Advances in Colloid and Interface Science 330 (2024) 103203

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Advances in Colloid and Interface Science

journal homepage: www.elsevier.com/locate/cis

Review Article

Sputtering thin films: Materials, applications, challenges and

future directions
Renuka Garg a, Spandana Gonuguntla b, c, Saddam Sk b, c, Muhammad Saqlain Iqbal d,
Adewumi Oluwasogo Dada b, e, Ujjwal Pal b, c, **, Mohsen Ahmadipour f, *
a
Department of Chemical and Biological Engineering, American University of Sharjah, Sharjah, PO Box 26666, United Arab Emirates
b
Department of Energy & Environmental Engineering, CSIR-Indian Institute of Chemical Technology, Hyderabad 500007, India
c
Academy of Scientific and Innovative Research (AcSIR), Ghaziabad 201002, India
d
Department of Chemistry, COMSATS University Islamabad, Lahore campus, 54000 Lahore, Pakistan
e
Industrial Chemistry Programme, Nanotechnology Laboratory, Department of Physical Sciences, Landmark University, P.M.B.1001, Omu-Aran, Kwara, Nigeria
f
Institute of Power Engineering, Universiti Tenaga Nasional, Serdang, Malaysia

A R T I C L E I N F O A B S T R A C T

Keywords: Sputtering is an effective technique for producing ultrathin films with diverse applications. The review begins by
Sputtering providing an in-depth overview of the background, introducing the early development of sputtering and its
Ultrathin films principles. Consequently, progress in advancements made in recent decades highlights the renaissance of sput­
Structures
tering as a powerful technology for creating thin films with varied compositions, structures, and properties. For
Photocatalyst
the first time, we have discussed a thorough overview of several sputtered thin film materials based on metal and
Fuel cell
Biomedical applications metal oxide, metal nitride, alloys, carbon, and ceramic-based thin film along with their properties and their
applicability in various fields. We further delve into the applications of sputter-coated thin films, specifically
emphasizing their relevance in environmental sustainability, energy and electronics, and biomedical fields. We
critically examine the recent advancements in developing sputter-coated catalysts for eliminating water pol­
lutants andhydrogen generation. Additionally, the review sheds light on advantages, shortcomings, and future
directions for developing sputter-coated thin films utilized in biodegradable metals and alloys with enhanced
corrosion resistance and biocompatibility. This review is a comprehensive integration of recent literature,
covering diverse sputtering thin film applications. We delve deeply into various material types and emphasize
critical analysis of recent advancements, particularly in environmental, energy, and biomedical fields. By of­
fering insights into both advancements and limitations, the review provides a nuanced understanding essential
for practical utilization.

1. Introduction of micrometers [1–4]. The fundamental benefit of thin film technology is

the reduction in size and the ability to tune material properties. Thin
A thin film can be described as a layer with the remarkable capacity films also help to reduce costs and miniaturize devices. The character­
to stretch infinitely in two dimensions while having constraints in the istics of the film are primarily dictated by its structure, although the
third dimension. Its thickness can span from a few nanometers to a range mechanical and thermal properties of the film are interlinked with the

Abbreviations: YSZ, Yttria stabilized zirconia; PVD, Physical vapor deposition; HIPIMS, High-power impulse magnetron sputtering; WO3, Tungsten trioxide;
DSSCs, Dye-sensitized solar cells; NIR, Near-infrared; TCE, Transparent conductive electrodes; DLC, Diamond-like carbons; GQD, Graphene quantum dot; ITO, Indium
tin oxide; HEA, High-entropy alloy; CCTO, Calcium copper titanate-based ceramics; Ca10(PO4)6OH2, Hydroxyapatite; US EPA, United States Environmental Pro­
tection Agency; SDGs, Sustainable development goals; PLD, Pulsed laser deposition; TBA, Tertiary-butyl alcohol; LYS-NIS, Lysozyme-nisin; NaTaO3, Sodium tantalate;
EMA, Bruggeman’s effective medium approximation; TFFC, Thin film fuel cells; BIMEVOX, Bismuth vanadium copper oxide; LSGM, Lanthanum strontium gallium
manganite; CGO, Ceria gadolinia oxide; SRFC, Solar rechargeable flow cells; CdTe, Cadmium telluride; ECM, Extracellular matrix; Si-HA, Silicon-doped hydroxy­
apatite; CAR, Chimeric antigen receptor.
* Corresponding author.
** Corresponding author at: Department of Energy & Environmental Engineering, CSIR-Indian Institute of Chemical Technology, Hyderabad 500007, India.
E-mail addresses: [email protected] (U. Pal), [email protected] (M. Ahmadipour).

