverse
precursor onto a substrate, which is then spun at high speeds applications.
to spread the liquid in the form of a thin uniform film. As the 3) Speed: The spin coating process is relatively fast, with
substrate spins centrifugal force causes the liquid to spread typical spin times ranging from a few seconds to a few minutes,
outwards, resulting in a thin layer with controlled thickness depending on the desired film thickness and spinning speed.
(see Fig. 5). Here is an overview of the spin coating process:[28]

Fig. 4 Represents the Hydrothermal autoclave system. Reproduced with the permission from [27], Copyright 2021 Elsevier B.V.

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Fig. 5 Steps of spin-coating of thin-film on a substrate.[28]

2.4 Dip coating method c) Withdrawal: After the immersion period, the substrate is
This is a simple and widely used technique for depositing thin slowly withdrawn from the coating solution at a controlled rate.
films onto substrates. It involves immersing a substrate into a As the substrate is lifted, the liquid film adhering to its surface
liquid solution or suspension of the desired material, then forms a thin layer due to capillary action and surface tension.
withdrawing it at a controlled rate to form a thin, uniform film The withdrawal speed and withdrawal angle can influence the
on the substrate's surface. Fig. 6 indicates the sequential stages thickness and uniformity of the resulting thin film.
of the dip-coating technique for thin film deposition: (a) the d) Drying: Once withdrawn from the coating solution, the
substrate is dipped and immersed in the sol precursor, (b) the substrate is allowed to dry to evaporate the solvent and solidify
substrate is withdrawn at constant speed rate and (c) solvent the thin film. The drying process can be carried out at ambient
evaporation yields to the gelation of the layer. Dip coating is temperature or under controlled conditions, such as elevated
commonly used in various industries, including electronics, temperature or reduced pressure, to accelerate solvent
optics, coatings and nanotechnology.[29] Here's an overview of evaporation and improve film quality.
the dip coating process: e) Annealing (optional): In some cases, the thin film may be
a) Preparation: The substrate, typically made of glass, silicon, subjected to annealing or baking to remove residual solvent,
or another suitable material, is cleaned thoroughly to remove improve adhesion, enhance film properties, or induce phase
any contaminants that could affect the quality of the thin film. transformations.
The liquid precursor, often referred to as a coating solution, is f) Advantages
prepared by dissolving the desired material in a suitable 1) Simple and cost-effective: Dip coating requires minimal
solvent to form a homogeneous solution or suspension. equipment and can be performed using readily available
b) Dipping: The substrate is slowly immersed into the coating materials, making it a cost-effective technique for thin film
solution until fully submerged. The immersion speed, deposition
immersion angle, and immersion depth can all affect the 2) High uniformity: With proper control of immersion and
thickness and uniformity of the resulting thin film. The withdrawal parameters, dip coating can produce thin films
substrate is held in the solution for a predetermined period, with excellent uniformity and thickness control.
allowing the liquid to wet the substrate's surface and form a 3) Versatility: Dip coating can be carried out using various
uniform film. materials such as polymers, ceramics, metals, nanoparticles

Fig. 6 Sequential stages of the dip-coating technique for thin film deposition. Reproduced with the permission from [29], Copyright
2010 American Chemical Society.

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and organic compounds, making it suitable for diverse electrons at the cathode and are reduced to form a solid metal
applications. layer. Meanwhile, metal atoms from the anode are oxidized
and dissolve into the plating solution to replenish the metal
2.5 Electroplating method ions.
Electroplating, also known as electrodeposition, method used e) Control: The plating process is typically carried out at
to deposit a thin layer of metal onto a conductive surface, controlled conditions of temperature, pH, and current density
typically a metal substrate. It involves passing an electric to optimize plating efficiency, adhesion, and uniformity.
current through a solution containing dissolved ions of the Various parameters, such as plating time, current density and
metal to be deposited (the plating metal), causing the ions to agitation may be adjusted to succeed the desired plating
migrate to the substrate and plate out as a thin, uniform coating. thickness and properties.
The electroplating or electrodeposition process diagram is as f) Finishing: After the plating process is complete, the plated
illustrated in Fig. 7. Electroplating is widely used in various substrate may undergo additional finishing steps, such as
industries for decorative, functional, and protective purposes. rinsing to remove excess plating solution, drying, and post-
It is mainly used to change the appearance of a substance by plating treatments (e.g., passivation, polishing) to improve
making a dull surface look shiny. Many metals like gold, silver, surface quality and corrosion resistance.
copper, nickel, and chromium are plated this way. Non-metals g) Advantages
like plastic, wood or glass that does not conduct any electricity It is commonly used for decorative finishes, corrosion
must be prepared conductive before plating. Here's an protection, wear resistance and improving electrical
overview of the electroplating process:[30] conductivity in various applications across industries such as
a) Preparation: The substrate to be plated is known as the automotive, electronics, aerospace and jewelry manufacturing.
cathode. It is carefully cleaned to remove any dirt, grease, or h) Factors affecting: Electroplating of metals can take time
oxides that could interfere with the plating process. The depending upon factors include:
plating metal is called as the anode is typically in the form of 1) The strength of electric current
a solid metal electrode or a soluble metal salt dissolved in the 2) The concentration of the electrolyte
plating solution. 3) The surface area of the electrodes
b) Plating bath: The plating solution is nothing but the 4) Temperature
electrolyte is prepared by dissolving the desired metal salt in a 5) The distance between the cathode and the anode. Increasing
suitable solvent or aqueous solution. The choice of plating the current or concentration increases the speed at which the
solution depends on factors such as the type of metal to be ions move and hence, the deposition process.
plated, the desired plating thickness, properties, and Electroplating is a material additive process in that it deposits
environmental concerns. material to the surface of an object or base metal. Before
c) Setup: The cathode (substrate to be plated) and the anode further describing the process, the four important features of
(plating metal) are immersed in the plating solution with the an electroplating system need to be explained.
cathode connected to the negative terminal and the anode a) Rectifier: A rectifier is a device that receives power from
connected to the positive terminal of a DC power supply. The the electrical lines we see outside and converts the incoming
distance between the cathode and anode, as well as the current alternating current (AC) to a direct current (DC) that will be
density is carefully controlled to ensure uniform plating. used in the process. An important part in the electroplating
d) Plating process: When an electric current is passed the process, the rectifier transforms the high voltage, low
metal ions from the plating solution are attracted to the amperage AC supply that is not suitable for most metal
cathode and deposit onto its surface. The metal ions gain finishing operations, to a substantially reduced voltage and

Fig. 7 Schematic diagram of Electroplating deposition process. Reproduced with the permission from [30], Copyright 2020 Elsevier
Inc.

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increased amperage DC supply. desired film thickness and uniformity.

b) Electrolyte: The electrolyte is an aqueous ionic solution c) Deposition: The atomized droplets are sprayed onto the
comprised of many ingredients that assist in the substrate surface using a spraying device or system. The
electrodeposition process. Some of these ingredients include substrate may be held stationary, or it may be moved relative
the metal or metals that are being deposited and conducting to the spraying device to achieve uniform coverage. Multiple
salts that promote good electrochemical stability. passes may be made to build up the desired film thickness.
c) Anode: In most cases, the anode, or positively charged d) Drying or curing: After deposition, the sprayed coating
electrode, is made of the same metal being deposited onto the undergoes drying or curing to remove the solvent or carrier
object. In other cases, like with chromium, the anode will only fluid and solidify the thin film. The drying process can be
be used to transmit the electrical current. In these cases, the carried out at ambient temperature or under controlled
anode needs to be made out of a material that will not dissolve conditions, such as elevated temperature or reduced pressure,
or deteriorate, like lead. depending on the properties of the coating material and the
d) Cathode: The cathode is the object to be plated. It is a desired film characteristics.
negatively charged object that attracts the ions reduced at the e) Post-treatment (optional): Depending on the specific
anode. application and requirements, the deposited coating may
undergo additional post-treatment steps, such as annealing,
2.6 Spray coating curing, or surface modification, to enhance its properties,
This technique used to deposit thin films of materials onto adhesion, or performance.
substrates by spraying a liquid precursor or dispersion onto the f) Advantages
substrate surface and diagram is presented (see Fig. 8). This 1) Versatility: Spray coating can be used with a wide range of
method is widely used in various industries, including materials, including polymers, ceramics, metals, nanoparticles,
electronics, coatings, optics, and biomedical applications. and organic compounds, making it suitable for diverse
Spray coating offers several advantages, including versatility, applications.
scalability, and the ability to deposit thin films on complex- 2) Scalability: Spray coating can be easily scaled up for large-
shaped substrates. Here's an overview of the spray coating scale production, making it suitable for industrial
process as per published report:[31] manufacturing processes.
a) Preparation: The substrate, typically made of glass, metal, 3) Uniformity: With proper control of spraying parameters,
ceramic, or polymer, is cleaned thoroughly to remove any spray coating can produce thin films with excellent uniformity
contaminants that could affect the quality of the thin film. The and thickness control.
liquid precursor or dispersion, often referred to as a spray 4) Ability to coat complex shapes: Spray coating can be used
solution, is prepared by dissolving or dispersing the desired to deposit thin films on substrates with complex geometries or
material in a suitable solvent or carrier fluid to form a irregular surfaces, making it suitable for a wide range of
homogeneous solution or suspension. applications.
b) Atomization: The spray solution is atomized into fine
droplets using a spray nozzle or atomizer. Atomization can be 2.7 SILAR method
achieved by various methods like pneumatic atomization, SILAR stands for "Successive Ionic Layer Adsorption and
ultrasonic atomization, or airless atomization. The size and Reaction." It is a thin film deposition technique used to grow
distribution of the droplets can be controlled to attain the thin films with controlled thickness and composition,

Fig. 8 Schematic diagram of spray coating method. Reproduced with the permission from [31], Copyright 2018 American Chemical
Society.

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Review article ES Materials & Manufacturing

particularly for semiconductor materials and solar cell the thin film layer with the desired thickness and composition.
applications. SILAR is based on the sequential adsorption of The number of cycles and the choice of precursor solutions
precursor ions or molecules onto a substrate surface, followed can be adjusted to control the film properties such as thickness,
by a chemical reaction to form a thin film layer. Here's how com position, and crystallinity.
the SILAR process typically works and the process diagram is g) Advantages
extracted from published paper (see Fig. 9).[32] 1) Controlled thickness: SILAR allows precise control over
a) Substrate preparation: The substrate, often a solid the thickness of the deposited thin films by adjusting the
material such as glass, silicon, or a metal oxide, is cleaned number of deposition cycles.
thoroughly to remove any contaminants and ensure good 2) Composition control: By choosing different precursor
adhesion of the thin film. solutions, SILAR enables the deposition of thin films with
b) Precursor solutions: Two or more precursor solutions are complex compositions and hetero-structures.
prepared, each containing ions or molecules of the desired 3) Low cost: SILAR is a relatively simple and low-cost
materials to be deposited in the thin film. These precursor deposition technique compared to some other thin film
solutions may be dissolved in solvents or aqueous solutions, deposition methods, making it attractive for research and
depending on the specific materials and deposition conditions. development applications. SILAR has been used to deposit
c) Adsorption: The substrate is immersed in the first precursor thin films of various materials, including metal oxides,
solution, allowing the precursor ions or molecules to adsorb chalcogenides, semiconductors, and hybrid organic-inorganic
onto the substrate surface through electrostatic interactions or materials, for applications such as solar cells, sensors,
chemical bonding. The duration of immersion and the photodetectors, and electrochromic devices.
concentration of the precursor solution are typically controlled
to achieve the desired thickness of the adsorbed layer. 3. Thin film characterization techniques
d) Rinsing: After the adsorption step, the substrate is rinsed In recent years Nano-structured materials of different metals
with a suitable solvent or rinsing solution to remove excess and metal oxide are widely synthesized for various
precursor solution and any unreacted species from the applications.[33] These Nano materials properties are different
substrate surface. from that of bulk and depend upon their size and morphology.
Reaction: The substrate with the adsorbed precursor layer is Once a material is developed it becomes essential to
then immersed in the second precursor solution, which characterize. An important issue is the correct interpretation of
contains ions or molecules that react with the adsorbed species the experimental outcomes obtained through characterization
from the first solution to form a thin film layer. The reaction tools. So, it is necessary to characterize physical, structural
may involve chemical reactions, complexation, or and optical properties of the materials to qualify as a Nano
precipitation processes, depending on the specific materials material. Without characterize tools for Nano materials
and deposition conditions. analysis, it would be not possible to find out nanoscale.[34] Of
e) Rinsing and drying: After the reaction step, the substrate course, a technique that measures macroscopic objects around
is rinsed again to remove any residual reactants or by-products since the beginning of intellectual thoughts. One of major
from the thin film surface. The substrate may then be dried or distinction to keep in mind is that although to measure
annealed to remove solvent residues and improve the thin macroscopic properties at Nano level. Characterization and
film's adhesion and crystallinity. outcome reporting are fundamental to science. Measurements
f) Repeat: Steps 3 to 6 are repeated sequentially to build up are accompanied by tools: the instruments, machines,

Fig. 9 SILAR method for preparation of thin films.[32]

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ES Materials & Manufacturing Review article

computer hardware and software.[1,35] Measurement is (a) Compositional or chemical characterization

accompanied by fundamental to science through communicate The properties of the elements and composites are varying
our scientific achievements. The magnification power of with respect to material. Thus, it is very much essential to have
human eye is up to 10-3M and its resolving power is 1’. Thus, a proper knowledge about the composition of the thin films.
nanoparticles cannot be directly visualized. The size and shape Usually, the thin films are might be deposited on the surface
of nanoparticles determines its activity.[36] If an electron of glass and stainless steel which may be amorphous in nature.
impinging on a solid surface may be scattered once. Multiple Therefore, some advance techniques are to apply for the
scattering occurs if the dimension of the material is greater determination of the internal chemical composition can be
than almost twice the mean free path of electron. The classified as under:
probability of scattering of light is measured by the scattering (b) Morphological or structural characterization
cross-section and mean free path of electrons. When a high The term morphology is of biological origin that indicates the
energy beam of electron is incident upon a thick specimen, a external appearance of the organisms. Generally, morphology
pear-shaped region is known as interaction volume. The indicates the shape, size, structure, color and pattern of
interaction volume increases with increasing beam voltage and material. Thus, the terminology is used for the appearance of
decreases with increasing specimen density is normally the materials under study. The properties of the material at
between 1 and 5µ.[37,38] Thus it can be indirectly analyzed by nanoscale is affected by size and shape. Therefore,
advanced instrumental methods. The instruments used for determination of the morphology of the nanostructure is
analysis is of two types: 1) Spectroscopes and 2) Microscopes. compulsory in the research of nanostructure and thin films.[1]
The characterization techniques can be broadly classified as There are various advanced techniques used for the
under:[39] determination of morphology of materials at nanoscale are
summarized in Table 1.
Table 1. Physical properties used in analysis.
Sr.
Physical properties Instrumental methods based upon physical property
No.

• Spectrophotometry X-Ray, UV, Visible, IR,

colorimetric
• Photometry
Absorption of Radiation
• Radiography
(Determination of absorption of radiations
• Neutron Activated Analysis
1 involve several steps and techniques
• Atomic Absorption
depending upon types of radiations being
• Calorimetry
studied)
• Thermo-luminescence dosimetry
• Nuclear Magnetic Resonance
• Electron Spin Resonance Spectroscopy (ESR)

Emission of Radiation • Emission Spectroscopy X-Ray, UV, Visible

(Emission of radiation is the phenomenon in • Inductively Coupled Plasma Optical Emission
2
which energy is released from a source in the Spectroscopy
form of electromagnetic waves) • Flame photometry

• Polarimetry
• Ellipsometry
Rotation of Radiation • Faraday Rotation
(Also known as optical rotation. Optical • Circular Dichroism Spectroscopy
3
rotation occurs when linearly polarized light • Optical Rotatory Dispersion
passes through certain materials) • Optical Rotatory Dispersion
• Optical Rotatory Sensors
• Dispersion

• X-Ray
Diffraction of Radiation • Electron Diffraction Method
4 (Electromagnetic waves spread out as they • Light Diffraction
encounter an obstacle) • Neutron Diffraction
• Acoustic Diffraction

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• Refractometer
• Interferometry
Reflection of Radiation • X-ray Reflection Technique
5 (It is the process in which electromagnetic • Acoustic Reflection Technique
radiations bounce after they strike the surface) • Optical Reflection Measurement
• Neutron Reflection Techniques
• Electron Reflection Techniques
• Turbidimetry
• Nephelometry
Scattering of Radiation • Raman Spectroscopy
(Electromagnetic waves or particles are • Dynamic Light Scattering
6
redirected or deflected from the original path • Static Light Scattering
when they interact with the matter) • Particle Scattering Technique
• Raman and Inelastic Scattering Techniques
• X-Ray and Neutron Scattering Techniques
• Potentiometry
• Chronopotentiometry
• Kelvin Probe
Electrical Potential
• Voltmeter
7 (It is the amount of electrical potential energy
• Electrostatic Voltmeter
per unit charge)
• Electrochemical Techniques
• Numerical Modeling
• Electrostatic Field Mapping
• Conductivity
• Impedance Spectroscopy
Electrical conductance
• Four Probe Method
8 (It is measurement of material’s ability to
• Two Probe Method
conduct electricity)
• Electrochemical Methods
• Kelvin Probe
• Polarography
• Ammeter
• Shunt Resistance
Electrical Current
9 • Half Effect Clamp Meter
(Flow of electric current through a conductor)
• Current Transformers
• Half Effect Sensors
• Amperometric Titration
• Thermal Conductivity
• Dilatometry
Thermal Properties • Calorimetry
10 ( It is the characteristic of the material that • Thermal Gravimetric Analysis
describe response to the heat) • Differential Scanning Calorimetry
• Thermomechanical Analysis
• Enthalpy Methods
• Mass Spectroscopy
• Ionization
Mass to charge ratio • Acceleration
11
(It is the ratio of ion’s mass to the charge) • Deflection
• Detection
• Data Analysis

Meanwhile, the modern analytical techniques particularly demonstrated in Table 3. The characterization technique can
for analysis of nanoscale parameters of nanomaterials and also be classified in two main type’s viz. spectroscopic and
biological materials are discussed in Table 2. microscopic techniques.
On the other hand, various analytical techniques were used Spectroscopy is a branch of science which deals with the
to characterize the nanomaterials and thin films as interaction of electromagnetic radiations with matter. It is one

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Table 2. Modern characterization techniques for analysis of nanomaterials and biological materials.
Sr.No Abbreviation Characterization techniques Main information (Utility)
Crystal structure, Phase identification, Stress and
XRD X-Ray Diffraction Deformation, Quantitative Analysis, Orientation and Texture,
1
Crystallite size and Strain, etc.
X-ray absorption co-efficient, Elemental identification,
Quantitative Analysis, Local Structural Distortions, Chemical
X-Ray Absorption
XAS State of Species, Co-ordination Geometry, Interatomic
2 Spectroscopy
Distances, Chemical Speciation, Electronic Structure, Debye-
Waller factors, and non-crystalline NPs
Particle Size, Size distribution, Shape and Morphology,
3 SAXS Small Angle X-Ray Scattering Porosity and Surface Area, Inter-particle Interactions, Growth
Kinetics
Electronic structure, Elemental composition, Depth profiling,
X-ray photoelectron
4 XPS Chemical Bonding, Quantitative Analysis, Oxidation States,
Spectroscopy
Ligand Binding, Surface Sensitivity, etc.
Surface Composition, Ligand Binding, Chemical
Fourier Transform Infrared
5 FT-IR compositions, Functional Group Analysis, Chemical Bonding,
Spectroscopy
Quantitative Analysis, Structural Analysis, etc.
Ligand Density and Arrangements, Electronic Core Structure,
Nuclear Magnetic Resonance Chemical shift, Relaxation Times, Spin-Spin Coupling
6 NMR
Spectroscopy Integration, NOE, Atomic Composition, The Influence of
Ligands on NP shape, NP size
Surface Area, Monolayer Adsorption, Multilayer Adsorption,
7 BET Brunauer Emmett Teller
Pore Volume, Pore Size Distribution, Specific Surface Area
Mass and Composition of Stabilizers, Thermal Analysis,
8 TGA Thermogravimetric Analysis Decomposition Kinetics, Moisture Content, Oxidative
Stability, Evaporation and Desorption, etc.
Thickness and Chemical Composition of Self-Assembled
Monolayers of NPs, Elemental Composition, Surface Stability,
9 LEIS Low Energy Ion Scattering
Isotopic Composition, Surface Structure, Chemical Bonding,
Depth Profiling, Surface Sensitivity, etc.
Electronic Transition, Absorption Spectra, Identification of
UV-Visible Ultra-violet Visible Functional Groups, Optical Properties, Size, Concentration,
10
spectroscopy Spectroscopy and Agglomeration State, Hints at Nanoparticles Shape,
Quantitative Analysis, Detection Limit, etc.
Optical Properties, Relation to Structural Features such as
PL Photoluminescence Defects, Size, Emission spectra, Energy Band Structure,
11
Spectroscopy spectroscopy Dopant and Defect States, Quantum Yield, Lifetime and Decay
Dynamics, Composition, etc.
Hydrodynamic Size, Particle Size Distribution, Temperature
and Solvent Effect, Dynamic Effect, Aggregation and
12 DLS Dynamic Light Scattering
Agglomeration Effect, Poly-dispersity Effect, Concentration
Effect, Detection of Agglomeration, etc.
Nanoparticles Size Distribution, Temperature and
13 NTA Nanoparticle Tracking Analysis Environment Effect, Dynamic Behaviour, Aggregation and
Agglomeration, Concentration, Mobility, etc.
Nanoparticles Size and Their Distribution, Protein Structure
Prediction, Biological Insights, Protein Engineering, Co-
14 DCA Direct Coupling Analysis
Evolutionary Signals, Functional Insights, Long Range
Interactions, Residue-Residue Contact, etc.
Elemental Composition, Size, Size Distribution, NP
Inductively Coupled Plasma
15 ICP-MS Concentration, Elemental Composition, Trace Element
Mass Spectroscopy
Analysis, Isotopic Analysis, Matrix Effect and Interferences,