https://doi.org/10.1016/j.cis.2024.103203
Received in revised form 11 May 2024;
Available online 22 May 2024
0001-8686/© 2024 Elsevier B.V. All rights are reserved, including those for text and data mining, AI training, and similar technologies.
R. Garg et al. Advances in Colloid and Interface Science 330 (2024) 103203

reaction conditions and the method of deposition [5–7]. Physical and involving gas discharge tubes, such as the Crookes tube developed by
chemical methods have been identified as the major thin film deposition William Crookes in the 1890s [17], Fig. 2. Crookes used sputtering to
routes with various techniques classified under these two general routes deposit thin films of various metals and alloys onto substrates, leading to
as illustrated in Fig. 1(a). the discovery of preferential sputtering from alloy targets. Arthur
Sputtering is a physical process of depositing thin films. It falls under Wright, an American physicist, utilized sputtering to deposit metal films
the category of thin film technology known as physical vapor deposition onto glass microscope slides and designed a system for depositing films
(PVD) [9]. Sputtering is a phenomenon in which energetic particles of of uniform thickness by mounting the substrate on a pendulum. Wright’s
plasma or gas collide with the surface of a solid and detach small par­ films were highly reflective and were used in the manufacturing of
ticles from it. In high-precision circumstances, the phenomenon happens commercial mirrors [18,19]. Over the past few years, there has been
naturally in outer space and might induce undesirable surface wear. The notable traction in the utilization of thin film materials. Towards the end
coating material (the sputtering target) is blasted with plasma ions, and of the 19th century, sputtering deposition became a standard practice in
the particles that are removed enter the gas phase. The vapor then manufacturing commercial mirrors. Sputtering is an extensively
condenses on the substrate surface, strongly adhering to it and forming a employed method for depositing thin films across diverse sectors such as
very thin coating. This process allows for the uniform application of very microelectronics, optics, and coatings. The historical development of
different substances (metals, alloys, oxides, and nitrides) on a broad sputtering technology laid the foundation for modern materials science
range of substrates, ranging from semiconductor wafers to architectural and continues to drive technological advancements in various fields.
glass. Sputtering deposition is a well-known coating process utilized in However, the technique garnered substantial attention during the
thin film technology for decades in various applications [10]. Thin late 1950s and early 1960s, driven by advancements in vacuum tech­
deposition by sputtering has been used for over a century and there are nology and the realization that a broad spectrum of materials could be
numerous types of sputtering namely: Magnetron, reactive, and ion deposited through direct current (DC) sputtering, as reported by Kay in
beam sputtering. Magnetron sputtering involves a vacuum-based pro­ 1963 [20], and radio frequency (RF) sputtering, which was mainly
cess for the deposition of metals, textiles, or other materials having a utilized for dielectrics, as reported by Anderson et al. in 1962 [21]. In
thickness advantage. Reactive sputtering on the other deals with sput­ the 1970s, magnetron sputtering was introduced, which improved the
tering the elemental target under a gaseous atmosphere which eventu­ efficiency of sputtering by using a magnetic field to restrain the plasma.
ally would result in sputter compound formation by a reaction between Reactive sputtering was also developed during this time, which allowed
the gas and the targeted material. The deposition rate and film charac­ for the creation of thin films with specific chemical compositions [22].
teristics are heavily influenced by the gas flow rate and partial pressure In the 1990s, pulsed laser deposition (PLD) was introduced as an
management. The ion beam sputtering technique involves bombarding approach to depositing thin films using a laser to ablate a target. In the
the target material with an intense ion beam from a source to create 2000s, high-power impulse magnetron sputtering (HIPIMS) was intro­
uniform thin layers as depicted in Fig. 1(b). The resulting film achieves duced as a method of improving the density and quality of sputtered
high levels of purity, with the deposition of target atoms remaining films [23,24].
unaffected by the vapor pressure of the material. This method operates Therefore, thin film materials have shown tremendous potential in
within a high vacuum environment and is costly due to the requirement environmental sustainability, energy, and electronic, and biomedical
for premium-grade targets. Despite its expenses, a notable benefit of applications due to their unique properties such as flexibility, biocom­
sputtering is the facilitation of refractory metal deposition. Neverthe­ patibility, and high surface area-to-volume ratio. They can be prepared
less, sputtered films are more prone to contamination. using various methods such as PVD, chemical vapor deposition (CVD),
With the rapid development of technology, biomedical engineering and spin coating. Thin film materials have been employed in various
has emerged as a rapidly growing field. Biomedical engineering is an devices such as sensors, biosensors, drug delivery systems, and tissue
interdisciplinary field that combines principles of biology, medicine, engineering scaffolds, among others [25,26]. In previous studies, re­
physics, and engineering to develop innovative solutions for healthcare searchers have provided insights into the sputter-coated thin films for
problems [9–11]. Over the past few years, there has been notable trac­ one or two specific applications. Magnetron sputtering offers several
tion in the utilization of thin film materials within the realm of advantages over other techniques such as CVD and PVD. These advan­
biomedical engineering. Thin film materials offer several advantages tages include fast deposition speed, minimal substrate temperature rise,
over traditional materials such as metals and polymers, including the and minimal damage to the film. It is capable of depositing a wide va­
ability to tailor surface properties, improved corrosion resistance, and riety of materials including insulators, metals, alloys, and composites,
the ability to release drugs for controlled drug delivery [12–15]. and it works well for insulating targets. Additionally, magnetron sput­
Sputtering technology was developed with the invention of the tering allows for the simultaneous sputtering of different metals, alloys,
Sprengel mercury pump by Herman Sprengel in the 1860s [16]. This and oxides onto the substrate. The particle size of the film can be
pump improved vacuum technology and allowed for experiments controlled by adjusting process parameters. Other benefits include a

Fig. 1. Diagram of the (a) thin film deposition technique [8] and (b) sputtering process [6].