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High Throughput, Quantitative Analysis, Multi-element

Analysis, etc.
Chemical Information on Functional Groups Especially
Surface Sensitivity, Elemental and Molecular Composition,
SIMS, ToF- Sputtering Ion Mass Depth Profiling, Isotopic Analysis, Spatial Resolution, Surface
16
SIMS, MALDI Spectroscopy Contamination, Surface Chemistry, Material Characterization,
Molecular Orientation, and Conformation, Surface
Topography, MALDI for Nanoparticle Size
Magnetic Properties of Nanomaterials, Magnetic Moment,
Vibrating Sample
17 VSM Magnetic Hysteresis, Magnetic Field Dependence, Curie
Magnetometer
Temperature, Sample Properties, etc.
Determination of Hydrophobic Characters of Thin Films,
Wettability, Surface Energy, Surface Roughness, Surface
18 Contact Angle Contact Angle
Modification, Adhesion and Spreading, Surface cleanliness
and contamination, Surface Heterogeneity, etc.
Nanoparticle Size and Distribution, Shape, Crystallographic
Imperfections, Surface Composition, M value, Magnetic
Ferromagnetic Resonance
19 FMR Anisotropic Constant, Demagnetization Fields. It is widely
Spectroscopy
used to determine magnetic anisotropy, magnetic domain
structure, spin dynamics in materials.
X-Ray Magnetic Circular Site symmetry and magnetic moments of transition metal ions
20 XMCD
Dichroism in ferro and ferri magnetic materials element-specific
Confocal Laser Scanning
21 CLSM Imaging, Ultrafine Morphology,
Microscope
22 BAM Brewster Angle Microscope Gas-liquid Interface Imaging
Three-Dimensional Imaging, Surface Topography, Surface
Roughness and Texture, Surface Friction and Adhesion, Nano-
23 APM Atomic Probe Microscopy
mechanical Properties, Chemical composition and
Interactions, etc.
Magnetic Material Analysis, Magnetic Field Measurement,
24 MFM Magnetic Force Microscopy Magnetic Domain Imaging, Surface Mapping, Magnetic
Interactions, etc.
Surface/Adsorbate bonding, Crystalline Structure
Low Energy Electron Determination, Surface Morphology, Surface Symmetry,
25 LEED
Diffraction Surface Reconstruction, Surface Defects and Ordering,
Dynamic Surface Processing, etc.
Chemical Surface Analysis, Elemental Composition, Depth
26 AEM Auger Electron Microscopy Profiling, Quantitative Analysis, Spatial Resolution, Surface
Sensitivity, Chemical State Analysis, etc.
Chemical/Surface Analysis, Used in Material Sciences,
27 CFM Chemical Force Microscopy Biological Sciences, Nanotechnology, Surface Chemistry and
Molecular Interactions
Chemical Profile/ Atomic spacing, Surface Topography,
28 FIM Field Ion Microscopy Surface Dynamics, Defect Analysis, Chemical Composition,
Crystallographic Information, Atomic Resolution Imaging, etc.
Surface Analysis, Electronic Band Structure, Work Function,
Ultraviolet Photoemission
29 UPS Chemical Composition, Surface Sensitivity, Fermi level
Spectroscopy
Position, etc.
Chemical Analysis, Elemental Identification, Quantitative
Atomic Absorption
30 AAS Analysis, Sensitivity, Selectivity, Accuracy and Precision,
Spectroscopy
Sample Matrix Compatibility, etc.
Inductively Coupled Plasma Elemental Analysis, Sensitivity, Selectivity, Isotopic Analysis,
31 ICPMS
Mass Microscopy Speed and Throughput, Accuracy and Precision, etc.
Surface Characterization, Size and Shape of Particle, Polymer
32 SANS Small Angle Neutran Scattering
Conformations and Dynamics, Inter-particles Interactions,

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Phase Separation and Domain Structure, Internal Structure

Porosity, etc.
Characteristic Emission, Elemental Composition, Defects and
33 CL Cathodoluminescence Impurities, Microstructural Analysis, Dopant Distribution,
Opto-electronic Properties.
Latent Heat of Fusion, Heat Capacity, Chemical Kinetics,
Nano-
34 Nano-calorimetry Thermal Conductivity, Calorimetric Imaging, Energetics of
calorimetry
Nanomaterials, Phase Transitions, etc.
Colloidal size, Specific Surface Area, Dynamic Structure
35 Sears Method Sears Method Factors, Phase Diagram and Phase Transition, Collective
Excitation, Dynamic Heterogeneity, etc.
Elemental Analysis, Identification of Molecules, Energy
36 FS Fluorescent Spectroscopy Transfer, Dynamics and Kinetics, Environmental Sensing and
Structural Information, etc.
Nano-sized Particle Analysis, Enhanced Optical Properties,
Localized Surface Plasmon Sensing of Environmental Parameters, Detection of Molecular
37 LSPR
Resonance Binding Events, Refractive Index Sensing, Surface Chemistry
and Functionalization, etc.
Quantitative Elemental Analysis, Elemental Composition,
Rutherford
38 Rutherford Backscattering Depth Profiling, Surface Roughness, Material Identification,
Backscattering
Isotopic Analysis, Thickness Measurement, etc.
NP size, Monodispersed shape, Aggregation State, Defect and
Localize Quantify Nanoparticles in Matrices, Study Growth
Transmission Electron
39 TEM Kinetics, Microstructure characterization, Electron Diffraction
Microscopy
Pattern, Nanoparticle Analysis, Elemental Analysis,
Crystallography, etc.
All Information by Conventional TEM and also on the Crystal
Structure of a Single Particle. It is used to Distinguish
High-Resolution Transmission
40 HR-TEM Between Monocrystalline, Polycrystalline, and Amorphous,
Electron Microscopy
Atomic Scale Imaging, Lattice Parameter Determination,
Defect Analysis, Crystallography, etc.
Depict Nanoparticle Growth in Real-time, Study Growth
Mechanism, Single Particle Motion, and Super-lattice
Liquid Transmission Electron formation, Surface Chemistry and Catalysis, Environmental
41 Liquid TEM
Microscopy and Biological Imaging, Electrochemical Processes, Bio-
molecular Dynamics and Interactions, Real Time Observations
of Dynamic Processes
Study Complex Growth Mechanisms, and Aggregation
Pathways, Good for Molecular Biology and Colloidal
Cryo Transmission Electron Chemistry to Avoid the Presence of Artifacts or Destroyed
42 Cryo-TEM
Microscopy Samples, High Resolution Imaging, Drug Delivery System,
Virus Structure Assembly, Membrane Biology, Structural
Biology, High resolution Imaging, etc.
Crystal Structure, Lattice Parameter, Study Order, and
Disorder Transformation, Long-Range Order Parameters,
43 ED Electron Diffraction Crystallographic information, Phase Identification, Texture
Analysis, Grain Size and Microstructure, Strain Analysis and
Thin Film Analysis, etc.
Combined with HAADF, and EDX for Morphology Study,
Crystal Structure, and Elemental Composition, Study the
Scanning Transmission
44 STEM Atomic Structure of Hetero-interface, Atomic Structure,
Electron Microscopy
Chemical Composition, Strain Mapping, Electronic Structure,
Magnetic Properties, Nano-structure Characterization, etc.

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Aberration- Aberration corrected Scanning Atomic structure of NP clusters, especially bimetallic ones, as
45 corrected Transmission Electron a function of composition, alloy, homogeneity, phase
STEM, TEM Microscopy segregation
Type and Quantity of Atoms Present, Chemical States of
Atoms, Collective Interaction of Atoms with Neighbors, Bulk
Electron Energy Loss Plasma Resonance, Energy Loss Measurement, Core and
46 EELS
Spectroscopy Valence Electrons Interactions, Chemical Composition,
Chemical Bonding and Coordination, Optical and Electrical
Properties, etc.
Realistic 3D article visualization, snapshots, video, and
Electron quantitative information down to atomic scale, Structural
Electron tomography
46 tomography Dynamics and Conformational Changes, Co-relative imaging,
Subcellular and Structural Organelles.
Morphology, Dispersion of Nanoparticles in cells and other
Matrices/ Supports, Surface Morphology, surface Analysis and
Scanning Electron Microscopy- Metrology, Pore Structure and Porosity, Surface Modification
SEM-HRSEM,
47 High-Resolution Scanning and Nanostructure, Chemical Mapping, Elemental
T-SE-EDX
Electron Microscope Composition, Microstructure Analysis, Precision in the Lateral
Dimension of Nanoparticles, Quick Examination-Elemental
Composition
Structure, Crystal Orientation, and Phase of Matrices in SEM.
Examine Microstructure, Phase Identification, Deformation
Electron Backscattered
and Recrystallization, Microstructural Characterization,
48 EBSD Diffraction Microscopy
Texture Analysis, Grain Boundary Characterization, Reveal
Texture, Defects, Grain Morphology, Deformation, etc.
Nanoparticle Size and Shape in 3D mode, Evaluate the Degree
of Covering of a Surface with Nanoparticle Morphology,
Dispersion of Nanoparticles in Cell and other Matrices/
Supports, Surface Topography, Surface Roughness and
Atomic Force Microscope Texture, Electrical and Magnetic Properties, Nano-
49 AFM
manipulation and Nanolithography, Molecular Recognition
and Interactions, Friction and Adhesion, Mechanical
Properties, Precision in the Lateral Dimension of
Nanoparticles, Quick Examination- Elemental Composition
Standard AFM Imaging Together with the Information of
Magnetic Moments of Single NPs. Magnetic contrast, Material
Characterization, Surface Topography, Sample Magnetization,
MFM Magnetic Force Microscopy
50 Magnetic Properties Characterization, Magnetic Field
Mapping, Study Magnetic NPs in the Interior of cells.
Discriminate from Non-magnetic NPs
Fiber orientation angle and distribution of fiber orientation (for
non-woven fabric)
Pore size and porosity
Absorbency, Thickness, Basis weight, Stiffness, Tensile
Gravimetric Absorbency
51 GATS strength, Bursting strength
Testing System
Elements of Tear strength, Air permeability
Comparative analysis, Wrinkle Properties, Retention Capacity,
Rate of Absorption, Absorption Capacity, Surface tension
effect,

of the most powerful tool available for the study of atomic and instrument details are listed in Table 4.
molecular structure and is used in analysis of a wide range of The various spectroscopic techniques include XRD, UV-
samples. Electromagnetic radiations are widely used in for Visible spectroscopy, FT-IR, Raman, Mass and NMR
spectroscopic technique of characterization and each spectroscopy which are highly used to analyses of thin films

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Table 3. Analytical techniques for nanoscale parameters.

Entity characterized Possible characterization techniques
TEM, XRD, DLS, NTA, SAXS, HRTEM, SEM, AFM, EXAFM, FMR, DCS,
Size (structural properties)
ICP-MS, UV-Vis, MALDI, NMR, TRPS, EPLS, magnetic susceptibility
Shape TEM, HRTEM, AFM, EPLS, FMR, 3D-tomography
Elemental chemical composition XRD, XPS, ICP-MS, ICP-OES, SEM-EDX, NMR, MFM, LEIS
Crystal structure XRD, EXAFS, HRTEM, STEM, electron diffraction
DCS, DLS, SAXS, NTA, ICP-MS, FMR, DTA, TRPS, SEM,
Size distribution
superparamagnetic relaxometry
Magnetic properties SQUID, VSM, MFM, FMR, XMCD, magnetic susceptibility
Optical properties UV-Visible spectroscopy, Photoluminescence spectroscopy, EELS-STEM
Detection of Nanoparticles TEM, SEM, STEM, EBSD, magnetic susceptibility
Structural defects HRTEM, EBSD
Dispersion of nanoparticles in
SEM, AFM, TEM
matrices
3D visualization 3D topography, AFM, SEM
Single-particle properties Sp-ICP-MS, UV-Vis, RMM-MEMS, PTA, DCS, TRPS
Density DCS, RMM-MEMS
Agglomeration state Zeta potential, DLS, DCS, UV-Visible spectroscopy, SEM, Cryo-TEM, TEM
Concentration ICP-MS, UV-Visible, RMM-MEMS, PTA, DCS, TRPS
Surface charges Zeta potential, EPM
Surface area, specific surface area BET, liquid NMR
Ligand binding/ composition/ density/
arrangement/ mass, surface XPS, FTIR, NMR, SIMS, FMR, TGA, SANS
composition
Growth kinetics SAXS, NMR, TEM, Cryo- TEM, liquid-TEM
Chemical state –oxidation state XAS, EELS, XPS, Mossbauer

are discussed in the following section; Later, in 1935 Le Galley first assembled X-ray powder
diffractometer.[41] After this magnificent discovery,
3.1 X-ray diffraction technique (XRD) metallurgist and mineralogist exhaustively used X-ray powder
In 1895 by German physicist Wilhelm Conrad Rontgen has diffractometer primarily to investigate structural
invented the X-rays, immediately called X-rays because their imperfections. According to the idea of classical physics, state
nature was unknown at that time. X-rays are invisible, highly of matter can be classified into five different types such as
penetrating electromagnetic radiations of much shorter solid, liquid, gas, plasma and condensed matter. The solid state
wavelength than visible light.[40] X-rays are electromagnetic is again of two types viz. amorphous and crystallite. XRD
radiations with wavelength of the order of 10-10 m. Van Lave technique is the one relevant to measure the crystallite state of
verified in 1912 that X-rays could be diffracted by crystal. matter alone.
Table 4. Electromagnetic spectrum and their possible applications.
Electromagnetic Wave
Applications Orientations Frequency
Radiations Length
Ionization and Gamma
Gamma rays Nuclear 1021 3×10-11
garden
Removal of inner shell
X rays XRD 1019 3×10-9
electrons
Removal of outer shell
Ultraviolet rays UV-visible spectroscopy 1017 3×10-7
electrons
Excitation of valence
Visible UV-visible spectroscopy 1015 3×10-5
electrons
IR/ Raman absorption
IR Molecular vibration 1013 3×10-3
spectroscopy
Magnetically induced
Microwaves EPR 1011 3×10-1
spin state
Radio NMR Spin rotation 109 3×101

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XRD is a powerful versatile and non-destructive The energy used for this process is provided from a generator,
characterization technique suitable for study of crystal connected by an electrical circuit connected to the X-ray tube.
structures such as phase composition, crystal structure, layer The AC is to be converted into DC. The reason for this is to
thickness and orientation of power of solid and thin films. It ensure a constant unidirectional flow of electrons from the
detects crystalline material having crystal domain greater than negatively charged cathode to the positively charged anode.
3-5 nm. The material science domain researchers are The quality and the quantity of the X-ray radiation are
extensively used this technique to find out the crystallite controlled by adjusting the electrical parameter KV-tube
internal structure.[42] Many materials are made up of tiny voltage, potential difference applied across the tube, mA tube
crystallite and chemical composition and structure of these current and exposure time, usually a fraction of second.
crystallite are called phase. The materials can be single phase b) Incident Beam Optics Condition the X-ray beam before it
or multiple phase and may contain crystalline and non- hits the sample.
crystalline components. In XRD analysis, a collimated beam c) The Goniometer
of X-rays, with a wavelength typically ranging from 0.7 to 2 It is the platform which holds and moves the sample, optics,
A0 is incident on a specimen and diffracted by crystalline detector and 100 tube. Goniometer is used to measure joint
phases in the specimen. The famous Bragg’s law:[43] range in each plane of the joint. The term goniometer is of
nλ =2d sin θ (1) Greek origin where “gonia” means angle and “metron” means
where d is the space between atomic planes in the crystalline measurement. A goniometer is most common instrument used
phase and λ is the wavelength of X ray. to measure range of motion.[46] The goniometers are many
types are viz;
3.1.1 Principle and instrumentation a) Universal goniometer: It comes in two forms: short and long
In X-ray diffractometer beam of single wavelength is used to arm form.
examine the specimen. During the analysis of sample, the b) Gravity goniometer: Here one arm has a weighted pointer
angle of X-ray beam is continuously changed. Thus, a that remains vertical under the influence of gravity.
spectrum of diffraction intensity versus the angle between c) Software based goniometer: Here the goniometer may be
incident and diffraction beam is recorded. The basic principles smartphone based. This has several advantages such as easy
of X-ray diffraction can be studied using various published availability, ease of measurement, application based tracking
papers.[44] measurement and one hand use. It is also used as
The main component of diffractometer is mentioned below: accelerometer in phones to calculate the joint angle.
d) Arthrodial goniometer: This is ideal for measuring cervical
a) X-ray tube rotation, anteroposterior flexion, and lateral flexion of the
It is the main source for X-rays. The tube function is specific cervical spine.
energy converter, receiving electrical energy and converting it e) Twin axis electro goniometer: The inter-rater and intra-rater
into two other forms of energy (Radiation) which is reliability of the electro goniometer is higher than the
approximately 1% and remaining 99% part is heat. Here heat universal goniometer but challenging to apply in patient’s
is considered as byproduct or undesired product of this clinical evaluation, hence used more often for research
conversion process. Therefore, X-ray is created by taking the purpose.
energy from electron and converting it into photons. This is f) The sample and sample holder: The solid samples are
very specific energy conversion which takes place in X-ray prepared for X-ray diffraction by grinding also to accomplish
tube. Normally, X-ray tube contains two main components by several other methods, depending on the sample matrix,
such as (1) filament which acts as cathode and boils off sample size and quantity of materials required. Before
electrons by thermionic emissions. (2) Component is target grinding the sold sample is to be freeze for at least 12 h and
which acts as anode and electrons strike to produce X-rays. the sample is to be grinded into fine powder like talk by
The additional components of X-ray tube include expansion different methods such as agate mortar and pestle, shatterbox,
bellows, tube envelope, tube housing, cooling dielectric oil, mixer mill and rock lab hardened steel smasher. Then the fine
rotor, induction stator, tube window, usually made from powered sample is to be transferred into appropriate labelled
beryllium, not glass. The filament which acts as cathode and glass bottle. Gently press the power flush with the sample
target which acts as anode are enclosed in the vacuum in holder using a glass slide. The surface of the power must be
electrical insulation condition. An X-ray tube can have two smooth. Then excess power should be removed from the
filaments at the cathode where a smaller filament produces a sample holder edges taking necessary care and can be placed
smaller focal spot, thus images with greater detail. An X-ray at appropriate place in XRD slot.[47]
tube can have two filaments at the cathode where the smaller g) Receiving field optics Condition the X-ray beam after it has
filament produces a smaller focal spot, thus images with encountered the sample.
greater details. The larger filament produces high intensity X- h) Detector Count the number of X-rays scattered by the
rays with quick response, thus less influenced by movement sample.
artefacts.[45]

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3.1.2 Production of X-rays binding energies of the shell involved.[50]

The production of X-rays involves bombardment of a thick Diffraction basis: In crystals the typical interatomic
target with energetic electrons. This can be summarized as X- spacing is ~ 2.3 Å are the suitable radiation is X-rays.
rays produced in the standard ways, i.e. by heating the filament, Neutrons and Electrons are also being used for diffraction
which releases the electron known as thermionic emission. studies from material. X-ray diffraction is the nondestructive
The released electrons are accelerated with high voltage and contactless method which provides many useful information
allowed to collide with the focal spot on the target anode. The such as presence and composition of phase, film thickness,
X-rays are generated by interaction with anode. Electrons crystalline size and strain state. In the powder method, the
undergo a complex sequence of collision and scattering crystal to be examined is reduced to a fine powder in a beam
processes during the slowing down process which results in of monochromatic X-ray. Here all the particles of the powder
the production of Bremsstrahlung and Characteristic are the tiny crystal or assemblage of smaller crystals. These
Radiations, as described below:[48] particles are oriented at random with respect to incident beam.
a) Bremsstrahlung X-rays According to Braggs law, for a particular value the
Bremsstrahlung X-rays electrons loose kinetic energy as they constructive interference of X ray should occur only at
travel through the anode because the negatively charged particular θ value, i.e. Braggs angle and for all other angle
electrons are attracted towards the positively charged nuclei. there should be destructive interference and intensity of
The closure the nucleus the electrons passes, the more kinetic diffracted beam will be minimum there.
energy is lost and it is deflected to the continue moving in
another direction at lower energy or stopped altogether. Thus,
maximum kinetic energy is transferred to the production of X-
rays which is emitted from the anode.
Detector
b) Characteristic radiations: Once the electron acquire
Diverging Slit
energy greater than or equal to the binding energy of the X-ray Receiving Slit
orbiting electron in the target atoms, these electrons can be Source

ejected from the atom. This phenomenon most often takes

place from the inner electron shell known as K shell. The
ejected electron is termed as photoelectron. The vacancy
created in the K-shell must be filled in order to keep the atom 2
stable. This process of electron transfer between the shells Sample 
produces X-rays which are characteristic of the binding energy
of that particular element.
The energetic electrons are mostly slowed down in matter
by either Collisions and scattering interaction, or Excitation
interactions. If an electron comes close to an atomic nucleus,
the attractive coulomb force causes a change in electron
trajectory. An accelerated electron or an electron changing its
direction emits electromagnetic radiations and given the name
Bremsstrahlung radiation. The energy of emitted photon is Fig. 10 Schematics of X-ray diffractometer. Reproduced with the
subtracted from the kinetic energy of the electron. The energy permission from [50], Copyright 2016 Elsevier B.V.
of Bremsstrahlung photon depends upon attractive coulomb’s
force and consequently on the distance of the electron from the In crystalline solids the atoms are ordered in a particular
nucleus.[49] repeated pattern referred as unit cell with its interatomic
spacing comparable to wave length of X-ray (0.5 to 2.5Å).
3.1.3 Fundamentals of X- ray production Hence crystals are the best gratings for the diffraction of X-
Figure 10 indicates the schematics of X-ray diffractometer. In rays. The directions of diffracted X-ray provide the
increase in electron energy increases the number of thin layer information about the atomic arrangements; hence the crystal
and each radiating X-rays. The triangular area grows structure and phase formation can be confirmed by X-ray
proportional to the square of electron energy. The last electron diffraction. The way of satisfying Bragg’s condition is devised
colliding with an electron of an atomic shell could knock out and this can be done by continuously varying either  or 
the electron once. If the kinetic energy exceeds the binding during the experiment. The way, in which these quantities are
energy of the electron in that shell. The scattered primary varied and distinguished the three main diffraction methods
electron carries away the difference of kinetic energy and are tabulated in Table 5.
binding energy. The vacancy in the shell is then filled with an In powder method the crystal to be examined is reduced to
electron from an outer-shell accompanied by the emission of a fine powder and placed in a beam of a monochromatic x-
X-ray photon with an energy equivalent to the diffraction in rays. Each particle of the powder is the tiny crystal, or

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Table 5. X-ray diffraction methods.

Sr. No. Method  
1 Laue method Variable Fixed
2 Rotating crystal method Fixed Variable (in part)
3 Powder method Fixed Variable

assemblage of smaller crystals, oriented at random with parameters, arrangement of individual atoms in a single crystal
respect to incident beam. Some of the crystals will be correctly or the phase analysis in case of polycrystalline materials. XRD
oriented so that their (100) planes, for example, can reflect the also useful to identify unknown materials, quantity of amounts
incident beam. Other crystals will be correctly oriented for of different phase present in a sample, and thickness of one or
(110) reflections and so on. The result is that every set of more layer in the micrometer range. To elucidate the 3D
lattice planes will be capable of reflection. This is the principle atomic structure of the crystalline phase of materials and
of a powder diffractometer. Ideally, according to Bragg’s law, qualitative, semi-qualitative and full quantitative riveted
for the particular d value, the constructive interference of x- analysis.
rays should occur only at particular  value, i.e. Bragg’s angle The main applications of XRD can be enlisted as below:
and for all other angles there should be destructive interference 1. Identification of fine-grained minerals such as clays and
and intensity of diffracted beam will be minimum there. mixed layer clays that cannot be easily determined through
optical instruments.
3.1.4 Identification of phases 2. Characterization of crystalline materials.
From the d-spacings, phases can be identified in a film using 3. Determination of purity of the sample.
the standard JCPDS powder diffraction file and the reflections 4. Determination of modal amounts of minerals.
can be indexed with miller indices. However, if the size of the 5. The thin films can be characterized.
diffracting tiny crystal is small, there is no more complete 6. Determination of the thickness, roughness and density of
destructive interference at d, which broadens the peak the thin film using glancing incidence X-ray reflectivity
corresponding to diffracted beam in proportion to the size of measurement.
the tiny crystal. This can be used to calculate the particle size. 7. Measurement of super-lattice in multilayer epitaxial;
The relation for the same is given by Debye Scherrer formula structure.
as:[51] 8. Determination of dislocation density and quality of the film
0.9𝜆 by rocking curve measurement.
𝑡= (2)
𝛽 𝑐𝑜𝑠 𝜃𝐵
9. Determining lattice mismatch between film and substrate
where, t=particle size, B = diffraction angle,  =wavelength
and to inferring stress and strain.
of X-rays and  line broadening at Full Width at Half Maxima
(FWHM).
3.1.6 Strength and Limitations of XRD
Further, the powder diffractometer can also be used for X-
a) Strength
ray diffraction from thin films. Epitaxial or polycrystalline
1) XRD units are widely available and easy to operate.
(may or may not be oriented) thin films can be considered as
2) This is non-destructive method of analysis. This means the
single crystal or powder (crystals or assembly of crystals
sample can be further used for other purposes.
spread on substrate) respectively. Hence, a typical epitaxial or
3) Minimal sample preparation is required.
oriented film may not show all corresponding reflections and
4) Powerful and rapid technique for identification of unknown
show only few reflections for example say, a c-axis oriented
material.
film will show only (hkl) for which h and k indices are zero
5) Data interpretation is simple and straightforward.
and l is non zero. However, these hidden peaks can be detected
6) In most cases it provides an unambiguous mineral
by small angle X-ray diffraction technique.
determination.
7) This a relatively rapid technique for structure and
3.1.5 Applications of XRD composition determination.
The X-rays can be categorized into two main types: soft X- b) Limitations
rays and hard X-rays. The soft X-rays are widely in diagnostic 1) This technique requires 2 gm of sample which must be
purposes in veterinary and human medicines whereas hard X- ground into fine powder.
rays can be employed for determination of structures and 2) There must be access to standard reference files of inorganic
defects of the crystalline structures. The detection limit of compounds.
XRD range is from 0.1 to 1%. Using the XRD pattern 3) In absence of standard reference file, comparison of the
crystallographic structure, chemical composition and physical XRD pattern would not be possible.
properties of the materials are measured. The phase 4) Homogeneous and single-phase material is best for
composition, crystal structure and orientation of powder, solid, identification of an unknown.
liquid and gaseous samples. Also can be calculate the lattice 5) In case of mixture of the materials, the materials having at

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least 2% amount can only be determined. light with thickness of absorbing medium is directly
6) The unit cell determinations, indexing of patterns for non- proportional to the intensity of light as well as concentration
isometric crystal systems is complicated. of solution".[53] This law is followed by eq. (3):
𝐼 = 𝐼𝑜𝑒 −𝑘𝑐𝑥 (3)
3.2 UV-Visible spectroscopy The Beer Lambert’s Law indicates that there is exponential
In this technique the absorption of electromagnetic radiations decrease in the intensity of light with thickness and
is in near Ultraviolet or visible range. This instrument can be concentration of the solution.
effectively used for (1) qualitative and (II) quantitative
analysis of samples.[52] 3.2.2 Instrumentation of UV-Visible spectroscopy
UV-visible spectroscopy is widely used in various fields,
3.2.1 Qualitative determination including chemistry, biochemistry, environmental science and
It is based upon the concept of surface plasmon resonance materials science for qualitative and quantitative analysis of
(SPR) phenomenon of collective oscillation of surface substances. Instrumentation for measuring the absorption of
electrons due to interaction with electromagnetic radiations. UV or visible radiation can be summarized as (a) source (for
Surface plasmon resonance become nice substantial at Nano generation of UV-visible radiations), (b) wavelength selector
regimes as number of surface electron increases at Nano level. (monochromator), (c) sample container, (d) detector, and (e)
When the sample under study absorbs UV or visible light, it signal processer and screen.[54] A pictorial representation of the
promotes an electron from a bonding or nonbonding orbital UV-Vis Spectrophotometer is exhibited ( see Fig. 11).
into one of the empty anti-bonding orbitals. In each possible
case, an electron is exited from a full orbital into an empty a) Source of UV-Visible radiation
anti-bonding orbital. Each wavelength of light has a particular In the instrumentation of UV-Visible (UV-Vis.) spectroscopy
energy associated with it. If a particular wavelength of light is it is of paramount importance to have a suitable source which
having sufficient energy just for excitation of electron, then can effectively generate UV-Vis. radiations. For this purpose,
the electron will be excited ground state to higher energy level. in today’s practice generally tungsten made filament lamp is
The relationship between energy and electromagnetic employed as a source of UV-Vis. radiations. Normally, the
radiation is given as E=hν or E=hc/λ, where E= Energy of each lamp is used in UV-Vis. should be wavelength range between
quanta of light, h = plank’s constant, c =velocity of light in air 350-2500 nm. Tungsten filament is commonly regarded as
or vacuum, and λ = wavelength of electromagnet radiation. incandescent because it radiates light when heated by electric
UV-visible radiations can measure both intensity and energy. Even the filaments of modern light bulb (or lamp) are
wavelength. Also, UV-vis. spectroscopy can be effectively normally composed of tungsten. In modern incandescent lamp
used for quantitative analysis of sample. The quantitative sometimes, carbon arc can be employed. The energy emitted
analysis is based upon Beer-Lambert’s Law; "When a beam of by the tungsten filament is directly proportional to the fourth
monochromatic light is passed through homogenous power of the operating voltage. Electronic voltage regulator or
absorbing medium then the rate of decrease of intensity of constant voltage transformers are used to ensure this stability.

Fig. 11 A pictorial representation of UV-Vis Spectroscopy. Reproduced with the permission from [54], Copyright 2023 Kingfa
Scientific and Technological Co. Ltd.

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Review article ES Materials & Manufacturing

pass through to the sample.

c) Sample container
The sample container holds the sample solution or solid
material to be characterised. Quartz cuvettes are commonly
used for UV-vis. spectroscopy because of their transparency to
UV and visible light. Solid samples may require special
holders or cells to allow for transmission or reflection
measurements.
d) Detector
The detector measures the intensity of light transmitted
through or reflected from the sample at the selected
wavelength. Photomultiplier tubes (PMTs) and photodiodes
are commonly used detectors for UV-visible spectroscopy due
Fig. 12 Localised Surface plasmon resonance. to their sensitivity in the UV and visible ranges. Charge-
coupled device (CCD) detectors are also used, especially in
As shown in the Fig. 12 at room temperature metal atoms modern instruments, for their ability to detect a wide range of
lose their electrons from outermost shells. Once metal atom wavelengths simultaneously.
loses electron from outermost shell it becomes positively e) Signal processor and screen
charged. The positively charged metal ions are called kernels. The signal processor amplifies and processes the signal from
The lost electrons are called as free electron and form a sea of the detector. The processed signal is typically displayed on a
electron. There is the force of attraction between the positively screen, showing the absorption spectrum as a plot of
charged metal ion and negatively charged free electron. This absorbance (or percent transmittance) versus wavelength.
force of attraction is known as the metallic bond. Once the Software may also be used for data analysis, including peak
electromagnetic radiation is incident on the surface of metal identification, quantification, and spectral manipulation.
atom, there is the interaction between the electromagnetic These components work together to calculate the absorption
radiation and free electron. Such interaction leads to resonance of UV or visible radiation by the sample, providing valuable
phenomenon. As at nanoscale number of surface electrons information about its chemical composition, concentration
increases SPR phenomenon becomes more prominent. In fact, and structure.
this phenomenon is also present in bulk condition but not
much significant.[55] The force of attraction between the 3.3 Photoluminescence Spectroscopy
positively charged kernel and negatively charged electron This is the contactless, non-destructive method of probing the
varies from metal to metal. Thus, it is the characteristic of electronic structure of material. Here light is incident on the
metals. sample, where absorbed excess energy is imported into the
b) Wavelength selector (Monochromator) sample. This phenomenon is called as photo-excitation. The
The wavelength selector, often a monochromator is used to excess of energy is imparted on the sample and can be used in
isolate a narrow range of wavelengths from the source. This is different ways such as (a) to increase in internal energy of the
crucial for selecting the specific wavelength of light to be sample, (b) the excess amount of energy is reflected, (c) the
absorbed by the sample. Monochromators can be based on incident energy is transmitted to neighboring molecules, (d)
diffraction gratings, prisms, or interference filters. They allow the phenomenon of luminescence is observed (see Fig. 13).[56]
only a single wavelength or a narrow band of wavelengths to One of the important aspects of the photoluminescence

Fig. 13 A typical photoluminescence spectroscopy.[56]

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spectroscopy is the phenomenon of luminescence, which is energy is released in the form of light. The phenomenon of
described as below: fluorescence and phosphorescence can be well explained with
Luminescence: It is a process of spontaneous emission of light the help of Jablonski diagram (see Fig. 14).[59]
due to some cause other than heat. Luminescence may take
place as a result of chemical reactions, electrical energy, 3.4 Fourier transform infrared spectroscopy (FT-IR)
subatomic motion or stress on the crystal. On the other hand, Infrared spectroscopy is a common spectroscopic technique
incandescence is the phenomenon of emission of used to identify the chemical functional groups present in the
electromagnetic radiations from a hot body. Thus sample. It is an excellent tool to study the interactions and
incandescence is the thermal emission. As in case of mechanism of reduction of metal ions. Spectroscopy in middle
luminescence, spontaneous emission of electromagnetic IR region is extremely useful for study of organic compounds.
radiations takes place without heating. Thus, sometimes IR spectroscopy has been widely used for the identification of
radioactivity may be also considered as luminescence. There organic compounds because of the fact that their spectra are
are various types of luminescence such as bio-luminescence, generally complex and provides numerous maxima and
chemi-luminescence and another type is called minima that can be used for comparison purposes. Modern
photoluminescence. The phenomenon of emission of light can spectrometers working in the infrared region generally use the
take place as a result of biochemical reactions taking place Fourier transform technique for spectral detection and
inside the living organisms.[57] The well-known example is the analysis.[60]
production of light from glow worm. There are number of The atoms in a molecule do not remain in a fixed relative
marine animals which emits light as a result of biochemical position and keep vibrating about their mean positions. Due to
reactions such as star fish, jelly fish, etc. Similarly, as a result this vibrational motion if there is a periodic alternation in the
of chemical reactions sometimes light is generated such type dipole moment, such modes of vibration are IR active. The IR
of phenomenon is known as chemi-luminescence.[58] region of electromagnetic spectrum ranges from 100µm to
When electron at ground state absorbs energy it gets 1µm wavelength. The vibrating molecules absorb energy only
excited to higher energy state. High energy state is unstable. from those radiations with which it can coherently interact, i.e.
Electron resides in higher energy state for short span of time radiations of its own oscillation frequency. Thus, each
and then returns to ground state by emission of energy. functional group has its own specific vibrational frequencies
Depending upon amount of energy absorbed electron can be which are very sensitive to its chemical environment and
promoted to various higher energy states. While coming back neighboring species. The molecular structure of compound
to lower energy state excess energy can be released in the form can be guessed from the appearance or non-appearance of
of heat and light. certain vibrational frequencies. The vibrational frequency is as
Sn → S1 It is called internal conversion and energy is released given in eq. (4), where k is force constant and 𝜇 is reduced
in the form of heat. mass.[61]
Sn → T1 It is called as inter system crossing and this 1 𝑘
𝜈 = 2𝛱 √𝜇 (4)
phenomenon is iso energetic. Hence energy is not given out.
S1→ S0 This phenomenon is called as fluorescence. Here The key concept in FT-IR is the use of mathematical operation
energy is emitted in the form of light. called as Fourier transformation which converts a signal in
Tn → S0 This phenomenon is called as phosphorescence. Here time domain to frequency domain. The frequency

Fig. 14 Jablonski diagram explaining photoluminescence, fluorescence and phosphorescence.[59]

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domain transformation speeds up the estimation of IR which radio frequency waves induce transition between
spectrum of the signal. The time required here is 1 sec or less
magnetic energy level of nuclei of a molecule. The magnetic
vs 10-15 minutes for normal system. The reduction in time energy levels are created by keeping the molecule in the
allows to take number of sample scans and thereby improving
magnetic field. In absence of magnetic field, the spin state of
the resolution and quality of the FT-IR imaging. In FT-IR nuclei is degenerate. When a magnetic field is applied, the
spectroscopy, we are using the term wave-number which is separate levels and radiofrequency radiations can cause
reciprocal of wavelength. The choice of capping agent may transition between these two energy levels.[65]
also affect FT-IR image. When the capping molecules are Among all types of electromagnetic radiations, radio-
adsorbed on nanoparticle surface, their vibration modes will
waves are of lowest energy. The frequency of radio-waves
varies from 107 to 108 cycles per seconds. Thus, the amount of
change. Hence the vibrational frequencies characteristics of
functional group will be either shifted and the extent of such
energy associated with radio waves is very less. Thus the radio
shifting depends upon nature and strength of interactions.[62]
waves are unable to vibrate, rotate or excite an atom or a
Infrared spectrometer has similar components to those of
molecule. But the amount of energy associated with radio
ultraviolet and visible instrument. The essential components
waves are enough to affect nuclear spin of atoms or molecules.
of an infrared spectrometer are such as (a) Light source (b)
Two types of NMR spectroscopy are commonly used today,
Monochromatic and optical material, (c) Sample holder, (d)i.e. 1H and 13C spectroscopy.[66] When a compound is subjected
Detector, (e) Instrument for the measurement of response of
to PMR spectroscopy we obtain three types of information:
the detector. Modern spectrometers working in the infrareda) The relationship between the number of signals in the
region generally use the Fourier transform technique for spectrum and number of different kinds of hydrogen atoms in
spectral detection and analysis. The essential part of an FT-IR
the molecule. Thus, one can know the different kinds of
instrument is the Michelson’s interferometer,[63] which consists
environments of the hydrogen atoms in the molecule.
of static and a movable mirror (see Fig. 15). The source is
b) The principle signal may get split into smaller peaks, i.e.
generally a Nernst filament consisting of a spindle of rare-
spin-spin splitting may be observed. The types splitting pattern
earth oxides. The beam is then guided and made to pass observed depends on the number of neighboring non-
through a beam splitter (a part of the interferometer, a equivalent protons. For many simple compounds, one can
component which reflects about half of the radiation that hits
predict splitting pattern with the n+1 rule, where n is the
it and transmits the rest). The beam is thus divided into 2 parts
number of neighboring protons. Spin-spin splitting thus help
recombines again either constructively or destructively in deducing molecular structure.
depending on the path difference created by the movable c) Spacing between the peaks is labelled J which gives the
mirror. An actual signal thus consists of radiation spanning a
units of cycle per second. J is coupling constant between two
large number of wave numbers and the total intensity is thus
protons and J values give further information on molecular
integration from the individual contributions.[64] structure and stereo-chemical features. Thus, e.g. J value
between adjacent axial hydrogen in a cyclohexane is 10-13 Hz,
3.5 Nuclear Magnetic Resonance Spectroscopy (NMR) while J between axial and equatorial or between two equatorial
NMR spectroscopy is a type of spectroscopic techniques in hydrogens is 3-5Hz.