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R. Garg et al. Advances in Colloid and Interface Science 330 (2024) 103203

Fig. 2. Summary of the development history of sputter-coated thin films.

large sputtering area, which is advantageous for manufacturing large- foreign particles like dust or debris in PVD coatings [28]. Himanshu
sized parts, high-energy atoms that promote good interfacial adhesion et al. review diverse techniques for cobalt oxide thin films, emphasizing
between the film and substrate, compactness, high purity, and uniform their potential in portable devices and energy storage [29]. Yang et al.
film formation. However, there are some disadvantages to magnetron provide a review on (yttria-stabilized zirconia) YSZ electrolyte prepa­
sputtering, including plasma instability and the inability to achieve ration for solid oxide fuel cells (SOFCs) via magnetron sputtering. Focus
high-speed sputtering at low temperatures for strong magnetic materials on reducing operating temperature through thin electrolyte films with
due to magnetic flux limitations. Despite these drawbacks, magnetron stability and performance. Comparison of methods, effects of processing
sputtering has emerged as the leading coating technology for various parameters, and perspectives for high-performance SOFCs discussed
applications due to its numerous advantages. [30]. But in this review, we aim to provide a comprehensive overview of
Ju et al. discuss hydrophobic thin films (oxides, Diamond-like car­ sputter-coated thin films (e.g. magnetron sputtering), including their
bons (DLC), polytetrafluoroethylene) produced through magnetron principles, methods, materials, and applications. We begin by discussing
sputtering deposition. These films find use in self-cleaning, anti-corro­ the basic principles of sputtering to give the readers a clear under­
sion, and other applications [27]. Peter et al. provide a comprehensive standing of this technique. we then explore the wide range of applica­
overview of growth defects resulting from substrate imperfections and tions that can benefit from coated thin films through sputtering,

Fig. 3. a) shows the trend in the number of publications since 2010 b) shows the number and percentage of articles published in different subject areas and c) articles
published on this subject using the keywords “sputter coated thin films” [Source-Science direct].

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R. Garg et al. Advances in Colloid and Interface Science 330 (2024) 103203

magnetron sputtering, and other types, including the development of oxidized copper layer (60 nm) onto a polyimide substrate, followed by
thin films for energy and electronics (e.g. fuel cells), environmental and wet etching using a photoresist mask. The subsequent fabrication of
sustainability, coatings for biomedical implants and other applications. high-performance composites hinged on the utilization of hybrid Cu
Throughout this overview, we underscore recent progress in the evolu­ mesh electrodes, onto which RF-sputtered ZnO or AZO were coated.
tion of sputter-coated thin films, while also addressing the hurdles that These composites demonstrated transmittance levels exceeding 90% at
necessitate attention to enhance their efficacy and broaden their scope 550 nm [66].
of applications. As far as our knowledge extends, there hasn’t been a The impressive stability and exceptional performance exhibited by
comprehensive review article encompassing all the applications from Cu mesh hybrid electrodes even in challenging environments underscore
recent literature on this subject. their substantial potential for integration in applications such as smart
The statistical data in Fig. 3 [a, b, c] shows the number/type/per­ displays and solar cells. This fabrication approach enables the efficient
centage of articles published on the subject over the past 14 years. The production of flexible, large-area transparent conductive electrodes
number of articles published each year has been steadily increasing over (TCEs) on a mass scale. By employing reactive magnetron sputtering and
time, with a total of 48,392 articles published since 2010. This indicates subsequent ex-situ post-annealing, Fridriksson and his research team
a growing interest in the topic and a continuous effort towards research successfully generated diverse phases of niobium oxides (NbxOy) [67].
and development. This article will be a comprehensive compilation of all The study reveals that cubic NbO, tetragonal NbO2, and monoclinic
the relevant and up-to-date research on sputter-coated thin films pub­ Nb2O5 thin films can be synthesized through DC reactive magnetron
lished in recent years (2010-2024). It aims to provide readers with a sputtering at moderate temperatures, followed by post-annealing within
thorough understanding of the current state-of-the-art in this field and the range of 600–800 ◦ C. In another study, Chawla et al. observed that a
cover all significant advancements and findings. This article will serve as variety of structural morphologies of the titanium films as the substrate
a valuable resource for researchers, students, and professionals who seek [silicon (Si)] temperature varied in the range of 100 ◦ C to 600 ◦ C. The
to stay informed and updated on the latest developments in the area of scanning electron microscopic (SEM) images revealed that 2-D and 3-D
sputtering technology and its applications. Out of the total number of hexagonal structures of the grains in Ti thin films were obtained as
articles published on sputter-coated thin films, the majority are research shown in Fig. 4a(i-vi) [68]. In a similar study by Hendri et al. [69] cone-
articles. There is a comparatively low percentage of review articles like structure of the as-grown ZnO transformed into rod-like ZnO NCs
available for readers to get a comprehensive overview of the topic. after thermal annealing at 600 ◦ C Fig. 4b (i-ii). Further annealing at
Therefore, to fill this gap and provide readers with an in-depth under­ 800 ◦ C promotes the increase in rods density. Thus, it can be inferred
standing of sputter-coated thin films, we have taken the initiative to that temperature has a significant effect on the structural and morpho­
compile all the relevant data and publish it in the form of an article. logical properties of thin film materials.
The fabrication of metal oxide heterostructures, especially using
2. Materials for thin film preparation metal oxides as building blocks, has been exploited for gas sensing ap­
plications. Some of the examples of n-type metal oxide heterostructures
Magnetron sputtering is considered the most important physical include tin dioxide (SnO2), indium oxide (In2O3), tungsten trioxide
deposition process for depositing oxide layers. Magnetron-sputtered (WO3), vanadium oxide (V2O5), gallium oxide (Ga2O3), and iron oxide
thin-film materials have demonstrated applicability across a diverse (Fe2O3) and p-type metal oxides such as nickel oxide (NiO), copper oxide
array of sectors, primarily in the realms of manufacturing, electronics, (CuO), cobalt oxide (Co3O4), manganese oxide (Mn3O4) and chromium
semiconductor devices, transparent thin-film transistors, photoelectric oxide (Cr2O3) for fabrication of metal oxides heterostructures [31–34].
detectors, optical coatings, solar cells, aerospace, biomedical domains, It was found that the uniform thickness of the integrated ZnO nano­
and more. Devices often necessitate specific materials possessing distinct particle thin film used as a multi-color photodetector over a p-Si sub­
chemical, mechanical, electrical, and optoelectronic properties based on strate was around 60 nm. Recent times have witnessed a surge of interest
their application. Therefore, for the first time in this review we have in tungsten oxide-based materials owing to their remarkable effective­
discussed a thorough overview of several sputtered thin film materials ness in Near-infrared (NIR) shielding. Notably, in heat shielding exper­
based on metal and metal oxide, metal nitride, alloys, carbon and iments, thin films of tungsten oxide (WO3-x, 0 < x < 1) deposited onto
ceramic-based thin film along with their properties and their applica­ soda-lime glass substrates at 500 ◦ C, exhibited superior capacity to lower
bility in various fields (Table 1). Moreover, in this section, the effect of the interior temperature of a heat box compared to soda-lime glass and
various reaction conditions on the growth and properties of thin-film indium tin oxide (ITO) coated glass. This observation suggests that these
materials have also been discussed in detail. deposited films hold potential for use as thermal insulating materials,
contributing to energy-saving endeavors [72]. Further, metal oxides
2.1. Metal and metal oxide-based material such as molybdenum oxide (MoOx), titanium dioxide (TiO2), bismuth
oxide (Bi2O3), cuprous oxide (Cu2O), and ITO have emerged as vital
Metal and metal oxides-based sputter-coated thin films have materials for solar cell applications. For many years, the transparent
emerged as potential options for various industrial applications owing to conducting oxide material most utilized has been ITO. However because
their biocompatibility, excellent stability, ability to generate charge the supplies of elemental indium are rapidly depleted, the indium
carriers, longevity, advantageous electronic structure, and charge element is poisonous, less stable in hydrogen plasma, and costly [73]. As
transport properties. Metallic and metal oxide-based thin films a result, producing ITO-free TCEs from low-cost alternatives is ideal for
frequently exhibit exceptional electrical and electronic characteristics, mass manufacturing. TiO2 is a highly researched material because of its
which are commonly employed in electronic applications. For instance, low cost, ease of production, and great performance in dye-sensitized
ZnO, TiO2, CdO, BiO, AlO, RuO, and NiO-based metal oxide films are solar cells (DSSCs) and perovskite solar cells.
frequently preferred for use in optoelectronic applications, such as Bi2O3 thin films have attracted a lot of interest in solar cell appli­
photodiodes, photodetectors, photocatalysis, and photocells [63,64]. cations due to their high refractive index and extraordinary photosen­
Various types of dopants such as graphene, Zn, Fe, Co, Gd, Cu, and Ni sitivity. In 2017, Hrostea and his colleagues developed oxide/metal/
have also been used to achieve the desired properties of the thin films oxide (oxide = ITO, AZO, TiO2, and Bi2O3, Metal = Au) electrodes. They
[65]. It has been shown that transparent conductive films with good demonstrated that excellent quality translucent conducting thin film
electrical and mechanical properties may be constructed using Cu frameworks with resistance of 104 cm and transmittance of 75% were
nanowires. Mesoscale hexagonal copper mesh structures were used in achieved [35]. In another work, Venkatesan produced a bismuth vana­
Kim and his team’s demonstration of a transparent conductive hybrid. In date (BiVO4) photoelectrode using an RF-sputtering approach with a
achieving this, an initial step involved RF-sputtering a high-quality, non- circular target of BiVO4 nanopowder and employed it to degrade

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Table 1
List of selected thin film materials synthesized via magnetron sputtering technique along with their properties and applications in various fields.
Metal oxides Magnetron Remarks Applications References
sputtering