Fig. 15 Schematic diagram of basic principle of Michelson’s interferometer.[63]

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Each atom contains proton, neutrons and electron. In case crystals are very stable. The electromagnets interact much less
of Hydrogen atom there is no neutron. The unpaired proton with external magnetic effect as compared with permanent
can act as tiny magnet. This proton acts as tiny magnet due to magnets. The homogeneous magnetic field can be developed
spin movement. When an atom is having spin quantum both by permanent magnets and electromagnets by carefully
number I=0, then it is NMR active for example 12C. When the machining and alignment of pole faces. The current shims are
atom is having I ≥ 0, are NMR active. Thus, 13O, 31P, 13N, etc., used to produce field gradient in various directions so as to
are also NMR active. These all can be used in NMR analysis. cancel out gradient inherent in the main field. The magnet used
But generally, C-13 and H-1 are used as NMR active materials. in NMR spectroscopy should be such that it can produce very
This is because there is very little abundance of other elements strong magnetic field. It is also important that magnetic field
in the compounds. Hence generally hydrogen and carbon are be constant over long period of time. For this reason, adequate
used in the NMR spectroscopy. In case of Hydrogen I= ½ and temperature control is necessary to maintain the constant
is NMR active. When an external magnetic field is applied physical dimension of the magnet. The adequate temperature
then the protons get aligned. Each proton is having different control is necessary to maintain. For this, the magnet system
capacity to align in the presence of external magnetic field. is usually thermostatically controlled, also it is advantageous
A high-resolution NMR spectroscope is having complex to control the temperature of room in which the instrument is
collection of electronic equipment.[67] The schematic diagram placed.
of NMR spectroscope (see Fig. 16). Here we have to deal with b) Radio frequency generator: Radio frequency is essential
the intense magnetic field and requires precise controlled for operating the NMR instrument. Hence in order to generate
power supply as well as frequencies. It is worth to note that radio frequency, radio frequency oscillators are used. In order
most of the power required by the instrument is dissipated in to achieve maximum interaction of the radio frequency waves
the form of heat and very small amount of it obtained as a with the sample under study, the coil of oscillator is wound
signal which has to be amplified by a complex electronic around the sample container. The oscillator irradiates the
system. The instrument consists of permanent magnet, radio sample with radio frequency radiation. The oscillator coil is
frequency generator, radio frequency detector, sample holder wound perpendicular to the applied magnetic field. This is
and magnetic coils. done so that the applied radio frequency field should not
change the effective magnetic field in the process of
a) Permanent magnet: This is an important component of irradiation.[68]
NMR spectroscopy. The permanent magnet should be such c) Radio frequency receiver: When the sample is irradiated
that it should provide homogeneous magnetic field, i.e. with radio frequency two phenomenon: absorption and
strength and direction of magnetic field should remain desorption are taking place simultaneously. The observation of
uniform in all points. Also, the strength of the field should be either absorption or desorption will enable the resonance
very high as much as 20,000 gausses. The chemical shift is frequency to be determined. The interpretation of absorption
directly proportional to the field strength. Permanent magnets spectrum is easy as compared with the absorption of
can provide fields that are sufficiently constant provided that desorption spectrum.
they are thermostatically maintained carefully. The d) Sample holder: The NMR spectroscope requires a sample
conventional electromagnets are not less stable but the holder. The sample holder should be chemically inert, durable
expected stability can be obtained by producing ancillary and transparent to radio frequency radiations. Generally, glass
stabilizing devices. The electromagnets containing tubes are used which can be easily cleaned, economical, sturdy,
superconducting solenoids operating in inert gas liquid helium etc. The glass tubes are generally made up of borosilicate glass

Sample tube

Fig. 16 Schematic presentation of a typical Nuclear magnetic resonance spectrometer. [67]

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Review article ES Materials & Manufacturing

of 8.5 cm long and 0.3 cm diameter. anti-Stokes scattering. The energy shifts in the scattered light
e) Magnetic coil: This is another very important component correspond to the energy levels of the molecular vibrations,
of NMR spectroscopy. There is relationship between the providing information about the chemical bonds and
resonance frequency of the nucleus and the strength of molecular structure of the sample.[70]
magnetic field in which the sample is placed, which is The Raman spectrum is generated by measuring the
represented as Γ= constant Ho. For any nucleus to resonant the intensity of the scattered light at different wavelengths. Each
precession frequency of the nucleus must be equal to the peak in the Raman spectrum corresponds to a specific
applied radio frequency of radiation. Thus, we note that if Ho vibrational mode of the molecules present in the sample. By
is kept constant, the precession frequency also remains fixed. analyzing the positions and intensities of these peaks,
It is not easy to change magnetic field of a large stable magnet. researchers can identify the molecules present and gain
But it is possible to overcome by superimposing a small insights into their structure, composition, and interactions.
variable magnetic field on the main field. This is done by using Raman spectroscopy is widely used in various fields,
pair of Helmholtz in the pole faces of permanent magnet. including chemistry, materials science, pharmaceuticals, and
These coil induce the magnetic field that can be varied by biology, for purposes such as identifying unknown substances,
varying the current flowing through them. The small magnetic characterizing materials, studying chemical reactions, and
field is produced in the same direction as the main field is monitoring biological processes. It offers several advantages,
added. The sample is exposed to both fields, which appear as including minimal sample preparation, non-destructive
one of the molecules. analysis, and the ability to analyze samples in various states
(solid, liquid, or gas).[71]
3.6 Raman spectroscopy
Raman spectroscopy is a technique used in spectroscopic 3.7 Mass spectroscopy
analysis to provide information about molecular vibrations Mass spectrometry (MS) is a powerful analytical technique
within a material. It's named after the Indian physicist Sir C.V. used to identify and quantify molecules based on their mass-
Raman, who discovered the phenomenon in 1928.In Raman to-charge ratio. It is widely utilized in various fields such as
spectroscopy, a sample is illuminated with a monochromatic chemistry, biochemistry, pharmacology, environmental
light source, typically a laser.[69] When photons from the laser science, and forensic science.[72] Mass spectrometry is a
interact with the sample, most of them are elastically scattered, versatile technique that can be coupled with various separation
meaning their energy remains unchanged (see Fig. 17). methods, such as gas chromatography (GC-MS), liquid
However, a small fraction of the incident photons undergoes chromatography (LC-MS), or capillary electrophoresis (CE-
inelastic scattering, meaning they lose or gain energy during MS), to enhance its analytical capabilities and broaden its
the interaction with the sample. This inelastic scattering applications. It is a fundamental tool in modern analytical
phenomenon is called the Raman effect. It occurs due to the chemistry and continues to be at the forefront of scientific
interaction of photons with the vibrational modes of molecules research and innovation. The schematic diagram of Mass
in the sample. When a photon loses energy during scattering, spectrometer is presented in Fig. 18. Here's a general overview of
it's called Stokes scattering, and when it gains energy, its called how mass spectrometry works:[73]

Fig. 17 Schematic diagram of Raman spectroscopy. Reproduced with the permission from [71], Copyright 2011 Elsevier B.V.

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Fig. 18 Mass spectrometer. Reproduced with the permission from [73], Copyright 2007 Springer-Verlag.

a) Ionization: The process begins with ionization, where the electrical signal that human learn and recognize as light and
sample is converted into ions. This is typically achieved by colour. Naked eye is the practice of engaging in visual
bombarding the sample with high-energy electrons, causing perception unaided by a magnifying or light collecting optical
the molecules to lose or gain one or more electrons, resulting instrument such as telescope or microscope.[75] For the
in the formation of positively or negatively charged ions. observation of a nearby object, without magnifying glass or
b) Acceleration: The generated ions are then accelerated by microscope, the size of the object depends upon viewing
an electric field, causing them to move at high speeds towards distance. Under the condition of normal light or brightness the
the analyzer. angular size recognized by naked eye is around 1 arc minutes
Separation: In the analyzer, the ions are separated based on = 1/60 degrees = 0.003 radians. If one is desirous to visualize
their mass-to-charge ratio (m/z). This is typically achieved objects smaller than this, some external aid is required.
using one of several methods, such as magnetic sector, Microscope is the instrument used for magnification and
quadrupole, time-of-flight (TOF), or ion trap analyzers. The resolution of the smaller objects. Microscopy is the science of
analyzer sorts the ions based on their mass-to-charge ratio, investing small objects and their structure using such an
with lighter ions reaching the detector faster than heavier ones. instruments. Microscopy means invisible to eye unless aided
c) Detection: Finally, the separated ions are detected by a by the instrument microscope. A significant contribution in the
detector, which measures the abundance of ions at different area of microscope is devoted by Dutch Physicist Antonie
mass-to-charge ratios. The resulting data is then used to Philips van Leeuwenhoek.[76] Later on much advancement has
construct a mass spectrum, which displays the intensity of ions taken place in the area of microscopes. The developmental
as a function of their mass-to-charge ratio.[74] scenario in the microscopy can be summarized in Table 6.
Mass spectrometry can provide a range of valuable The two main properties of microscopy are resolving
information about a sample, including: power and objective numerical aperture, which are described
1) Identification: Mass spectra serve as unique fingerprints for in the following section:
molecules, allowing for the identification of unknown
compounds by comparing their spectra to databases of known 3.8.1 Resolving power
compounds. The resolving power of an optical instrument is its ability to
2) Quantification: Mass spectrometry can quantify the amount differentiate between two adjutant lines or points. The greater
of specific molecules present in a sample by measuring the is the resolving power, the smaller is the minimum distance
abundance of ions at specific mass-to-charge ratios. between two lines or points that can still be distinguished. The
3) Structural Analysis: Fragmentation patterns observed in basic limitation of a light microscope is its resolving power.
mass spectra can provide insights into the structure and Mere magnification of objects without the ability to
composition of molecules, including the arrangement of atoms distinguish structural details is not beneficial. The largest
and functional groups. magnification produced by a microscope may not be most
useful because the image obtained may be unclear or fuzzy.
3.8 Microscopic techniques Therefore, for better clarity high-resolution image is desired.
Animal eye is an optical instrument. It translates photons into The resolving power of a microscope is a function of the

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Table 6. Chronological developmental scenario in microscopy.

Year Major Development
167 BCE The Chinese use water made of a lens and water-filled tube to visualize the unseen
Reading stone. The first vision aid called the reading stone was invented. It is a glass sphere placed
1000 AD
on the top of the text which magnifies readability.
1021 Optics book: Muslim scholar Ibn al Hytham writes his book on optics.
1284 The first eyeglass was invented. Salvino DArmate invented the first wearable glass
14th century Spectacles were first made in Italy
Dutch spectacle maker Hans Jansen and his son Zacharias Jansen were claimed by later writers to
1590
have invented the compound microscope
1609 Galileo Galilei developed a compound microscope with a convex and a concave lens
1619 Cornelius Drebbel presents, in London a compound microscope with two convex lens
Christian Huygens, another Dutchman developed a simple 2 lens ocular system that was
1620
chromatically corrected.
Robert Hooke published Micrographia a collection of biological micrographs. He coins the word
1665
cell for the structures he discovers in cork bark
Anton van Leeuwenhoek improved a simple microscope for visualizing biological objects. He was
1674
the first person to visualize bacteria.
Joseph Jackson Lister discovered that using weak lenses together at various distances provided
1830
clear magnification.
1878 Ernest Abbe developed a mathematical theory linking resolution to light wavelength.
Richard Zsimondy invented the ultramicroscope, which allows for observation of specimens
1903
below the wavelength of light.
Ernest Ruska started to build the first electron microscope. It is a Transmission Electron
1931
Microscope.
Transparent biological materials were studied for the first time using Frits Xernike’s invention of
1932
the phase-contrast microscope.
1938 James Hillier built another TEM
Zernaik, a professor of theoretical Physics was awarded the Nobel prize for the invention of the
1953
phase-contrast microscope
George Nomarski, professor of microscopy published the basis of differential interference contrast
1955
microscopy
1981 Gerd Binning, Qutar, and Gerber invented Atomic Force Microscopy
1988 Kingo Itaya invented the electrochemical scanning microscope
1991 Kelvin probe the force microscope invented

wavelength of light used, refractive index and the numerical section.

aperture or angular aperture of the lens system.[77]
1) Optical microscope
3.8.2 Objective numerical aperture This type of microscope is the oldest design of microscopes
The numerical aperture of a microscope is a measure of its and was probably invented during 17 centuries in Europe.
ability to gather light and resolve fine specimen detail at a Such type of microscope contains one or more lenses
fixed object distance. The numerical aperture of the producing an enlarged image of the sample placed in focal
microscope is given below, plane. This type of microscope is the simplest form of
𝑁𝐴 = 𝑛 𝑠𝑖𝑛 𝜃 (5) microscopes which contains mainly eye pieces (ocular lens),
Where n is the refractive index and θ is the one-half of the objective (resolve or resolving noise), focus knob, light source,
angular aperture A. Apart from above mentioned important condenser, etc. The optical microscope is also known as light
factors the resolving power of an optical instrument depends microscope which commonly uses visible light and a system
upon type of specimen, coherence of illumination, degree of of lenses to generate magnified images of the objects. The
aberration correction and other factors such as contrast basic optical microscope can be very simple, although many
enhancing methodology either in optical system of the complex designs aim to improve resolution and sample
microscope or in specimen itself. The microscope can be contrast.[78] There are many types of optical microscope such
broadly classified in three main types given as Optical as Simple microscope, Compound microscope, Digital
Microscope, Electron Microscope, and Scanning Probe microscope, Stereo microscope, Comparison microscope,
Microscope. These types are described in the following Inverted microscope, Phase Contrast Microscope and

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Confocal Microscope. technique for increasing resolution and contrast of the

i) Simple microscope: Here a single lens is employed to micrograph by means of using a spatial pinhole to block out of
magnify the image of the sample under study. This is very focus light in image formation. The object of the confocal
much similar to the magnifying glass. microscope is to provide a point source of light and reject out
ii) Compound microscope: Here the series of lenses are used of focus light. As we use point source of light it provides the
to magnify the sample under study. Here higher resolution is ability to image deep into tissue with high resolution and
observed. This type of microscope is routinely used in optical sectioning for 3D reconstructions of imaged sample.
common biological laboratory for histological studies. The basic principle of confocal microscopy is that the
iii) Digital microscope: This type of microscope may have illumination and detection optics are focused on the same
simple or compound lenses. Here computer is used to visualize diffraction limited spot, which is moved over the sample to
the image without the use of eyepiece to view samples. build the complete image on the detector. The complete field
iv) Stereo microscope: This type of microscope provides of view is illuminated during confocal imaging, anything
stereoscopic images which is useful for dissection especially outside the focal plane contributes small to the image,
in tumor surgery. lessening the haze observed in standard light microscopy with
v) Comparison microscope: This microscope provides thick and scattered samples, and providing optical sectioning.
simultaneous view of two different samples one in each eye. Scholar Marvin Minsky put forward the idea of rejection of
vi) Inverted microscope: This type of microscope views the out of focus light. In the configuration of confocal microscope,
sample from underneath, which is useful to examine liquid cell one pinhole is placed in front of the zirconium arc light source
culture. to provide a point of light focused on the sample by an object
v) Bright Field microscopy: In bright field microscopy, the lens.[80] The second objective lens focused the illuminated
microscopic field is brightly lightened. The optical part of the sample point onto the second pinhole in front of the detector.
typical bright field microscope and the path light rays follow Now, the system is double focusing which can effectively
to produce enlargement or magnification. Generally, reject the out of focus rays from the illuminated sample, so
microscope of any type produces a uniform magnification of they do not reach the detector, which was a low noise
1000X to 2000X. At magnification greater than 2000X, the photomultiplier. The confocal microscope is made up of
image becomes fuzzy. components such as the pinhole, the objective lens, low noise
vi) Dark field microscopy: The effect produced by dark field detectors in common with the original design but also typically
technique is that of a dark background against which objects include fast scanning mirrors, filters for wavelength selection
are brilliantly illuminated. This is accompanied by equipping and laser illumination.[81]
the light microscope with a special type of condenser that 2) Electron microscope: Such type of microscope uses beam
transmits a hollow cone of light from the source of of accelerated electrons as a source of illumination. The
illumination. Most of light directed through condenser does wavelength of an electron is 100,000 times shorter than the
not enter the objective, the field is essentially dark. However, visible photons. Consequently, electron microscopes are
some of light rays will be scattered if transparent medium having higher resolving power than optical microscopes. The
contains objectives. In this case will appear bright in an electron microscope can be further sub classified into different
otherwise dark microscope.[78] types such as SEM and TEM based upon their construction
vii) Fluorescence microscope: Many chemical substances and type of action and information.[82] Another advanced type
absorb light. After absorbing light of a particular wavelength of electron microscope is combined SEM and TEM where two
and energy. Some substances will emit light of a larger type of electron microscopes are combined together.
wavelength and lesser energy content. Such substances are 3) Scanning probe microscope:
called as florescent and the phenomenon is known as Scanning Probe Microscopy (SPM) is a group of techniques
fluorescence microscopy. used for imaging and analyzing surfaces at the nanometer
viii) Phase contrast microscope: This technique is based on scale. Unlike traditional optical or electron microscopy, which
the fact that light passing through one material and into other rely on lenses and electromagnetic fields to produce images,
material is slightly different refractive index will undergo a SPM operates by scanning a sharp probe over the surface of a
change in phase. This difference in phase or wave-front sample to measure various surface properties with extremely
irregularities are translated into variations in brightness of the high resolution. Here is an overview of scanning probe
structure and hence are detective to the eyes. With phase microscopy.[83]
contrast microscopy, it is possible to reveal difference in cells a) Basic Principle: SPM works by bringing a sharp probe tip
and their structures not describe by other microscopic material. into close proximity or contact with the surface of a sample.
In order to overcome the limitations, set by the diffraction As the probe tip interacts with the surface, various physical
limit of visible light and also to image materials in label-free properties are measured, such as forces, currents, or
conditions, other microscopes have been designed which we mechanical vibrations.
use waves other than light.[79] b) Components of SPM:
ix) Confocal microscope: This is an optical imaging Probe Tip: The heart of SPM is a sharp probe tip, typically

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Review article ES Materials & Manufacturing

made of materials like silicon or silicon nitride, with a radius Scientists and Engineers were continuously trying to get high
of only a few nanometers. magnification and resolutions of microscopic and nanoscopic
c) Cantilever: The probe tip is mounted on a flexible entities. In this area attempts were made by several researchers.
cantilever, which deflects in response to interactions with the A prominent and successful attempt in this area was made by
sample surface. German Physicist Ernest Ruska and German Electrical
d) Scanner: A precise scanning mechanism moves the probe Engineer Max Knoll in 1931.[85] A scanning electron
tip laterally across the surface of the sample, allowing for the microscope is the type of electron microscope which can
acquisition of high-resolution images. produce image by scanning the surface with a focused beam
e) Detector: Various detection methods are used to measure of electrons. The ejected electron interacts with atoms present
the interactions between the probe tip and the sample surface. in the sample under study. The interaction of electron with
These can include mechanical deflection of the cantilever, atoms produces various signals which contain information
changes in tunneling current, or shifts in resonance frequency. about the surface topography and the composition of the
f) Feedback System: A feedback loop controls the distance sample. The electron beam is scanned in the raster manner, and
between the probe tip and the sample surface to maintain a the position of the beam is combined with the intensity of the
constant interaction force or tunneling current. This ensures detected signal to produce an image. The SEM is used for
that the probe tip stays in close proximity to the surface during observation of the specimen surface. When the specimen is
scanning. irradiated with a fine electron beam secondary electrons are
g) Main techniques within SPM: emitted from the specimen surface. Topography of surface can
Atomic Force Microscopy (AFM): Measures surface be observed by two dimensional. When a specimen is hit with
topography by scanning a sharp probe tip over the sample a beam of electrons called as incident beam it emits X-rays and
surface and detecting the deflection of a cantilever. three kinds of electrons primary backscattered electrons,
1) Scanning Tunneling Microscopy (STM): Measures the secondary electrons and Auger electrons.[86] In SEM device
tunneling current between the probe tip and the sample surface, primary backscattered electrons are used.
providing atomic-scale resolution of conductive surfaces.
2) Scanning Kelvin Probe Microscopy (SKPM): Measures 3.9.1 Instrumentation and working of SEM
variations in surface potential by detecting changes in the The essential component of SEM are such as: electron source
electrostatic force between the probe tip and the sample (Gun), electron lenses, sample stage, detectors for all signals
surface. of interest, display/data output device, infrastructure
3) Scanning Capacitance Microscopy (SCM): Maps variations requirement, power supply, vacuum system, cooling system,
in the capacitance between the probe tip and the sample vibration free floor, room free ambient magnetic and electric
surface, providing information about carrier concentrations in field. Fig. 19 shown the variety of interaction products evolved
semiconductors. due to interaction of electron beam and sample.[87]
4) Scanning Thermal Microscopy (SThM): Measures a) Electron gun
variations in temperature on the sample surface by detecting An electron gun is responsible for the production of electron
changes in the thermal conductivity or expansion of the beam. The electron gun can emit electrons either by heating
cantilever. the filament known as thermionic emission or can emit the
5) Applications of SPM: SPM is used in a wide range of electron by applying high potential difference known as field
scientific and technological fields, including nanotechnology, emission. An electron microscope generally uses a magnetic
materials science, biology, and semiconductor device lens. To make a strong magnetic lens it is necessary to increase
characterization. It can provide high-resolution images of the density of magnetic lines. A portion with a near row gap
surfaces, reveal atomic-scale details, measure mechanical called pole piece is fabricated with high accuracy. The main
properties, and map variations in surface potential or feature of magnetic lens is that when the current passing
conductivity. Applications include surface roughness analysis, through the coil is changed the strength of lens is also changed.
nanoscale patterning, biological imaging, characterization of This is not possible in case of optical microscopes.
thin films, and investigation of surface chemistry.[84] b) Condenser lens and objective lens
4) X-Ray Microscope: Such type of microscope uses When a lens is placed below the electron gun, the diameter of
electromagnetic radiations in the soft X-ray band so as to electron beam can be adjusted. SEM requires a fine electron
generate the magnified image of the object under study. The beam (probe). Thus, there are two stage lenses which combine
resolution of X-ray microscopy lies in between optical the condenser and objective lens. Thus, the electron beam
microscope and electron microscope. The main advantage of from electron gun is focused by the two stages lens and a small
X-ray microscope is the visualization of visualization of electron probe is produced.
biological sample in their native state. Table 7 Illustrates the c) Specimen stage
distinguish between light microscope and electron Microscope. In an electron microscope the specimen is observed under high
magnification and resolution. Therefore, a specimen stage
3.9 Scanning electron microscope which can support the specimen and can move smoothly is

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Table 7. Differentiate between light microscope and electron microscope.

Sr. No. Light Microscope Electron Microscope
1 Light microscope is also known as optical microscope Electron microscope is also known as beam microscope
It is believed that Dutch spectacle maker Zcharius Janes
In 1931 physicist Ernst Ruska and Max Knoll invented
2 and his father Hans first time invented compound
electron microscope
microscope in 16th century
Electron microscopes are complicated structure, very
Light Microscopes are smaller and lighter hence are
3 big, heavy and delicate, therefore it is difficult to move
easier to move and set up
electron microscopes
As far as cost is concerned, light microscopes are very As far as cost is concerned electron microscopes are
4
cheap as compared to electron microscope very costly as compared to light microscope
Light microscope uses electromagnetic radiations in the Electron microscope used beam of electrons
5
visible range, i.e. visible light approximately equivalent to 1nm
The magnification power of electron microscope is
The magnification power of light microscope is limited much higher as compared with the light microscope. The
6
and much less than electron microscope. electron microscopes have highest magnification power
among all as per 7today’s scientific developmental stage.
In light microscope images can be controlled via glass In electron microscope beam of electron can be focused
7
lenses using electromagnets due to negative charge on electrons
Light microscope has much less resolution as compared Electron microscope have much better resolution as
8
to the electron microscope compared to the light microscope
In electron microscope specimen is coated with heavy
9 In light microscope specimen is stained by colored dyes
metals in order to reflect electrons
10 In light microscope vacuum is not required In light microscope vacuum is required
In light microscope specimen preparation takes place In electron microscope sample preparation takes place
11
usually minutes to few hours. few days
In light microscope thickness of specimen is about 5 In electron microscope ultra-thin specimen particularly
12
micrometer or more below 0.1 micrometer is required
In light microscope specimen is mounted on glass In electron microscope specimen is mounted on metal
13
substrate substrate, i.e. metallic grid
In light microscope focusing is done by adjusting the In electron microscope focusing is done by adjusting the
14
lens position mechanically power of electric current to the electromagnetic lenses.
In light microscope living and dead samples can be In electron microscope in ordinary condition only non-
15
observed living or dead samples can be observed
In light microscope images are observed by eyes through In electron microscope images are produced on
16
ocular lens fluorescent screen or photographic plate
Electron microscope produces 2D and 3D images. TEM
17 Light microscope produces 2D images produces 2D images whereas 3D images are possible in
SEM
18 In light microscope there is no risk of radiation leakage In electron microscope there is risk of radiation leakage
Electron microscope uses tungsten filament to produce
19 Light microscope does not use any filament
electrons
Light microscope does not require high voltage of
20 Electron microscope requires high voltage of electricity
electricity
21 Light microscope does not require any cooling system Electron microscope requires cooling systems

required. The specimen stage for SEM is designed so as it can specimen are known as secondary electrons. The secondary
perform following types of movements in all possible ways electron detector is used for detecting the secondary electrons
such as: (a) Horizontal movement, (b) Vertical movement, (c) emitted from the specimen. A scintillator is coated on the tip
Specimen tilting, (d) Rotation. The X and Y movements are of detector and a high potential difference is created. The
used for the selection of field of view whereas Z movement secondary electrons from the specimen are attracted to this
provides the change in image resolution and depth of focus. high voltage and then generates the light. When an electron
d) Secondary electron detector beam strikes the sample, some of the incident electrons will
The specimen emits electrons as a result of bombardment of interact with the nucleus of the atom. The negatively charged
electrons from electron gun. These emitted electrons from the electron will be attracted towards positively charged nucleus.

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The incident electron will encircle the nucleus and come back The working principal of SEM can be briefly explained as
out of sample without slowing down its speed. These electrons ahead: The mono energetic beam is incident on a solid
are called backscattered electrons. The backscattered electrons substrate surface gives various types of signals depending
are coming back out of sample.[88] The secondary electrons upon the nature and morphology of the substrate. In the SEM
originate from surface regions. The backscattered and imaging backscattered or secondary electron are particularly
secondary electrons carry different types of information. The used. Their intensity depends upon the atomic number of host
backscattered electrons show high sensitivity towards atomic materials. Each of the backscattered electron can be collected,
numbers. The regions of higher brightness possess atoms with amplified and utilized to control the brightness spot-on
higher atomic numbers. Whereas the regions of lower cathode-ray tube.[90] In order to obtain signals from an area, the
brightness possess the atoms with lower atomic numbers. electron beam is scanned over the specimen surface by two
Secondary electrons can provide information about surface of pairs of electro-magnetic deflection coils and so is the C.R.T.
the sample. The most common BSE detectors are solid state beam in synchronization with this. The signals are transferred
extrinsic semiconductor devices which typically contain p-n from point to point and signal map of the scanned area is
junction. The working principle is based on the generation of displayed on a long persistent phosphor C.R.T. screen. Change
electron-hole pairs by backscattered electron which generates in brightness represents change of a particular property within
electron-hole pairs. The backscattered electron is responsible the scanned area of the specimen. The ray diagram of scanning
for the generation of electron-hole pair. The backscattered electron microscope can be pictorially represented (Fig. 20).
electrons (BSE) are escaped from the sample and are absorbed The scattering cross section for back-scattered electrons is
by the detectors. The amount of electron-hole pair generated given as,[6] where, Z is atomic number and E is electric field.
depends on the energy of the backscattered electrons. The p-n 𝑍 2 𝜑
𝑄 = 16.2 ∗ 10−30 [ ] 𝑐𝑜𝑡( ⁄2) (6)
junction generated as a result of impact of backscattered 𝐸
2
electron is connected to two electrodes. One of the electrode Here the cross-section is proportional to Z . Hence, the back-
attracts electrons whereas another electrode attracts holes. scattered electrons are used for the Z contrast or for
Thus, an electric current is generated in the system. The compositional mapping.
current generated depends upon the amount of backscattered
electrons generated. The BSE detectors are placed above the 3.10 Transmission electron microscope
sample, concentrically to the electron beam in a doughnut Transmission Electron Microscope is a type of electron
arrangement.[89] microscope that has three essential components viz. electron
e) Secondary electrons: The secondary electron originates gun, image producing system, imaging recording system.[91]
from the surface of the sample under study. The secondary a) Electron gun: An electron gun is an electrical component
electrons are generated as a result of inelastic interaction that produces an electron beam that has precise kinetic energy.
between the primary electron beam and the sample. Secondary The electron gun at the top of a TEM emits electrons that travel
electrons are having lower energy than primary or through the microscope or vacuum tube. There are two types
backscattered electrons. Secondary electrons play a crucial of electron gun i. e. thermionic emission and field emission.
role in determination of topography of the sample. The primary component of electron gun are the electron
emitter, the biasing cylinder and the anode. The tungsten
3.9.2 Principle of SEM filament is covered by a control grid known as Wehnelt

Fig. 19 Variety of interaction products evolved due to interaction of electron beam and sample. Reproduced with the permission from
[86], Copyright 2019 Springer Nature Switzerland AG.

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ES Materials & Manufacturing Review article

Fig. 20 The ray diagram of scanning electron microscopy. Reproduced with the permission from [90], Copyright 2016 Tsinghua
University Press Limited.

cylinder made up of a central hole which lies columnar to the fluorescent screen fixed at the base microscope. The image can
tube. The cathode lies on top of or below the cylindrical be captured digitally and displayed on the computer and stored
column hole. The cathode and the grid are negatively charged in a JPEG format.
with an end of the anode is disc shaped that also has an axial
hole. When electrons are transmitted from the cathode, they 3.10.1 Working principle
pass through the columnar aperture to the anode at high TEM is a microscopic technique in which a beam of the
voltage with constant energy, which is efficient for focusing electron is transmitted through an ultra-thin specimen,
the specimen to produce an accurately defined image. interacting with the specimen as it passes through. The
b) Image Producing System: The image producing system is working principle of TEM is very much similar to the light
made up of objective lens, a movable stage or holding the microscope. The prime difference between light microscope
specimen, intermediate and projector lenses. They function by and electron microscope is that, in case of light microscope,
focusing the passing electron through the specimen forming a light rays are used to focus and produce image whereas in case
highly magnified image. The objective has a short focal length of TEM, electron beams are used to focus on the specimen and
of about 1-5 mm and it produces an intermediate image from to produce image.[92] Electrons are having shorter wavelength
condenser which are transmitted to the projector lenses for as compared with light. The mechanism of a light microscope
magnification. The projector lenses are of two types: is that an increase in resolution power decreases the
intermediate lens which allows great magnification of the wavelength of light, but in TEM when electrons are
image and the second one is projector lens which gives illuminated, the specimen, the resolution power increases
generally greater magnification over the intermediate lens. increasing the wavelength of the electron transmission. An
c) Image Recording System: The image recording system is image is formed from the interaction of the electrons
made up of florescent screen used to view and to focus on the transmitted through the specimen; the image is magnified and
image. They have digital camera that can effectively record focused onto the imaging device such as a fluorescent screen.
the image and capture after viewing it. They have vacuum In TEM analysis, a thin specimen is illuminated with electrons
system that prevents the bombardment or collision of electrons in which the electron intensity is uniform over the illuminated
with air molecules disrupting their movement and ability to area. As the electrons travel through the specimen, they are
focus. A vacuumed system facilitates the straight movement of either scattered by a variety of processes or they may remain
electrons to the image. The vacuumed system is made up of a unaffected by the specimen. The result is that a non-uniform
pump, gauge, valves and a power supply. The generated image distribution of electrons emerging from the surface of the
is known as monochromatic image, which is greyish or black specimen contains all the structural and chemical information
in color. The image should be such that it should be easily about the specimen. An electron microscope is constructed to
visible to human eyes. Therefore, it is allowed to pass through display this non-uniform distribution of electrons in two

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Fig. 21 A pictorial representation of the Transmission Electron Microscope. [92]

different ways viz. angular distribution of scattering that can i) Optical objective and selected area metal apertures can
be viewed in the form of scattering patterns, and spatial restrict the beam, the objective aperture enhancing contrast by
distribution of scattering that can be observed as contrast in blocking out high-angle diffracted electrons, and the selected
images of the specimen.[93] The advantages of this arrangement area aperture enabling the user to examine the periodic
are the possibility of directly viewing the area from which the diffraction of electrons by the ordered arrangement of atoms
diffraction pattern arises. The basic components of the in the sample.
transmission electron microscope is displayed in Fig. 21. j) The photographic image is recorded from the electron after
A technical explanation of a typical TEM working is as it has passed through a thin sample of the specimen under
follows: study.
a) The vital source, i.e. an electron gun produces a stream of k) The image is passed down the column through the
monochromatic electrons. intermediate and projector lenses.
b) TEM works with voltage electron beam. Here a focused The image strikes the phosphorus image screen and light is
beam of electrons instead of light is used to image. generated, allowing the user to see the image. The darker area
c) The magnification power is over 2 million times better than of the image represents those areas of the sample that fewer
that of light microscope. electrons were transmitted through.[94]
d) TEM uses electron beam for resolution.
e) The stream is focused to a small, thin coherent beam by the 3.11 Combing SEM and TEM together
use of condenser lenses 1 and 2. The first lens is usually There is one more analytical technique which uses
controlled by a spot size knob that largely determines the spot combination of both SEM and TEM. This instrument is called
size and the second lens is usually controlled by the intensity as scanning transmission electron microscopy. This instrument
or brightness knob that changes the size of the spot on the can be applied to a TEM tool. Most modern TEM can be
sample. The second lens usually controlled by the intensity or switched to STEM mode. In STEM mode, the beam is finally
brightness knob actually changes the size of the spot on the focused and scan the sample area while the image is generated
sample. by the transmitted electron. Combining Scanning Electron
f) The beam is restricted by the condenser aperture, knocking Microscopy (SEM) and Transmission Electron Microscopy
out high-angle electrons. (TEM) into a single instrument, often referred to as a "dual-
g) The beam strikes the specimen and part of it are transmitted. beam" or "dual-mode" microscope, offers several advantages
h) The transmitted portion is focused on the objective lens. for comprehensive material characterization. Although such

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instruments are not commonplace, they offer significant scale details of crystal structure, defects, and interfaces.
benefits in terms of sample preparation, imaging, and analysis. Combined SEM and TEM analysis would allow for
The difference between SEM and TEM is briefly addressed in comprehensive material characterization, including
Table 8, respectively. Here's an overview of how such a investigation of microstructure, phase identification, chemical
combined instrument might function and its potential composition, and elemental mapping.
applications:[95] d) Applications
a) Instrument configuration 1) Material Science: Combined SEM/TEM instruments would
The instrument would likely consist of a platform that find applications in materials science for studying a wide
integrates both SEM and TEM capabilities. This could involve range of materials, including metals, semiconductors,
a shared vacuum system, sample stage, and electron optics. ceramics, polymers, and composites.
The SEM component would typically be used for initial 2) Nanotechnology: Such instruments would be invaluable for
sample inspection, navigation, and coarse imaging due to its characterizing nanomaterials, nanoparticles, and
relatively large depth of field and ease of use. The TEM nanostructures, providing insights into their morphology, size
component would allow for higher-resolution imaging and distribution, and crystalline structure. Biological Sciences: In
detailed analysis of thin sections of the sample. biology and life sciences, combined SEM/TEM capabilities
b) Sample preparation could facilitate the study of biological specimens, such as cells,
The combined instrument would streamline sample tissues, and biomaterials, offering detailed imaging of
preparation, as the same sample could be examined using both ultrastructure and subcellular organelles.
SEM and TEM without the need for additional sample 3) Research and Development: Combined SEM/TEM
handling. Initial sample inspection and rough characterization instruments would be essential tools for research laboratories
could be performed using SEM, guiding subsequent TEM and industrial R&D facilities, enabling comprehensive
analysis of specific regions of interest. material characterization and supporting advances in materials
c) Imaging and analysis science, nanotechnology, and biological research. A combined
SEM imaging would provide detailed surface morphology and SEM and TEM instrument would provide a powerful platform
topography information at relatively low magnifications. TEM for comprehensive material characterization, offering
imaging would offer higher-resolution imaging of internal advantages in sample preparation, imaging, and analysis
structures and thin sections of the sample, providing atomic- across a wide range of scientific and technological disciplines.
Table 8. Difference between SEM and TEM.
Sr. No. Scanning Electron Microscope Transmission Electron Microscope
SEM creates image by detecting reflected or TEM creates image using transmitted electrons that
1
knocked-off electrons passes through the sample
TEM provides information about inner structure,
SEM provides information about the surface,
2 crystal structure, stress state information of the
elemental composition and topography
materials under study using broad beam of electron
In SEM specimen contrast is by electron
3 In TEM specimen contrast is by electron scattering
absorption
TEM requires very thin sample hence skilled
4 The preparation technique for SEM is easy
preparation techniques are essential
The recently developed TEM has images has
5 SEM has resolution limit to 0.5nm
resolution up to 50pm
6 SEM provides 3D images TEM provides 2D images
As the electron is transmitted from one end of the
There is no requirement of ultrathin sample
7 material to the another end, here ultra-thin sample
preparation
preparation is essential.
SEM produces images based upon scattering
TEM produces image based upon transmitted
of electrons by detecting secondary electrons
8 electrons by detecting primary electrons transmitted
which are emitted from the surface due to
from sample.
excitation by primary electron beam
TEM sample preparation is complex and tedious
SEM sample requires little or no sample
9 procedure which can be done by trained skill expert
preparation
only
In SEM specimens are mounted on In TEM specimens are deposited in very thin film
10
aluminium stubs. form on copper grid

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SEM operates in the accelerating voltage up TEM operates in the accelerating voltage up to 60-
11
to 30Kv 300Kv
12 In SEM field view is large In TEM field view is narrow
In SEM specimen stage is halfway down the In TEM specimen stage in the chamber is the
13
column bottom of the column
SEM can magnify the sample up to 1-2
14 TEM can magnify the sample up to 50 million times
million times
Sample is placed at the bottom of the electron In TEM sample is located in the middle of the
15 column and the scattered electrons are column. The transmitted electron pass through it
captured by electron detector. and through a series of lenses below the sample.
In SEM image is observed on fluorescent
16 In TEM image is observed on TV monitor
screen
In SEM electrons are captured and counted In TEM direct imaging on fluorescent screen or PC
17
by detectors, image on PC screen screen with CCD
18 SEM is faster technique TEM is slower technique
19 In SEM less sample restriction than TEM In TEM more sample restriction than SEM
20 SEM is less versatile than TEM TEM is more versatile than SEM
21 SEM is less expensive than TEM TEM is more expensive than TEM
In SEM surface, powders, polished and TEM is used to image dislocations, small
22 etched microstructures, IC chips and precipitates, grain boundaries and other defect
chemical segregation are all imaged. structures in solids.
TEM is used to study the interior of cells, the
structure of protein molecules, the organization of
SEM is used to study the topography and
23 molecules in viruses and cytoskeletal filaments and
atomic composition of the specimen.
the arrangement of protein molecules in the cell
membrane.