Metal and metal oxide based thin film materials

CuO DC Target gas: NO2 Gas sensing [31]
V2O3 DC Target gas: CH4 Gas sensing [32]
ZnO RF Target gas: H2S Gas sensing [33]
ZnO RF Target gas: H2 Gas sensing [34]
Oxide/Metal/Oxide (Oxide = DC High-temperature annealing (450 ◦ C) enhanced crystallinity but Solar cell [35]
ITO, AZO, TiO2 and Bi2O3, lowered transmittance and electric conductivity.
Metal = Au)
Cu2O Reactive Electron affinity 3.7 eV Solar cell [36]
sputtering Conversion efficiency: 12%
MoOx RF Electron affinity:5.92 eV Solar cell [37]
Refractive indices: ~1.8-2.05
gallium-doped zinc oxide Reactive Low sheet resistance (10.66 Ωsq− 1), high average transmittance Solar cell [38]
sputtering (90.04%), and superior figure of merit (328 Ω− 1)
β-Ta2O5 RF Superior cellular biocompatibility with human skin fibroblasts and Biomedical [39]
excellent antibacterial performance
TaxOy Pulsed Dental implants, improved pre-osteoblastic (MC3T3-E1) cell Biomedical [40]
magnetron spreading and morphology
ZrO2 DC Coating has Improved corrosion resistance of 316 L SS Biomedical [41]
Nb2O5 RF Favorable implant/bone bonding and can be used for dental Biomedical [42]
implants
TiO2-Ag DC TiO2-Ag had a higher absorption efficiency of 64.27% and 76.74% Photocatalytic degradation [43]
for methylene blue (MB) dye under UV and sunlight irradiation,
respectively.

Nitride based thin film materials

TiN/TiO2/Al2O3 DC TiN/TiO2/Al2O3 photoelectrode was used to generate H2 from Photoelectrochemical water splitting [44]
sewage water splitting
TiN Reactive TiN thin films have promising applications in the field of Supercapacitor electrode [45]
magnetron supercapacitors with a high energy density of 17.6 mWh cm− 3 at a
sputtering power density of 1.1 W cm− 3
ZrN/Cu DC Exhibited enhanced wear resistance and low friction coefficient. Biomedical [46]
Showed excellent antibacterial activities to P. aeruginosa.
TiN Reactive Superior corrosion resistance and bio-compatibility can be applied Orthopedic implant devices and [47]
magnetron in advanced bio-coatings with multifaceted features. neural electrodes
sputtering

Alloy based thin film materials

TiTaHfNbZr HEA films on RF Even when exposed to two extremely acidic bodily fluids, the Biomedical [48]
Nickel‑titanium (NiTi) TiTaHfNbZr HEA coating greatly limits Ni ion leakage from NiTi.
NiTiCu/AlN/ NiTiCu DC Heterostructures outperformed NiTiCu/AlN and pure NiTiCu in Microelectromechanical (MEMS) [49]
terms of mechanical and damping qualities. devices
Ta/TaxOy multilayer on NiTi DC and RF Coating provides enhanced surface qualities such as radiopacity, Biomedical stents [50]
in-vitro corrosion resistance, and biocompatibility.
TiZrHfNiCuCo DC TiZrHfNiCuCo HEA nitride film has higher hardness and elastic Coating material [51]
modulus than TiZrHfNiCuCo HEA metallic film.
Ti-Nb-Zr ternary alloy Magnetron co- The effects of Zr addition in Ti-Nb-based alloy coatings on phase Biomedical [52]
sputtering formation, shape, texture, and film growth were studied. There was
no evidence of coating delamination.

Carbon based thin film materials

Zr-doped GLC DC The film has a low friction coefficient and wear rate. Protective coatings in biomedical [53]
components
Cr/GLC film coupled with Si3N4, DC In saltwater, a Cr/GLC film linked to Si3N4 ceramic showed optimal Protective coatings in hydrolytic [54]
SiC, WC, Al2O3 and ZrO2 tribological performance. systems
Ge co-deposited DLC DC Light sensitivity, photosensitivity, and photoresponsivity increased Opeoelectronics [55]
as lighting intensity increased.
DLC/ hydroxyapatite Magnetron Superior corrosion resistance and the prevention of hazardous Beneficial to the formation and [56]
sputtering metal ions being discharged into the Simulated Body Fluid (SBF) reconstruction of new bone tissue
solution.
TiC/a:C DC Because of its outstanding chemical stability and mechanical Passivation layers [57]
qualities, it is used as a passivation layer in a variety of
applications.
C/TiO2/Ti/n+p-Si Magnetron A 5-nm thick carbon coating is sprayed onto the TiO2/Ti/n + p-Si Solar rechargeable batteries [58]
sputtering electrode. At the same bias, the photocurrent density increases
considerably after carbon modification to − 12.5 mA cm− 2.

Ceramic based thin film materials

HAp/Al2O3/TiO2 RF The triple-layered thin film coatings (HAp/Al2O3/TiO2) Prosthetic-orthopedic implant [59]
demonstrated great crystallinity, improved corrosion resistance,
and excellent biocompatibility.
(continued on next page)

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Table 1 (continued )
Metal oxides Magnetron Remarks Applications References
sputtering

hydroxyapatite (HA) coatings RF In vitro tests with primary dental pulp stem cells and mouse Dental implant [60]
fibroblast NCTC clone L929 cells revealed that HA coatings were
not cytotoxic. Different thicknesses of low-crystallinity HA coatings
encouraged cells to adhere, proliferate, and form mineralized
nodules on the surface better than uncoated titanium substrates.
CCTO thin films with HfO2 as a RF At 100 kHz, an improved dielectric constant of 1078 was reported. for capacitor and gate dielectric [61]
buffer layer and Zn as an The inclusion of an HfO2 buffer layer contributes to the better applications
intermediate layer morphological and electrical characteristics of CCTO films.
CCTO RF The maximum photocatalytic activity was demonstrated by a Photocatalysis [62]
CCTO thin film annealed at 600 ◦ C, which eliminated 67.4% of RhB
dye in 4 h at a rate constant of 0.217 min-1.

rhodamine 6G dyes when exposed to visible light [74]. The deposition of Fig. 4c and d [70]. DLC has been identified as a well-known biocom­
the film took place at ambient temperature and demonstrated patible and bioinert material. However, poor adherence and excessive
commendable degradation efficiency. Additionally, it was observed that internal stress have limited DLC’s practical use as a coating on metal
elevating the substrate temperature led to a reduction in the film’s implants. As a result, several elements like as Ti, Ag, S, Cu, and Si, among
thickness. Employing a reactive DC magnetron sputtering method, others, were introduced to improve the qualities of DLC for use in the
Madhavi et al. effectively deposited thin films of TiO2 and N-TiO2 on an biomedical area [82,83]. Liao et al. had used magnetron sputtering to
FTO-coated glass substrate. Notably, their work showcased the collab­ deposit nitrogen-doped DLC films on Si substrates at ambient tempera­
orative influence of Ag nanoparticles on these materials, revealing ture [78]. Liao and his colleagues demonstrated that nitrogen-
enhanced photocatalytic attributes. The assessment of their photo­ containing DLC coatings have improved biocompatibility and
catalytic properties involved the measurement of methyl orange (MO) increased mouse fibroblast growth and its attachment. These findings
dye degradation upon exposure to sunlight [75]. Further in the study were found to be important for the development and encapsulation of in-
due to Lenis et al., using the magnetron sputtering method, SiO2/TiN/Ti vivo devices. Additionally, a study conducted by Khamseh et al. in 2018
trilayer multilayer coatings were integrated between a Ti-6Al-4 V sub­ involved the fabrication of copper/ DLC composite films on mild steel
strate and a multilayer HA-Ag coating. The coatings were found to be through magnetron sputtering. The resultant Cu/DLC thin films
non-toxic in in-vitro biological tests, and antibacterial activity against exhibited remarkable corrosion resistance [84]. Furthermore, the
the Staphylococcus aureus strain was detected at a concentration of 0.25 incorporation of copper into the DLC film led to an enhancement in film
mg/L of Ag. The coatings’ effectiveness in prosthetic implants, including hardness. Notably, the investigation highlighted a decrease in internal
microplates and fixation screws, has been established [76]. stress values of Cu/DLC thin films with escalating Cu/C ratios. Another
exploration focused on the production of cobalt-DLC nanocomposite
films via the sputtering process on Si wafers and 316 L stainless steel, all
2.2. Carbon based materials conducted at room temperature [77]. Superparamagnetic characteris­
tics with significant saturation magnetization and corrosion resistance
Sputter-coated carbon-based films, such as graphene, fullerene, were observed in Co-DLC nanocomposite films with cobalt concentra­
carbon nanotubes (CNTs), graphite-like carbon (GLC), diamond-like tions ranging from 29 to 36 at. %, indicating that they might be
carbons (DLC), amorphous carbons, etc., are gaining popularity as film employed in biocompatible devices. Recently, Kheradmandfard and his
materials owing to their exceptional properties [77–79]. Thin film ma­ team [71] reported that the wear resistance and durability of Ti-29Nb-
terials incorporating graphene have demonstrated durability, resistance 13Ta4.6Zr (TNTZ) alloy were increased by coating it with a multilayer
to shocks, and favorable electrical characteristics. Nevertheless, the cost nanocomposite made of Si and DLC. The study demonstrated that Si/
remains a challenge, and the large-scale production of graphene-based DLC MNC on the TNTZ alloy has an extremely low wear rate of 6.2 ×
thin films presents difficulties. Additionally, CNTs possess remarkable 10− 10 mm3 N− 1 mm− 1. The hardness of the Si/DLC substrate was
physical and chemical attributes, encompassing thermal and electrical roughly 7 times that of the TNTZ substrate. The H/E and H3/E2 values
conductivity. Nonetheless, the production of sufficient CNT material for were 0.14 and 0.5 GPa, respectively, much higher than the TNTZ sub­
surface coating remains a challenging endeavor [55] Moreover, in the strate values (Fig. 4e and f). As a result, Si/DLC was identified as a
biomedical field, CNTs have negative effects on reproductive systems promising contender for utilization in long-term implant applications as
[80]. The DLC could be a suitable alternative in comparison to graphene well as other industrial applications.
and CNTs and can be applied in various applications due to its good
tribological properties, chemical stability, low coefficient of friction,
and good biocompatibility. The graphene quantum dot (GQD) was 2.3. Nitride based materials
produced by Zhu and his team directly from graphite using magnetron
sputtering and a simple chemical process. They also investigated the use Recent research has been focused on nitride-based thin films owing
of GQDs in thin-film transistors (TFT). The saturation current of the to their fascinating properties such as hardness, ductility, high thermal
GQD-ZnO TFT at 2.5 V was 45 A, which is about 9 times more than the stability, biocompatibility, and resistance to corrosion and wear
saturation current of the pure ZnO TFT. The electrical parameters of the [47,85]. Titanium nitride (TiN) is one of the most well-known metal
GQD-ZnO TFT were superior to those of pure ZnO TFT, including a nitrides for its unique physical, chemical, mechanical, and optical
higher field-effect mobility (FE) of 17.7 cm2/Vs, a higher on/off current properties. Since the 1980s, several nitride-based thin film coating
ratio (Ion/Ioff) of 1.7 × 107, and a lower SS value of 90 mV/decade. materials have been produced by alloying TiN with other metals such as
These qualities meet the standards for use in e-books and TFT-LCD ap­ aluminum (Al), molybdenum (Mo), vanadium (V), zirconium (Zr), etc.,
plications [81]. [86]. The electric conductivity of TiN is close to that of metals which
For industrial applications, DLC films should have a high sp3/sp2 makes TiN an interesting material for its utilization in supercapacitor
ratio, high hardness, resistance to corrosion, etc. reported the high value electrode applications. Wei et al. used magnetron sputtering to produce
of the refractive index (n = 2.45 at 400 nm) and high sp3 fraction content the TiN thin films on Si wafers [45]. The research found that TiN thin
(70–80%) based on the Raman Scattering spectra analysis as shown in films had a high energy density of 17.6 mWh cm-3 at a power density of