2.12 Atomic force microscope (AFM) is key to image interpretation in this mode. In feedback
The AFM can be operated in a number of ways. The basic operation, the force between tip and sample is kept constant.
difference between the mode of operation is how much the tip Controlling the force variation led to development of the force
touches the specimen surface, contact mode is when the tip modulation microscope. The up and down movement results
contacts the specimen all the time, intermitted contact mode is in a deflection of cantilever that will depend upon local forces
when the tip oscillates and touches the specimen some of the and local mechanical properties of sample.[97]
time, in non-contact mode the tip does not touch the specimen
at all.[96] 3.12.2 Intermitted contact mode
The application of contact mode AFM to soft material such as
3.12.1 Contact and associated mode polymers and biological specimen is highly restricted because
In contact mode AFM, the tip mounted on the cantilever is in of their delicate structure which can get damaged due to lateral
contact with sample surface during scanning. This is similar in forces. In IC-AFM the cantilever is forced to oscillate
principle to profilometer where a stylus is dragged over a vertically near its resonance frequency, which is typically
surface. In the AFM, a very smaller contact area and highly around 50-499 kHz. The amplitude of free cantilever
sensitive cantilever allow high resolution of topographical oscillation is typically a few tons of nanometers. The
surface feature, both laterally and vertically. During scanning, vibrational amplitude is reduced when cantilever is brought
the local variation of vertical force for a rigid sample is due to closure to the sample surface and begins to touch it.
variant ion in the height of the surface. Feedback control of Topographical images are produced as the amplitude depends
this force causes the vertical position of the tip to trace out the upon the mean height.[98]
surface topography. Because the tip stays in contact with
surface during scanning, the cantilever experiences forces 3.13 Contact angle (CA)
acting not only normal but also lateral to the sample surface. The contact angle can be defined in several ways.
The origin of lateral force is the shear force in the sample at Qualitatively, a contact angle is the macroscopic
the tip position. The diagram of AFM (see Fig. 22). The shear representation of microscopic phenomena. Microscopic
force can be very high and can cause damage to the soft characteristics such as surface roughness, surface energies of
polymer or biological samples under study. the materials involved, and surface coatings play an important
The force acting between the tip and sample surface plays role in the wettability of a material for a given fluid.
a vital role in contact mode AFM, and understanding this force Quantitatively, a contact angle is the interior angle formed by

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Fig. 22 Schematic diagram of atomic force microscopy in liquid. [96]

the substrate being used and the tangent to the drop interface of two liquids or two vapors.[101] The companies like Kyowa
at the apparent intersection of all three interfaces.[99] This ltd have developed equipment to measure microscopic contact
intersection is called the contact line. The contact angle is the angle and dynamic contact angle. Furthermore, the schematic
angle which is conventionally measured through liquid where modern contact angle instrument with Goniometer (see Fig.
liquid vapor interface meets. The angle of contact is 24).
determined by the interaction across the three interfaces as Meanwhile, the different Measuring methods of contact
shown in above diagram. Most often the concept is illustrated angle Different methods are having different requirements of
with a small liquid droplet resting on a flat horizontal solid the aggregate sample according to the different measurement
surface. The tangent line and angle of contact of a liquid theories. Regarding the measurement of surface free energy of
droplet is shown in the diagram. The static angle of contact on aggregates different methods are uses as: Wilhelmy method,
a flat surface can be determined by famous Young;s equation. wick method also known as capillary rise method, micro
In fact, Young equation is a force balance in the horizontal calorimeter method, universal sorption device, and inverse gas
direction. It is possible to determine ratio of interface surface chromatography. The different methods are such as, Static
tension using angle of contact.[100] The contact angle plays the sessile drop, Dynamic sessile drop, Powder contact angle,
role of a boundary condition. Contact angle is measured using Single fiber, Wilhelmy method, and Dynamic Wilhelmy
a contact angle goniometer and it is not limited to a method.
liquid/vapor interface; it is equally applicable to the interface

Fig. 23 Water drop on lotus leaf.

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Review article ES Materials & Manufacturing

Fig. 24 Schematic modern contact angle instrument. Reproduced with the permission from [101], Copyright 2013, Springer Science
Business Media New York.

Let us see the possible way of interaction of a liquid droplet wide range of industries and is often a critical parameter in the
with solid surface. There may be strong attraction of liquid manufacture of many products. Particle size has a direct
droplet with solid substrate surface or there may be weak influence on material properties such as reactivity, stability,
attraction of liquid droplet with the solid substrate surface. texture, viscosity, and porosity. Particle size analysis is the
When a liquid is very strongly attracted to the solid substrate statistical distribution of the particles of different sizes. It is
surface the droplet will completely spread on the solid common practice to represent this distribution in the form of
substrate surface and angle of contact will be acute and close either a frequency distribution curve or a cumulative
to 0. On the hand if the droplet of liquid is having less affinity distribution curve. Particle size distribution can be represented
with the solid substrate surface it will not penetrate inside. The in many ways such as number-weight, volume-weight and
liquid droplet will not spread. It will remain in the form of intensity-weight distribution.[104]
droplet only for longer time. In such cases the angle of contact
is higher than 0. Sometimes angle of contact may be as high 3.14.1 Number-weight distribution
as 150-180. In such case the liquid will not wet the surface. A counting technique such as image analysis will give a
Such materials are called as a hydrophobic material if liquid is number-weight distribution where each particle is given equal
water. These materials are super hydrophobic materials. The weighting irrespective of its size. This is most important where
super hydrophobic materials can be obtained on fluorinated knowing the absolute number of particle is important.
surfaces like Teflon’s. This phenomenon is popularly called as
Lotus effect as displayed (see Fig. 23). The contact angle thus 3.14.2 Volume-weight distribution
directly provides information on the interaction energy Static light scattering technique such as laser diffraction will
between the surface and the liquid. Sometimes the contact give a volume-weight distribution. Here the contribution of
angle is measured through the gas instead of through the liquid, each particle in the distribution relates to the volume of that
which reverses 0 and 180 in the above explanation.[102] particle; relative contribution will be proportional to the (size).
This is very useful from a commercial perspective.
3.14 Particle size distribution
Particle size distribution is also known as grain size 3.14.3 Intensity-weight distribution
distribution. Particle size of nanomaterials influences many dynamic light scattering technique will give an intensity-
properties. It is a valuable indicator of their quality and weight distribution where the contribution of each particle in
possible applications. This concept holds valid for all phases the distribution relates to the intensity of light scattered by
of materials such as powder, suspension, emulsion and aerosol. particle; for example, using the Rayleigh approximation the
If the particle size is small, then its solubility increases which relative contribution for very small particles will be
leads to higher surface charge (zeta potential). The particle proportional to the (size). When comparing particle size data
size analysis not only reveals the average particle size but also for the same sample measured by different techniques it is
other statistical distribution parameters such as mode, median, important to realize that the type of distribution being
distribution width, etc. which are equally important.[103] measured can produce very different particle size results (Fig.
Particle size measurement is routinely carried out across a 25).[105]

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Fig. 25 Dynamic Light Scattering. Reproduced with the permission from [103], Copyright 1990 Published by Elsevier B.V.

3.15 Surface area d) Catalysis and Separation: These are the substance which
The surface area becomes important factor at nanoscale. alters the rate of chemical reaction without taking part in it.
Hence when we consider phenomenon at nanoscale But the physical state of the catalyst may change at the end of
measurement of surface area is an important parameter. reaction. When the rate of chemical reaction gets accelerated
Brunauer-Emmett-Teller (BET) surface area analysis is the the phenomenon is called positive catalysis. There are some
multi-point measurement of an analyst’s specific surface area substances which can enhance the efficacy of the catalyst and
(m2/g) through gas adsorption analysis, where an inert gas are known as promoters. In presence of certain substances, the
such as nitrogen is continuously flowed over a solid sample, rate of chemical reaction is decreased and they are called as
or the solid sample is suspended in a defined gaseous volume. negative catalyst.
Small gas molecules adsorb to the solid substrate and its
porous structures due to weak van der Waals forces, forming a 3.15.1 Surface area dependent properties and applications
monolayer of adsorbed gas. This monomolecular layer, and a) Adsorption: This is phenomenon of accumulation of one
the rate of adsorption, can be used to calculate the specific substance on the surface of another substance. On the other
surface area of a solid sample and its porous geometry, hand, absorption can be defined as the phenomenon of
informing studies into the reactivity and bioavailability of penetration of one substance into the bulk or body of another
pharmaceutical products. At Nano scale there is an increase in substance. The term adsorption can also be defined as
surface area of material. The increased surface area imparts concentration at the interfacial layer between the two phases
exotic properties to the material at Nanoscale. But why to of a system. The adsorption can be categorized into different
determine Surface Area? Surface area directly correlates with types:[107]
several factors as under:[106] i) Positive Adsorption: When there is an increase in
a) Particle Size: The particle size is a notion introduced for concentration of one substance on the surface of another
comparing dimensions of solid particles, i.e. flakes, liquid substance, it is said to be positive adsorption.
particles i.e. droplets, gaseous particles i.e. bubbles. The ii) Negative Adsorption: When there is a decrease in
notion of the particle size applies to the particles in colloids, concentration of one substance on the surface of another
in ecology, in granular materials and the particles that forms a substance, it is said to be negative adsorption.
granular material. The particle size can be measured by Difference between adsorption and absorption: There is
various methods such as ultra sound or electric field or gravity difference between adsorption and absorption. Adsorption is
or centrifugation method. surface phenomenon while absorption is bulk phenomenon.
b) Particle: In nanoscience and technology a particle can be BET aims to explain the physical adsorption of gas molecules
defined as a small localized object which can be described by on the solid surface and serves as the basic for the important
several physical or chemical properties such as volume, analytical techniques for the measurements of the specific
density and mass. Anything that is composed of particle is surface areas of the material.
termed as particulate. But in practice the term particulate is The adsorption can also be classified as under:
normally used to refer to pollutants. i) Physical adsorption: Here adsorption of gas molecules
c) Morphology: This is the external appearance of the takes place due to Physical force of attraction. In physical
material. Actually, this word is derived from biology. In adsorption formation of multiple layer takes place. The
morphology of nanoparticles, different parameters considered adsorption of molecule takes place due to van der Waal’s
are Surface, Texture, Porosity, and Reactivity. physical force of attraction.

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Review article ES Materials & Manufacturing

ii) Chemical adsorption: Here adsorption of gas molecules the gas phase.
take place due to formation of chemical bonds. In chemical
adsorption of monolayer takes place. In chemical adsorption 3.15.3 BET assumption
formation of chemical bonds take place. In chemical Adsorption takes place on the uniform surface and the energies
adsorption, the gas molecules are held on the surface by of adsorption of all molecules in the first layer are identical.
chemical bonds and a surface compound is formed. Chemical 1) Each molecule adsorbed in a layer is itself a potential
adsorption is categorized by high heat of adsorption (20-100 adsorption site for next layer.
kcal/mole) chemical adsorptions are rarely reversible. To 2) There is no steric limitation to the thickness of the
remove the adsorbed a gas the solid must be heated to a higher multilayer.
temperature and pumped at higher vacuum. In chemical 3) It is only for the first layer that the differential energy of
adsorption only single molecules of adsorption layer may be physical adsorption E1 is higher than the energy of
formed. It is found only when there is tendency towards liquefaction E.
compound format.[108] BET theory explains physical 4) Interaction between molecules adsorbed in the same layer
adsorption of gas molecules on the solid surface and serves as does not play any part in the adsorption equation.
the basic technique for the measurement of the specific surface 5) All the molecules in the monolayer cover the same area
area of the material. Normally nitrogen gas is employed 6) The arrangement of these molecules is assumed to be
adsorption for surface probing by BET method. Therefore, hexagonal close packed.
standard BET analysis is often conducted at low temperature 7) The molecular cross section area can be derived from
i.e. Boiling temperature of N2 i.e.77K. density of the adsorption in the bulk liquid state.
𝑃 1 𝐶−1 𝑃
b) Pigments: A pigment can be defined as a powder used to = + (7)
𝑣𝑡(𝑃 0 −𝑃) 𝑉𝑚 𝐶 𝑉𝑚 𝐶 𝑃0
add color or change visual appearance. The pigments are
Where, P = Equilibrium Pressure
completely or partially insoluble in aqueous medium. The
P0 = Saturation pressure
pigments may be organic or inorganic in nature. The organic
Vt = Volume of adsorbed gas,
pigments may be azo pigments which contains Nitrogen
Vm = Monolayer of adsorbed gas
groups. These pigments are generally red in color.
C = BET constant
c) Pharmaceutical products: The pharmaceutical products (𝐸1 −𝐸2 )
consist of active ingredients which are combined with 𝐶 = 𝑒 𝑅𝑇 (8)
additional materials, selected to control dosage delivery. The where, E1=Heat of adsorption of first layer and E2= Heat of
pharmaceutical products have been traditionally manufactured adsorption of second layer
in batch facilities permitting the flexible use and operation of
equipment for the production of a variety of low volume and 3.15.4 Instrumentation of BET
high-volume products. The single-point method can be successfully applied for series
d) Chromatographic carriers: In case of gas of samples in powder form. These circumstances may be
chromatography, choice of mobile phase is important. verified by comparison with specific surface area determined
Hydrogen gas has the range of flow rates that are comparable by the single point method. The close similarity between the
to helium in efficiency. But helium may be more efficient and single point value and multiple point values indicates that 1/C
provide the best separation if we optimize the flow rate. approaches to zero. Fig. 26 indicates the BET measurement set
Therefore, helium is the most common carrier gas. But, use of up.[109]
helium is not always affordable due to its high cost. a) Sample preparation: Before the determination of specific
e) Sintered materials: Sintering or frottage is the process of surface area of the sample, it is necessary to remove gases and
compacting the forming of a solid mass of material by pressure vapors that may have been physically adsorbed on the surface
or heat without melting it to the point of liquefaction. Sintering after manufacture and during treatment, handling and storage.
This phenomenon is popularly known as outgassing. In case if
3.15.2 Theory or principle out gassing is not achieved, the specific surface area may be
The concept of BET is an extension of the Langmuir theory; reduced or may be variable because an intermediate area of the
Langmuir theory is applicable to monolayer adsorption. The surface is covered with molecules of the previously adsorbed
postulates are as under: gases or vapors. The outgassing conditions are critical for
1) Gas molecules physically adsorption on the solid in layer obtaining the required precision and accuracy of specific
infinitely surface area measurements on pharmaceuticals because of the
2) Gas molecules only interacts with adjacent layer and sensitivity of the surface of the materials.[110]
3) Langmuir theory is applicable to each other layer. b) Conditions: It is essential to demonstrate out gassing
4) The desorption is a kinetically limited process i.e. heat of conditions to yield reproducible BET plots. The outgassing
conditions defined by the temperature, pressure and time
adsorption must be supplied.
should be chosen so that the original surface of the solid is
5) The uppermost layer molecular layer is in equilibrium with
reproduced as closely as possible. The outgassing of many

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substances can be achieved by applying a vacuum. Here liquid nitrogen at 77.4 K up to a defined point on the sample
sample is purged in a flowing stream of non-reactive dry gas. cell. Admit a sufficient volume of adsorbate gas to give the
In either case, elevated temperatures are sometimes applied to lowest desired relative pressure. Measure the volume
increase the rate at which the contaminants leave the surface. adsorbed, Va. For multi-point measurements, repeat the
Caution should be exercised when outgassing powder samples measurement of Va at successively higher P/Po values. When
using elevated temperatures to avoid affecting the nature of the nitrogen is used as the adsorbate gas, P/Po values of 0.10, 0.20,
surface and the integrity of the sample. If heating is employed, and 0.30 are often suitable.[110]
the recommended temperature and time of outgassing are as e) Reference materials: Periodically verify the functioning of
low as possible to achieve reproducible measurement of the apparatus using appropriate reference materials of known
specific surface area in an acceptable time. For outgassing surface area, such as α-alumina, which should have a specific
sensitive samples, other outgassing methods such as the surface area similar to that of the sample to be examined.
desorption-adsorption cycling method may be employed. a) BET method is based on adsorption of gas on a surface.
c) Volumetric method principle: In the volumetric method b) The amount of gas adsorbed at a given pressure allows to
the recommended adsorbate gas is nitrogen which is admitted determine the surface area.
into the evacuated space above the previously outgassed c) It is cheap, fast and reliable method.
powder sample to give a defined equilibrium pressure, P, of d) It is very well understood and applicable in many fields.
the gas. The use of a diluent gas, such as helium, is therefore e) This method is not applicable to all types of isotherms.
unnecessary, although helium may be employed for other
purposes, such as to measure the dead volume. Since only pure
3.16 Thermogravimetric analysis
adsorbate gas, instead of a gas mixture, is employed,
Thermogravimetric analysis (TGA) is a thermal analysis
interfering effects of thermal diffusion are avoided in this
technique used to study changes in the mass of a sample as a
method.
function of temperature (or time) under controlled atmosphere
d) Procedure: In the sample tube admit a small amount of dry
conditions. It is widely used in various fields, including
nitrogen so as to prevent contamination of clean surface. Then
materials science, chemistry, pharmaceuticals, and
remove the sample tube and stoppered is to be removed and
environmental science, to characterize the thermal stability,
weighed. Calculate the weight of the sample. Attach the
composition, and decomposition kinetics of materials. The
sample tube to the volumetric apparatus. Cautiously evacuate
schematic diagram of Thermogravimetric analysis is
the sample down to the specified pressure. Alternatively, some
displayed (see Fig. 27). Here's how thermogravimetric
instruments operate by evacuating to a defined rate of pressure
analysis works:[111]
change and holding for a defined period of time before
a) Sample preparation: A small amount of the sample
commencing the next step.
(usually a few milligrams to tens of milligrams) is accurately
If the principle of operation of the instrument requires the
weighed and placed in a sample holder. The sample can be in
determination of the dead volume in the sample tube, for
the form of a solid, liquid, or gas, depending on the specific
example, by the admission of a non-adsorbed gas, such as
requirements of the analysis.
helium, this procedure is carried out at this point, followed by
b) Heating: The sample holder containing the sample is then
evacuation of the sample. The determination of dead volume
placed in a thermogravimetric analyzer, which is equipped
may be avoided using difference measurements, that is, by
with a high-precision balance. The temperature of the sample
means of reference and sample tubes connected by a
is gradually increased at a controlled rate (typically from room
differential transducer. The adsorption of nitrogen gas is then
temperature to several hundred degrees Celsius or higher)
measured as described below. Raise a Dewar vessel containing
while the mass of the sample is continuously monitored.