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R. Garg et al. Advances in Colloid and Interface Science 330 (2024) 103203

Fig. 4. Morphological characteristics of thin film materials; titanium films on Si deposited at substrate temperature: (a) (i) 100 ◦ C, (ii) 200 ◦ C, (iii) 300 ◦ C, (iv)
400 ◦ C, (v) 500 ◦ C and (vi) 600 ◦ C, [68] (b) (i) as-grown ZnO NCs, (ii) annealed-ZnO 600 ◦ C NCs [69] (c) Raman spectra with Gaussian curves fitting D and G peaks
for 532 and (d) at 633 nm [70] (e) Hardness, elastic modulus, (f) H/E and H3/E2 values for the bare TNTZ alloy and the TNTZ alloy with Si/DLC MNC [71].

1.1 W cm-3 and could be employed in supercapacitors. produce hard coatings, however, it quickly oxidizes at temperatures
Further TiN coatings have been employed in orthopedic implant approaching 550 ◦ C, resulting in rapid hard coating wear at higher
materials owing to excellent biological properties [47,87]. The long- temperatures [88].
term clinical events have been performed in patients by using Nowadays, the ternary nitride films (such as TiAlN, CrAlN, and
titanium-nitride-oxide-coated bio-active stents and paclitaxel-eluting TiCrN) and multilayer coatings (such as TiN/TiAlN, TiAlN/VN, ZrN/Cu)
stents. Clinical studies of TiNxOy-coated stents were found suitable for are most preferred over binary thin films owing to their exceptional
cardiovascular purposes. It was also reported that TiN-coated electrodes physio-mechanical properties and resistance to oxidation at high tem­
are used for the treatment of spinal cord injury in neurology, in cardi­ peratures [46,47,88–93]. An et al., [94] studied the stability of Ti2AlN at
ology for ventricular abet devices for patients with heart collapse, and in various temperatures ranging from 700 to 1600 ◦ C. The Ti2AlN was
dentistry for dental implants. The TiN material can be employed to discovered to be extremely stable, with a high-quality microstructure at

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R. Garg et al. Advances in Colloid and Interface Science 330 (2024) 103203