Fig. 26 Schematic representation of BET Surface area measurement instrument.[109]

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Fig. 27 Schematic representation of thermogravimetric analysis set-up.[111]

c) Mass measurement: As the sample is heated, various emitting diodes, photoconductors, light crystal displays,
physical and chemical processes may occur, leading to magneto-optic memories, audio and video systems, compact
changes in its mass. These processes can include evaporation, discs, electro-optic coatings, memories, multilayer capacitors,
desorption, decomposition, oxidation, reduction, or phase flat-panel displays, smart windows, computer chips, magneto-
transitions. The balance in the TGA measures any changes in optic discs, lithography, micro electromechanical systems and
the mass of the sample with high sensitivity. multifunctional emerging coatings with other developed
d) Data analysis: The data obtained from the TGA experiment cutting technologies.[112]
is plotted as a thermogram, which shows the mass loss of the The Major commercial application of thin films are given
sample as a function of temperature (or time). By analyzing below:
the thermogram, researchers can determine important
parameters such as the onset temperature of decomposition, 1) Semiconductor
the temperature at which maximum mass loss occurs, the The semiconductor industry has depended on flat, two-
extent of decomposition, and the decomposition kinetics. dimensional chips upon which to grow and deposit the thin
Thermogravimetric analysis is often combined with other films material that become electronic circuits for computers
techniques such as differential scanning calorimetry (DSC), and other electronic devices. This thin layer can be transferred
evolved gas analysis (EGA), and Fourier-transform infrared to glass, plastic or other flexible materials and flexible
spectroscopy (FTIR) to provide comprehensive information electronics. Also, the semiconductor film can be flipped as it
about the thermal behavior and chemical composition of is transferred to its new substrate, making its other side
materials. It is a valuable tool for studying polymers, available for additional components. This doubles the possible
composites, pharmaceuticals, catalysts, minerals, and various number of devices that can be placed on the film. The layers
other materials, helping researchers understand their stability, of double-sided, thin-film semiconductors can be fixed
degradation mechanisms, and performance under different together, creating powerful, low-power, and three-
temperature conditions. dimensional electronic devices. These are single-crystal films
of strained silicon or silicon germanium membranes. After
4. Applications of thin films addition the strain changes the arrangement of atoms in the
The area of material science and engineering group’s ability to crystal shown faster device speed while consuming less power.
apprehend the novel materials with amazing combination of For non-computer applications, solar cells, smart cards, radio
physical, chemical and mechanical properties has improved frequency identification (RFID) tags, medical applications,
the modern society. The worth of the optical properties of and active-matrix flat panel displays could all benefit from the
metal films and scientific curiosity about the behavior of two- development. The method could allow flexible
dimensional solids has been responsible for the enormous semiconductors to be embedded in fabric to create wearable
interest in the study of science and technology of the thin films. electronics or computer monitors that roll up like a window
Thin film materials have already been used in semiconductor shade. Silicon germanium membranes are particularly interest
devices, wireless communications, telecommunications, due to higher adsorption of light than silicon. By including the
integrated circuits, rectifiers, transistors, solar cells, light- germanium without destroying the quality of the material one

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can accomplish 2 or 3 folds of magnitude sensitivity. That 5) Optical coatings

increased sensitivity could be applied to create superior low- An optical coating is one or more thin layers of material
light cameras, or smaller cameras with greater resolution.[113] deposited on an optical component such as a lens or mirror,
which changes the way in which the optic reflects and
2) Photovoltaic cells transmits light. One type of optical coating is an antireflection
In rigid solar panel the energy of incoming photons are coating, which reduces unwanted reflections from surfaces,
converted to electricity in cells holding two thin layers of and is commonly used on spectacle and photographic
crystalline silicon. What makes roll-to-roll production of lenses.[117] Another type is the high-reflector coating which can
flexible film solar products possible is replacement of the be used to develop mirrors are reflect greater than 99.99% of
crystalline silicon with amorphous silicon, supplied in high- the light which falls on them. More complex optical coatings
solids slurries that can be deposited onto substrates by web- shown high reflection over some range of wavelengths, and
converting processes like slot die coating. The multiple layer- anti-reflection over another range, allowing the production of
to-layer interfaces create a torturous path for gas molecules dichroic thin-film optical filters.
and thus substantially increase the barrier properties of the
film. This is critical for photovoltaic applications, which 6) Optoelectronic lenses
require barrier layers to prevent performance losses caused by In optoelectronic thin-film chip, comprising at least one
infiltration of oxygen or moisture vapor. Many in the solar radiation mitting region in an active zone of a thin-film layer.
power industry and the investment community believe that the Second a lens disposed downstream of the radiation emitting
arrival of grid parity, the point when cost of electricity region, said lens being formed by at least one partial region of
generated by a rooftop photovoltaic cell system is equivalent the thin-film layer, the lateral extent of the lens being greater
to that purchased from an electrical utility will mark a major than the lateral extent of the radiation-emitting region. The
inflection point for the market that will deliver a huge increase thin-film layer is provided for example by a layer sequence
in growth. However, even when true grid parity arrives, it’s which is deposited epitaxial on a growth substrate and from
unlikely to generate an abrupt rise in solar system installations which the growth substrate is at least partly removed.[118] That
due to the high upfront costs and the long-term return of is to say that the thickness of the substrate is reduced. It is
investing in a rooftop photovoltaic system.[114] furthermore possible for the entire growth substrate to be
removed from the thin-film layer. The thin-film layer has at
3) Photo Electrochemical Cells (PEC) least one active zone suitable for generating electromagnetic
In photo electrochemical experiments, irradiation of an radiation. The active zone may be provided for example by a
electrode with light that is absorbed by the electrode material layer or layer sequence which has a pn junction, a double
causes the production of a current (a photocurrent). The heterostructure, a single quantum well structure or a multiple
dependence of the photocurrent on wavelength, electrode quantum well structure. Particularly preferably, the active
potential and solution composition provides information about zone has at least one radiation emitting region. In this case, the
the nature of the photo process, its energetics and its radiation-emitting region is formed for example by a partial
kinetics.[115] Photocurrents at electrodes can also arise because region of the active zone. Electromagnetic radiation is
of photolytic processes occurring in the solution near the generated in said partial region of the active zone during
electrode surface. Photo electrochemical studies are operation of the optoelectronic thin-film chip.
frequently carried out to obtain a better understanding of the
nature of the electrode-solution interface. 7) Flat panel displays
Developed from the Mykrolis contamination control
4) Super capacitor technologies, Energies provides a broad portfolio of liquid and
The knowledge of storing charge in the electric double layer gas contamination control technologies for the flat panel
that initiates at the interface between a solid and an electrolyte display fabrication. The Flat Panel Display (FPD) fabrication
has exhibited by the slander oil company, Cleveland, Ohio in environment is among the world's most competitive and
the 1960. The primary high power double layer capacitor was technologically complex. Device designers and manufacturers
developed for the military applications by the pinnacle continually strive to satisfy the worldwide consumer’s appetite
research institute in 1982. Conventional capacitor stores for larger displays, greater pixel resolution and feature rich
energy electrostatically on two electrode separated by a performance. The need to control contamination in air, gas and
dielectric, the capacitance of which is C= €A/d, where being liquid process streams is now a paramount focus of process
the dielectric constant, d the dielectric thickness and A surface engineers and designers. Entergy provides the solutions to
area. In a double layer capacitor, charges accumulate at the succeed under these extreme conditions.[119]
boundary between electrode and electrolyte to form two
charge layers with separation of several Angstroms. Now a 8) Data storage
days, the super capacitors are known as electrochemical As the data storage density in cutting edge microelectronic
energy storage device.[116] devices continues to increase, the superparamagnetic effect

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Review article ES Materials & Manufacturing

poses a problem for magnetic data storage media. One strategy for the analysis of materials at nanoscale. Thus, keeping this
for overcoming this problem is the use of thermomechanical in mind we tried discuss the advance characterization
data storage technology. In this methodology, data is written techniques, which are required in nanotechnology,
by a nanoscale mechanical probe as an indentation on a biotechnology, material and pharmaceutical sciences. Overall,
surface, read by a transducer built into the probe and then the review would be highly beneficial for the researchers,
erased by the application of heat. An example of such a device students and industrial persons working in nanoscience and
is the IBM millipede, which uses a polymer thin film as the technology.
data storage medium. It is also possible, however, to use other
kinds of media for thermomechanical data storage, and in the Acknowledgment
following work, we explore the possibility of using thin film The authors pay sincere tribute to Late Ms. Deepika Rai
Ni-Ti shape memory alloy (SMA).[120] Previous work has Dhirendra Prasad who suddenly left this world and lived a
shown that nanometer-scale indentations made in martensitic very short span of life, we all the authors remember her on this
phase Ni-Ti SMA thin films recover considerably upon occasion and pray to Almighty God for peace of her holy soul.
heating. Issues such as repeated thermomechanical cycling of The authors are thankful to the supportive staffs of Veterinary
indentations, indent proximity, and film thickness impact the Dispensary Grade 1, Navargaon, and District Chandrapur (MS)
practicability of this technique. While there are still problems India.
to be solved, the experimental evidence and theoretical
predictions show SMA thin films are an appropriate medium Conflict of Interest
for thermomechanical data storage. There is no conflict of interest.

9) Gas sensors Supporting Information

The sensor technology has developed immensely in the last Not applicable.
few decades having many scientific successes from countless
experiments, proposing new tasks and openings to the search References
for each smaller devices capable of molecular level imaging [1] R. D. Prasad, R. S. Prasad, R. B. Prasad, S. R. Prasad, S.
and monitoring of pathological samples. [121] But the scientific B. Singh, R. J. Prasad, P. Sinha, S. Saxena, A. K. Vaidya, S.B
community gave the concentration lately on macromolecules, Teli, U. R. Saxena, A. Harale, M. B. Deshmukh, M. N. Padvi,
particularly for remote monitoring because of increasing need G. J. Navathe, A review on modern characterization
for environmental safety and health monitoring. Gas sensors techniques for analysis of nanomaterials and biomaterials, ES
usually operate different principles and various gas sensing Energy & Environment, 2024, 23, 1087, doi:
elements have been fabricated, out of which resistive metal 10.30919/esee1087.
oxide sensors comprise a significant part. However, these [2] M. C. Rao, M. S. Shekhawat, A brief survey on basic
sensing elements typically operate at an elevated temperature properties of thin films for device application, International
for maximum performance. This makes higher power Journal of Modern Physics: Conference Series, 2013, 22, 576-
consumption which is not suitable for the inflation. Recently, 582, doi: 10.1142/s2010194513010696.
the carbon nanotube has received significant attention due to [3] Y. Yu, M. Gong, C. Dong, X. Xu, Thin-film deposition
their unusual electronic and mechanical properties. [122] These techniques in surface and interface engineering of solid-state
properties make them possible materials for generating blocks lithium batteries, Next Nanotechnology, 2023, 3-4, 100028,
of active materials in Nano electronics, field emission devices, doi: 10.1016/j.nxnano.2023.100028.
gas storage and sensors. Among these the room temperature [4] M. Yu, X. Feng, Thin-film electrode-based supercapacitors,
gas sensing characteristics are much attractive for many Joule, 2019, 3, 338-360, doi: 10.1016/j.joule.2018.12.012.
applications [5] J. J. Wang, D. Shi, Spectral selective and photothermal
nano structured thin films for energy efficient windows,
5. Conclusion Applied Energy, 2017, 208, 83-96, doi:
In the last 20 years, there has been immense change was found 10.1016/j.apenergy.2017.10.066.
in the characterization techniques for analyses of biological [6] O. Oluwatosin Abegunde, E. Titilayo Akinlabi, O. Philip
and nanomaterials. Also, the existing technique has advanced Oladijo, S. Akinlabi, A. Uchenna Ude, Overview of thin film
due to adaptation of new technology. Today large number of deposition techniques, AIMS Materials Science, 2019, 6, 174-
researchers are working in the research and development of 199, doi: 10.3934/matersci.2019.2.174.
nanomaterials for thin film technology. Thin films are widely [7] J. T. Gudmundsson, A. Anders, A. von Keudell,
used in construction of solar cells and supercapacitors. Even Foundations of physical vapor deposition with plasma
though, nanomaterial characterization is very important to assistance, Plasma Sources Science and Technology, 2022, 31,
bring better deposition to make superior thin films. As 083001, doi: 10.1088/1361-6595/ac7f53.
nanomaterials are beyond the perception of human eyes, it is [8] R. S. Pedanekar, S. K. Shaikh, K. Y. Rajpure, Thin film
very much essential to have proper characterization technique photocatalysis for environmental remediation: a status review,

42 | ES Mater. Manuf., 2024, 25, 1198 © Engineered Science Publisher LLC 2024
ES Materials & Manufacturing Review article

Current Applied Physics, 2020, 20, 931-952, doi: Technologies, 2018, 185-211, Woodhead Publishing, doi:
10.1016/j.cap.2020.04.006. 10.1016/B978-0-08-101975-7.00008-7.
[9] P. Salles, P. Machado, P. Yu, M. Coll, Chemical synthesis [22] N. S. Inchaurrondo, J. Font, Clay, zeolite and oxide
of complex oxide thin films and freestanding membranes, minerals: natural catalytic materials for the ozonation of
Chemical Communications, 2023, 59, 13820-13830, doi: organic pollutants, Molecules, 2022, 27, 2151, doi:
10.1039/d3cc03030j. 10.3390/molecules27072151.
[10] J. Budida, K. Srinivasan, Review of thin film deposition [23] C. A. Charitidis, P. Georgiou, M. A. Koklioti, A.-F.
and techniques, Materials Today: Proceedings, 2023, 92, Trompeta, V. Markakis, Manufacturing nanomaterials: from
1030-1033, doi: 10.1016/j.matpr.2023.05.004. research to industry, Manufacturing Review, 2014, 1, 11, doi:
[11] R. D. Prasad, A. K. Sahoo, O. P. Shrivastav, N. Charmode, 10.1051/mfreview/2014009.
S. R. Prasad, R. Kamat, N. G. Kajave, J. Chauhan, S. Banga, [24] A. Moumen, G. C. W. Kumarage, E. Comini, P-type metal
U. Tamboli, M. S. Pandharpatte, R. H. Atigre, V. Shaikh, M. oxide semiconductor thin films: synthesis and chemical sensor
N. Padvi, P. Salvalkar, N. R. Prasad, A review on aspects of applications, Sensors, 2022, 22, 1359, doi:
nanotechnology in food science and animal nutrition. ES Food 10.3390/s22041359.
& Agroforestry, 2022, 8, 12-46, doi: 10.30919/esfaf704 [25] S. Altimime, S. Q. Mohammed, M. H. Hassoni, A. N. Abd,
[12] M. Ruoho, J. P. Niemelä, C. Guerra-Nunez, N. Tarasiuk, Properties and Biomedical Applications of Hydrothermal
G. Robertson, A. A. Taylor, X. Maeder, C. Kapusta, J. Michler, method Synthesized of Vanadium Oxide nanoparticles,
I. Utke, Thin-film engineering of mechanical fragmentation Journal of Physics: Conference Series, 2021, 1963, 012043,
properties of atomic-layer-deposited metal oxides, doi: 10.1088/1742-6596/1963/1/012043.
Nanomaterials, 2020, 10, 558, doi: 10.3390/nano10030558. [26] L. Qin, F. J. Mawignon, M. Hussain, N. K. Ange, S. Lu,
[13] A.T. Petkoska, I. Nasov, Surface engineering of polymers: M. Hafezi, G. Dong, Economic friendly ZnO-based UV
case study: PVD coatings on polymers, Zastita Materijala, sensors using hydrothermal growth: a review, Materials, 2021,
2014, 55, 3-10, doi: 10.5937/zasmat1401003t. 14, 4083, doi: 10.3390/ma14154083.
[14] J. E. Crowell, Chemical methods of thin film deposition: [27] H. Zhu, M. Zhang, B. Li, Y. Liu, J. Zhuang, X. Zhao, M.
chemical vapor deposition, atomic layer deposition, and Xue, L. Wang, Y. Liu, X. Tao, Developing hydrothermal
related technologies, Journal of Vacuum Science & fabrication and energy storage applications for MTeMoO6
Technology A: Vacuum, Surfaces, and Films, 2003, 21, S88- (M=Zn, Mg, Mn), The Journal of Supercritical Fluids, 2021,
S95, doi: 10.1116/1.1600451. 171, 105187, doi: 10.1016/j.supflu.2021.105187.
[15] M. Saeed, Y. Alshammari, S. A. Majeed, E. Al-Nasrallah, [28] M. A. Butt, Thin-film coating methods: a successful
Chemical vapour deposition of graphene-synthesis, marriage of high-quality and cost-effectiveness-a brief
characterization, and applications: a review, Molecules, 2020, exploration, Coatings, 2022, 12, 1115, doi:
25, 3856, doi: 10.3390/molecules25173856. 10.3390/coatings12081115.
[16] S. J. C. Irvine, Photochemical vapour deposition of thin [29] M. Faustini, B. Louis, P. A. Albouy, M. Kuemmel, D.
films. Pauleau Y, Chemical Physics of Thin Film Deposition Grosso, Preparation of sol-gel films by dip-coating in extreme
Processes for Micro- and Nano-Technologies. Dordrecht: conditions, The Journal of Physical Chemistry C, 2010, 114,
Springer, 2002, 199-222, doi: 10.1007/978-94-010-0353-7_9. 7637-7645, doi: 10.1021/jp9114755.
[17] M. Mao, S. Ke, D. Tang, X. Sang, D. He, Structure and [30] A. Salam, H. Makhlouf, R. Rodriguez, Advances in smart
performance optimization of co magnetic thin films deposited coatings and thin films for future industrial and biomedical
by vacuum evaporation coating, Materials, 2023, 16, 3395, engineering applications, 2020, 407-427, doi: 10.1016/B978-
doi: 10.3390/ma16093395. 0-12-849870-5.00018-5.
[18] S. R. Abhilash, S. K. Saini, D. Kabiraj, Methods adopted [31] J. E. Bishop, T. J. Routledge, D. G. Lidzey, Advances in
for improving the collection efficiency in vacuum evaporation spray-cast perovskite solar cells, The Journal of Physical
technique, Journal of Radioanalytical and Nuclear Chemistry, Chemistry Letters, 2018, 9, 1977-1984, doi:
2014, 299, 1137-1139, doi: 10.1007/s10967-013-2674-9. 10.1021/acs.jpclett.8b00311.
[19] A. Hoseinpur, S. Andersson, K. Tang, J. Safarian, [32] M. Calixto-Rodriguez, J. S. Valdez Martínez, M. A.
Selective vacuum evaporation by the control of the chemistry Meneses-Arcos, J. Ortega-Cruz, E. Sarmiento-Bustos, A.
of gas phase in vacuum refining of Si, Langmuir, 2021, 37, Reyes-Mayer, M. González-Castañeda, R. O. Domínguez
7473-7485, doi: 10.1021/acs.langmuir.1c00876. García, Design and development of software for the SILAR
[20] H. J. Lunk, Incandescent lighting and powder control process using a low-cost embedded system, Processes,
metallurgical manufacturing of tungsten wire, ChemTexts, 2021, 9, 967, doi: 10.3390/pr9060967.
2014, 1, 3, doi: 10.1007/s40828-014-0003-8. [33] Z. Alhalili, Metal oxides nanoparticles: general structural
[21] R. M. Thankachan, R. Balakrishnan, Synthesis of description, chemical, physical, and biological synthesis
Inorganic Nanomaterials, Chapter-8, Synthesis strategies of methods, role in pesticides and heavy metal removal through
single-phase and composite multiferroic nanostructures, wastewater treatment, Molecules, 2023, 28, 3086, doi:
Advances and Key Technologies, Micro and Nano 10.3390/molecules28073086.

© Engineered Science Publisher LLC 2024 ES Mater. Manuf., 2024, 24, 1198 | 43
Review article ES Materials & Manufacturing

[34] S. R. Prasad, S. B. Teli, J. Ghosh, N. R. Prasad, V. S. [46] N. Gerard, A symmetrically moving theta - theta X ray
Shaikh, G. M. Nazeruddin, A. G. Al-Sehemi, I. Patel, Y. I. diffraction goniometer, Journal of Physics E: Scientific
Shaikh, A review on bio-inspired synthesis of silver Instruments, 1972, 5, 524-526, doi: 10.1088/0022-
nanoparticles: their antimicrobial efficacy and toxicity, 3735/5/6/006.
Engineered Science, 2021, 16, 90-128, doi: 10.30919/es8d479. [47] C. J. Gilmore, G. Barr, J. Paisley, High-throughput
[35] T. A. Ghaleb, Software energy measurement at different Powder diffraction. I. A new approach to qualitative and
levels of granularity, 2019 International Conference on quantitative powder diffraction pattern analysis using full
Computer and Information Sciences (ICCIS). Sakaka, Saudi pattern profiles, Journal of Applied Crystallography, 2004, 37,
Arabia. IEEE, 2019, 1-6, doi: 10.1109/ICCISci.2019.8716456. 231-242, doi: 10.1107/s002188980400038x.
[36] R. D. Prasad, C. B. Desai, O. P. Shrivastav, N. Charmode, [48] C. H. McCollough, The AAPM/RSNA physics tutorial for
S. R. Prasad, A. Samant, R. Mirajkar, S. Banga, V. Shaikh, M. residents. X-ray production, RadioGraphics, 1997, 17, 967-
N. Padvi, S. U. K. India, P. D. Sarvalkar, N. R. Prasad, A 984, doi: 10.1148/radiographics.17.4.9225393.
critical review on design and development of carbon [49] R. Baskaran, T. S. Selvakumaran, G. Rodrigues, D.
nanotubes for veterinary medicine, ES Food & Agroforestry, Kanjilal, A. Roy, Measurements and analysis of
2022, 9, 15-38, doi: 10.30919/esfaf770. bremsstrahlung X-ray spectrum obtained in Nanogan electron
[37] H. Shin, Electron microscopy for visualization of cyclotron resonance ion source, Review of Scientific
interfaces in adhesion and adhesive bonding. Interfacial Instruments, 2008, 79, 02A324, doi: 10.1063/1.2816785.
Phenomena in Adhesion and Adhesive Bonding. Singapore: [50] T. Lin, L. Wang, X. Wang, Y. Zhang, Y. Yu, Influence of
Springer, 2024: 17-112.10.1007/978-981-99-4456-9_2. lattice distortion on phase transition properties of
[38] N. Pandey, S. Tripathi, B. Kumar, D. K. Dwivedi, Thin polycrystalline VO2 thin film, Applied Surface Science, 2016,
film deposition and characterization for various applications, 379, 179-185, doi: 10.1016/j.apsusc.2016.04.007.
2018 5th IEEE Uttar Pradesh Section International Conference [51] A. O. Bokuniaeva, A. S. Vorokh, Estimation of particle
on Electrical, Electronics and Computer Engineering size using the Debye equation and the Scherrer formula for
(UPCON). Gorakhpur, India. IEEE, 2018, 1-6, doi: polyphasic TiO2 powder, Journal of Physics: Conference
10.1109/UPCON.2018.8596908. Series, 2019, 1410, 012057, doi: 10.1088/1742-
[39] A. Venkateshaiah, V. V. T. Padil, M. Nagalakshmaiah, S. 6596/1410/1/012057.
Waclawek, M. Černík, R. S. Varma, Microscopic techniques [52] A. M. Alshehawy, D.E A. Mansour, M. Ghali, M.
for the analysis of micro and nanostructures of biopolymers Lehtonen, M. M. F. Darwish, Photoluminescence
and their derivatives, Polymers, 2020, 12, 512-521, doi: spectroscopy measurements for effective condition
10.3390/polym12030512. assessment of transformer insulating oil, Processes, 2021, 9,
[40] A. A. Bunaciu, E. G. Udriştioiu, H. Y. Aboul-Enein, X- 732, doi: 10.3390/pr9050732.
ray diffraction: instrumentation and applications, Critical [53] V. K. Redasani, P. R. Patel, D. Y. Marathe, S. R.
Reviews in Analytical Chemistry, 2015, 45, 289-299, doi: Chaudhari, A. A. Shirkhedkar, S. J. Surana, A review on
10.1080/10408347.2014.949616. derivative UV-spectrophotometry analysis of drugs in
[41] A. Roy, A.G. ShilaRekha, A Review on X-Ray diffraction, pharmaceutical formulations and biological samples review,
International Journal of Pharmaceutical Research and Journal of the Chilean Chemical Society, 2018, 63, 4126-4134,
Applications, 2022, 7, 786-788, doi: 10.35629/7781- doi: 10.4067/s0717-97072018000304126.
0702786788. [54] P. Jagadeesh, S. M. Rangappa, S. Siengchin, Advanced
[42] A. Ali, Y. W. Chiang, R. M. Santos, X-ray diffraction characterization techniques for nanostructured materials in
techniques for mineral characterization: a review for engineers biomedical applications, Advanced Industrial and
of the fundamentals, applications, and research directions, Engineering Polymer Research, 2023, 7, 122-143, doi:
Minerals, 2022, 12, 205, doi: 10.3390/min12020205. 10.1016/j.aiepr.2023.03.002.
[43] S. Plaipichit, S. Wicharn, C. Puttharugsa, P. Wanakamol, [55] H. Nguyen, J. Park, S. Kang, M. Kim, Surface plasmon
P. Buranasiri, Virtual X-Ray Diffractometer using Acoustic resonance: a versatile technique for biosensor applications,
Wave for Material Science Education, Journal of Physics: Sensors, 2015, 15, 10481-10510, doi: 10.3390/s150510481.
Conference Series, 2018, 1144, 012140, doi: 10.1088/1742- [56] I. Pavić, J. Šoda, V. Gašparić, M. Ivanda, Raman and
6596/1144/1/012140. photoluminescence spectroscopy with a variable spectral
[44] E. S. Ameh, A review of basic crystallography and X-ray resolution, Sensors, 2021, 21, 7951, doi: 10.3390/s21237951.
diffraction applications, The International Journal of [57] S. Eaton-Magaña, C. M. Breeding, A. C. Palke, A.
Advanced Manufacturing Technology, 2019, 105, 3289-3302, Homkrajae, Z. Sun, G. McElhenny, Raman and
doi: 10.1007/s00170-019-04508-1. photoluminescence mapping of gem materials, Minerals, 2021,
[45] J.A. Seibert, X-ray imaging physics for nuclear medicine 11, 177, doi: 10.3390/min11020177.
technologists. Part 1: Basic principles of x-ray production, The [58] S. E. Crawford, P. R. Ohodnicki, J. P. Baltrus, Materials
Journal of Nuclear Medicine Technology, 2004, 32,139-47, for the photoluminescent sensing of rare earth elements:
PMID: 15347692. challenges and opportunities, Journal of Materials Chemistry

44 | ES Mater. Manuf., 2024, 25, 1198 © Engineered Science Publisher LLC 2024
ES Materials & Manufacturing Review article

C, 2020, 8, 7975-8006, doi: 10.1039/d0tc01939a. Spectroscopy, 2011, 57, 163-176, doi:

[59] S. N. Iyer, N. Behary, V. Nierstrasz, J. Guan, G. Chen, 10.1016/j.vibspec.2011.08.003.
Study of photoluminescence property on cellulosic fabric [72] G. L. Glish, R. W. Vachet, The basics of mass
using multifunctional biomaterials riboflavin and its spectrometry in the twenty-first century, Nature Reviews Drug
derivative Flavin mononucleotide, Scientific Reports, 2019, 9, Discovery, 2003, 2, 140-150, doi: 10.1038/nrd1011.
8696, doi: 10.1038/s41598-019-45021-5. [73] N. Rauniyar, S. M. Stevens, L. Prokai, Fourier transform
[60] A. Fadlelmoula, D. Pinho, V. H. Carvalho, S. O. Catarino, ion cyclotron resonance mass spectrometry of covalent
G. Minas, Fourier transform infrared (FTIR) spectroscopy to adducts of proteins and 4-hydroxy-2-nonenal, a reactive end-
analyse human blood over the last 20 years: a review towards product of lipid peroxidation, Analytical and Bioanalytical
lab-on-a-chip devices, Micromachines, 2022, 13, 187-194, doi: Chemistry, 2007, 389, 1421-1428, doi: 10.1007/s00216-007-
10.3390/mi13020187. 1534-2.
[61] A. C. S. Talari, M. A. G. Martinez, Z. Movasaghi, S. [74] S. Tamara, M. A. den Boer, A. J. R. Heck, High-resolution
Rehman, I. U. Rehman, Advances in Fourier transform native mass spectrometry, Chemical Reviews, 2022, 122,
infrared (FTIR) spectroscopy of biological tissues, Applied 7269-7326, doi: 10.1021/acs.chemrev.1c00212.
Spectroscopy Reviews, 2017, 52, 456-506, doi: [75] D. Kalaronis, N. M. Ainali, E. Evgenidou, G. Z. Kyzas,
10.1080/05704928.2016.1230863. X. Yang, D. N. Bikiaris, D. A. Lambropoulou, Microscopic
[62] V. Balan, C.-T. Mihai, F.-D. Cojocaru, C.-M. Uritu, G. techniques as means for the determination of microplastics
Dodi, D. Botezat, I. Gardikiotis, Vibrational spectroscopy and nanoplastics in the aquatic environment: a concise review,
fingerprinting in medicine: from molecular to clinical practice, Green Analytical Chemistry, 2022, 3, 100036, doi:
Materials, 2019, 12, 2884, doi: 10.3390/ma12182884. 10.1016/j.greeac.2022.100036.
[63] Y.C. Wang, L.H. Shyu, C.P. Chang, The comparison of [76] L. A. Robertson, Antoni van Leeuwenhoek 1723–2023: a
environmental effects on Michelson and fabry-perot review to commemorate Van Leeuwenhoek’s death, 300 years
interferometers utilized for the displacement measurement, ago, Antonie Van Leeuwenhoek, 2023, 116, 919-935, doi:
Sensors, 2010, 10, 2577-2586, doi: 10.3390/s100402577. 10.1007/s10482-023-01859-4.
[64] J. Coates, Interpretation of Infrared Spectra, A Practical [77] B. K. Johnson, Resolving power tests on microscope
Approach. In: Meyers R.A., McKelvy M.L. editors, objectives used with ultra-violet radiation, Proceedings of the
Encyclopedia of Analytical Chemistry. John Wiley & Sons Physical Society, 1929, 42, 16-27, doi: 10.1088/0959-
Ltd.; Chichester, UK: 2000, doi: 5309/42/1/303.
10.1002/9780470027318.a5606. [78] M. Xu, J. Liu, J. Sun, X. Xu, Y. Hu, B. Liu, Optical
[65] J. Krajczewski, K. Kołątaj, A. Kudelski, Plasmonic microscopy and electron microscopy for the morphological
nanoparticles in chemical analysis, RSC Advances, 2017, 7, evaluation of tendons: a mini review, Orthopaedic Surgery,
17559-17576, doi: 10.1039/c7ra01034f. 2020, 12, 366-371, doi: 10.1111/os.12637.
[66] K. Trainor, J. A. Palumbo, D. W. S. MacKenzie, E. M. [79] K. Toda, M. Tamamitsu, Y. Nagashima, R. Horisaki, T.
Meiering, Temperature dependence of NMR chemical shifts: Ideguchi, Molecular contrast on phase-contrast microscope,
tracking and statistical analysis, Protein Science, 2020, 29, Scientific Reports, 2019, 9, 9957, doi: 10.1038/s41598-019-
306-314, doi: 10.1002/pro.3785. 46383-6.
[67] K. Zia, T. Siddiqui, S. Ali, I. Farooq, M. S. Zafar, Z. [80] A. D. Elliott, Confocal microscopy: principles and
Khurshid, Nuclear magnetic resonance spectroscopy for modern practices, Current Protocols in Cytometry, 2020, 92,
medical and dental applications: a comprehensive review, e68, doi: 10.1002/cpcy.68.
European Journal of Dentistry, 2019, 13, 124-128, doi: [81] F. P. Martial, N. A. Hartell, Programmable illumination
10.1055/s-0039-1688654. and high-speed, multi-wavelength, confocal microscopy using
[68] K. C. Wong, Review of NMR spectroscopy: basic a digital micromirror, PLoS One, 2012, 7, e43942, doi:
principles, concepts and applications in chemistry, Journal of 10.1371/journal.pone.0043942.
Chemical Education, 2014, 91, 1103-1104, doi: [82] R. E. Gordon, Electron microscopy: a brief history and
10.1021/ed500324w. review of current clinical application. Histopathology. New
[69] G. S. Bumbrah, R. M. Sharma, Raman spectroscopy– York: Humana Press, 2014: 119-135.10.1007/978-1-4939-
Basic principle, instrumentation and selected applications for 1050-2_7
the characterization of drugs of abuse, Egyptian Journal of [83] A. Krull, P. Hirsch, C. Rother, A. Schiffrin, C. Krull,
Forensic Sciences, 2016, 6, 209-215, doi: Artificial-intelligence-driven scanning probe microscopy,
10.1016/j.ejfs.2015.06.001. Communications Physics, 2020, 3, 54, doi: 10.1038/s42005-
[70] D. Cialla-May, M. Schmitt, J. Popp, Theoretical 020-0317-3.
principles of Raman spectroscopy, Physical Sciences Reviews, [84] R.-Z. Liu, Z.-Z. Shen, R. Wen, L.-J. Wan, Recent
2019, 4, 20170040, doi: 10.1515/psr-2017-0040. advances in the application of scanning probe microscopy in
[71] R. S. Das, Y. K. Agrawal, Raman spectroscopy: recent interfacial electroanalytical chemistry, Journal of
advancements, techniques and applications, Vibrational Electroanalytical Chemistry, 2023, 938, 117443, doi:

© Engineered Science Publisher LLC 2024 ES Mater. Manuf., 2024, 24, 1198 | 45
Review article ES Materials & Manufacturing

10.1016/j.jelechem.2023.117443. Nanotechnology. Dordrecht: Springer, 2015: 1-

[85] J. van Gorkom, D. van Delft, T. van Helvoort, The early 9.10.1007/978-94-007-6178-0_108-2
electron microscopes: incubation, Advances in Imaging and [98] A. Dazzi, C. B. Prater, AFM-IR: technology and
Electron Physics. Amsterdam: Elsevier, 2018, 43-128, doi: applications in nanoscale infrared spectroscopy and chemical
10.1016/bs.aiep.2018.08.002. imaging, Chemical Reviews, 2017, 117, 5146-5173, doi:
[86] J. McKinley, Electron and ion beam characterization of 10.1021/acs.chemrev.6b00448.
glass. Musgraves JD, Hu J, Calvez L, Springer Handbook of [99] J. Zhang, B. Xu, P. Zhang, M. Cai, B. Li, Effects of
Glass. Cham: Springer, 2019: 931-954, doi: 10.1007/978-3- surface roughness on wettability and surface energy of coal,
319-93728-1_27. Frontiers in Earth Science, 2023, 10, 1054896, doi:
[87] A. A. Hilal, Microstructure of Concrete, In book: high 10.3389/feart.2022.1054896.
performance concrete technology and applications (pp.3-24), [100] S. M. Lößlein, R. Merz, D. W. Müller, M. Kopnarski, F.
Publisher: INTECH, Editors: Salih Yilmaz, Hayri Baytan Mücklich, An in-depth evaluation of sample and measurement
Ozmen, doi: 10.5772/64574. induced influences on static contact angle measurements,
[88] T. Kowoll, E. Müller, S. Fritsch-Decker, S. Hettler, H. Scientific Reports, 2022, 12, 19389, doi: 10.1038/s41598-022-
Störmer, C. Weiss, D. Gerthsen, Contrast of backscattered 23341-3.
electron SEM images of nanoparticles on substrates with [101] J. Wang, Liquid contact angle measurement. Wang QJ,
complex structure, Scanning, 2017, 2017, 4907457, doi: Chung YW, Encyclopedia of Tribology. Boston, MA: Springer,
10.1155/2017/4907457. 2013: 1989-1994, doi: 10.1007/978-0-387-92897-5_475.
[89] W.R. Lin, Y.J. Chuang, C.H. Lee, F.G. Tseng, F.R. Chen, [102] A. Skłodowska, M. Woźniak, R. Matlakowska, The
Fabrication and characterization of a high-performance multi- method of contact angle measurements and estimation of work
annular backscattered electron detector for desktop SEM, of adhesion in bioleaching of metals, Biological Procedures
Sensors, 2018, 18, 3093, doi: 10.3390/s18093093. Online, 1999, 1, 114-121, doi: 10.1251/bpo14.
[90] A. Yoshida, Y. Kaburagi, Y. Hishiyama, Scanning electron [103] A. B. Yu, N. Standish, A study of particle size
microscopy. Materials Science and Engineering of Carbon. distributions, Powder Technology, 1990, 62, 101-118, doi:
Amsterdam: Elsevier, 2016, 71-93, doi: 10.1016/b978-0-12- 10.1016/0032-5910(90)80073-8.
805256-3.00005-2. [104] G. B. Basim, M. Khalili, Particle size analysis on wide
[91] L. E. Franken, K. Grünewald, E. J. Boekema, M. C. A. size distribution powders; effect of sampling and
Stuart, A technical introduction to transmission electron characterization technique, Advanced Powder Technology,
microscopy for soft-matter: imaging, possibilities, choices, 2015, 26, 200-207, doi: 10.1016/j.apt.2014.09.009.
and technical developments, Small, 2020, 16, 1906198, doi: [105] P. de la Peña, M. Thomas, T. R. Molefyane, Particle size
10.1002/smll.201906198. distribution: an experimental study using southern African
[92] N. Brodusch, S. V. Brahimi, E. Barbosa De Melo, J. Song, reduction methods and raw materials, PLoS One, 2022, 17,
S. Yue, N. Piché, R. Gauvin, Scanning electron microscopy e0278867, doi: 10.1371/journal.pone.0278867.
versus transmission electron microscopy for material [106] F. Ambroz, T. J. MacDonald, V. Martis, I. P. Parkin,
characterization: a comparative study on high-strength steels, Evaluation of the BET theory for the characterization of meso
Scanning, 2021, 2021, 5511618, doi: 10.1155/2021/5511618. and microporous MOFs, Small Methods, 2018, 2, 1800173,
[93] M. Malatesta, Transmission electron microscopy as a doi: 10.1002/smtd.201800173.
powerful tool to investigate the interaction of nanoparticles [107] G. Zhu, H. Ren, Porous organic frameworks: design,
with subcellular structures, International Journal of synthesis and their advanced applications, Springer, 2014.
Molecular Sciences, 2021, 22, 12789, doi: [108] K. Kaneko, C. Ishii, Superhigh surface area
10.3390/ijms222312789. determination of microporous solids, Colloids and Surfaces,
[94] M. Malatesta, Transmission electron microscopy for 1992, 67, 203-212, doi: 10.1016/0166-6622(92)80299-h.
nanomedicine: novel applications for long-established [109] P. Majumdar, Thesis for: M. Tech. 2017, Development
techniques, European Journal of Histochemistry, 2016, 60, of electrodes for artificial photosynthetic system, doi:
2751, doi: 10.4081/ejh.2016.2751. 10.13140/RG.2.2.21857.71528.
[95] L. E. Franken, K. Grünewald, E. J. Boekema, M. C. A. [110] F. Ambroz, J. Thomas, V. Martis, I. P. Parkin, When
Stuart, A technical introduction to transmission electron nitrogen is used as the adsorbate gas, P/Po values of 0.10, 0.20,
microscopy for soft-matter: imaging, possibilities, choices, and 0.30 are often suitable, Small Methods, 2018, 2, 1800173,
and technical developments, Small, 2020, 16, 1906198, doi: doi: 10.1002/smtd.201800173.
10.1002/smll.201906198. [111] B. Chen, H. Chaouki, D. Picard, J. Lauzon-Gauthier, H.
[96] M. Baclayon, W. H. Roos, G. J. L. Wuite, Sampling Alamdari, M. Fafard, Physical property evolution of the anode
protein form and function with the atomic force microscope, mixture during the baking process, Materials, 2021, 14, 923,
Molecular & Cellular Proteomics, 2010, 9, 1678-1688, doi: doi: 10.3390/ma14040923.
10.1074/mcp.r110.001461. [112] B. Mouli Prasanth, A review on thin films, conducting
[97] B. W. Hoogenboom, AFM in liquids. Encyclopedia of polymers as sensor devices, Materials Research Express, 2022,

46 | ES Mater. Manuf., 2024, 25, 1198 © Engineered Science Publisher LLC 2024
ES Materials & Manufacturing Review article

9, 022001, doi: 10.1088/2053-1591/ac4aa1.

[113] M. Mirshojaeian Hosseini, R. Nawrocki, A review of the
progress of thin-film transistors and their technologies for
flexible electronics, Micromachines, 2021, 12, 655, doi:
10.3390/mi12060655.
[114] A. Maalouf, T. Okoroafor, Z. Jehl, V. Babu, S. Resalati,
A comprehensive review on life cycle assessment of
commercial and emerging thin-film solar cell systems,
Renewable and Sustainable Energy Reviews, 2023, 186,
113652, doi: 10.1016/j.rser.2023.113652.
[115] A. Kot, D. Dorosz, M. Radecka, K. Zakrzewska,
Improved photon management in a photoelectrochemical cell
with Nd-modified TiO2 thin film photoanode, International
Journal of Hydrogen Energy, 2021, 46, 12082-12094, doi:
10.1016/j.ijhydene.2020.05.094.
[116] T. K. Shivasharma, N. Upadhyay, T. B. Deshmukh, B. R.
Sankapal, Exploring vacuum-assisted thin films toward
supercapacitor applications: present status and future
prospects, ACS Omega, 2023, 8, 37685-37719, doi:
10.1021/acsomega.3c05285.
[117] R. R. Willey, O. Stenzel, Designing optical coatings with
incorporated thin metal films, Coatings, 2023, 13, 369-378,
doi: 10.3390/coatings13020369.
[118] A. Pandey, R. Yadav, M. Kaur, P. Singh, A. Gupta, S.
Husale, High performing flexible optoelectronic devices using
thin films of topological insulator, Scientific Reports, 2021, 11,
832, doi: 10.1038/s41598-020-80738-8.
[119] X. Liang, J. Xia, G. Dong, B. Tian, L. Peng, Carbon
nanotube thin film transistors for flat panel display application,
Topics in Current Chemistry, 2016, 374, 80, doi:
10.1007/s41061-016-0083-6.
[120] K. R. Laughlin, S. Jamieson, A. C. Pearson, H. Wang, R.
R. Vanfleet, R. C. Davis, M. R. Linford, B. M. Lunt, Thin-film
carbon nanofuses for permanent data storage, ACS Omega,
2017, 2, 2432-2438, doi: 10.1021/acsomega.7b00025.
[121] S. Dhall, B. R. Mehta, A. K. Tyagi, K. Sood, A review
on environmental gas sensors: materials and technologies,
Sensors International, 2021, 2, 100116, doi:
10.1016/j.sintl.2021.100116.
[122] A. K. Singh, N. K. Chowdhury, S. C. Roy, B. Bhowmik,
Review of thin film transistor gas sensors: comparison with
resistive and capacitive sensors, Journal of Electronic
Materials, 2022, 51, 1974-2003, doi: 10.1007/s11664-022-
09485-y.

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