1400 ◦ C and 5 GPa. Kumar et al. fabricated multilayer coatings of zir­ Mo, Ta, and niobium (Nb) using magnetron sputtering. The findings
conium nitrate/copper (ZrN/Cu) over 316 L SS and titanium substrates. from this study suggested that all three of these metals could potentially
The study showed increased crystallinity and hydrophobicity, according serve as suitable thin film materials for NiTi in medical applications
to structural and surface analyses. On titanium substrates, corrosion [102]. Thangavel et al. [104] studied the cytocompatibility of Ag-doped
resistance was significantly increased. The coatings also possessed NiTi coatings on commercially pure titanium substrates formed by
excellent antibacterial activities against P. aeruginosa on both substrates magnetron sputtering. Neonatal human dermal fibroblast cells showed
because of the ion release [46]. the highest level of cell viability. Moreover, the addition of Ag has
increased the corrosion resistance of NiTi. The results also revealed that
2.4. Alloy based materials 3 at.% Ag incorporated NiTi/Ag coatings were viable material for or­
thopedic implants. Wu et al. [105] fabricated the Al–SiO2 coatings on
Low infrared emissivity coatings are frequently needed for aerospace NiTi and stainless steel archwires by magnetron sputtering. No apparent
materials placed in high-temperature environments to limit thermal cytotoxicity was observed indicating good biocompatibility. Moreover,
radiation absorption. Because of its superior mechanical characteristics the coatings over NiTi and SS archwires have provided surface
in high-temperature environments, nickel-based superalloy is the most smoothness and increased the corrosion resistance leading to enhanced
often used material in aerospace. To reduce the emissivity of Ni-based efficiency of orthodontic treatment.
alloys at high temperatures, Sun et al. studied indium tin oxide (ITO)
films. The findings demonstrated that the sample’s emissivity remained 2.5. Ceramic based materials
low at 600 and 700 ◦ C after being annealed, exactly as it had been
before. Superalloy K424 can be coated with ITO film to reduce emis­ Ceramic materials have been used in thin-film thermocouples for
sivity up to 700 ◦ C. In 2004 Yeh et al. discovered a novel multi-element their stronger oxidation resistance and stable chemical structure. The
alloy called high-entropy alloy (HEA) [95]. Because of their high mixing perovskite-like calcium copper titanate-based ceramics (CCTO) have
entropy, they have a lower free energy and better phase stability. The attracted the attention of scientists around the globe for behaving as a
HEA consists of five or more main metal elements in equal or unequal nonohmic material. CCTO thin film is a favorable candidate for utili­
molar ratios that possess versatile properties, such as superior wear zation in a variety of applications including capacitors, microelectronic
resistance, excellent thermal stability, and high tensile strength at devices, antennas, biosensors, microwave devices, and solar panels [3].
ambient and cryogenic temperatures [96,97]. Recently, many studies based on CCTO films have been reported in the
Various studies have been published on HEAs and HEA-based ma­ literature [62,106–109]. Yuan and his team [106] effectively synthe­
terials, which can significantly improve the surface properties of the sized thin films of CCTO on platinized Si wafers using RF magnetron
substrate material. In recent times, refractory high entropy alloys sputtering. Their work underscored the significance of annealing tem­
(comprising elements such as Mo, Nb, Ta, V, W, Ti, Zr, Hf, Cr, and Re) perature in shaping the morphologies and dielectric characteristics of
have garnered rapid interest from researchers owing to their exceptional these films. Notably, the investigation identified two dielectric re­
strength at temperatures reaching 1600 ◦ C. Due to their outstanding laxations occurring at distinct frequency ranges. The low-frequency
attributes in high-temperature environments, these alloy films have relaxation was attributed to interfacial polarization at the electrode/
demonstrated significant potential for applications in diverse areas sample surface, while the high-frequency relaxation was linked to an
including aerospace vehicles, aircraft turbines, solar thermal conversion intrinsic mechanism. In a separate study, Ahmadipour et al. explored the
systems, corrosion-resistant coatings, and diffusion barriers in inte­ impact of RF power fluctuations (ranging from 100 W to 300 W) on the
grated circuit (IC) systems [51,98,99]. Li and colleagues conducted a structural, morphological, and optical attributes of a CCTO thin film
study involving the deposition of a range of TaWTiVCr RHEA films using produced on an ITO/glass substrate within a non-reactive environment
magnetron sputtering techniques. The findings demonstrated that the (argon, Ar). Their analysis utilizing Field-Emission Scanning Electron
Ta24W24Ti16V19Cr17 RHEA film variant displayed impressive mechani­ Microscopy (FESEM) indicated that the deposited films exhibited ho­
cal characteristics, including a hardness measuring 27.54 GPa, a mogeneity, porosity, and a granular structure, with grain sizes spanning
modulus of 274.39 GPa, an average friction coefficient of 0.34, and a 30 to 50 nm. The study also observed an increase in surface roughness
wear rate of 5.01 × 10− 9 mm3/(N⋅mm). These outcomes strongly sug­ from 1.6 to 2.3 nm corresponding to the growth of film grain size, as
gest that the RHEA films possess remarkable wear resistance capabilities corroborated by Atomic Force Microscopy (AFM) investigations.
[100]. Collectively, these findings suggest that by adjusting the strength of RF
Shape memory alloys are being investigated as viable damping ma­ magnetron sputtering, CCTO thin films hold potential for specific ap­
terials for a wide range of MEMS applications [49] In the biomedical plications [3].
field, NiTi shape memory alloy is extensively used for bone plates, Another ceramic material, hydroxyapatite, (Ca10(PO4)6OH2) with a
stents, dental wires, prosthetic joints, and drug delivery systems owing Ca/P ratio of 1.67, belongs to the calcium phosphate family with
to their shape memory effect, fatigue strength and superelasticity chemical and physical characteristics similar to bone tissues. Badea
[48,101–103]. Nonetheless, the introduction of nickel ions into the body et al., 2016 deposited hydroxyapatite coatings on Ti6Al4V alloy using
has been associated with toxic, carcinogenic, and immune-sensitizing magnetron sputtering and also studied the influence of various con­
effects. Consequently, there is a drive to mitigate the release of nickel centrations of Ag and SiC in HA coatings. It was observed that the
ions from NiTi surfaces, while also enhancing its corrosion resistance incorporation of Ag has increased antibacterial properties that help to
and biocompatibility. To address this, researchers have pursued surface reduce the incidence of implant-associated periprosthetic infection
modification strategies employing metallic thin film materials like mo­ whereas SiC was added to enhance film corrosion resistance. HA is
lybdenum (Mo), zirconium (Zr), titanium (Ti), and tantalum (Ta) resistant to resorption and insoluble when in contact with human fluid.
[52,102]. In 2016, Park and colleagues employed DC magnetron sput­ Researchers have also focused on developing HA coatings for metallic
tering to deposit Ta coatings onto NiTi alloy substrates [101]. The out­ implants for use in dentistry and orthopedics. Inorganic antibacterial
comes demonstrated that, unlike a bare NiTi stent, a NiTi stent with a agents such as Ag, Zn, Mn, and Cu have been incorporated into the
substantial Ta coating, at least 10 μm thick, exhibited notably improved calcium phosphate (CaP) phase to attain antibacterial CaP coatings. In
visibility in X-ray images. Furthermore, the application of this thick Ta 2016, Malchikhina and his team reported that the TiO2/HAp bilayer
coating led to the suppression of Ni ion release and the development of a coatings were produced by hybrid methods, i.e., thermal oxidation and
persistent Ta oxide layer, resulting in significantly enhanced in vitro radio frequency magnetron sputtering. The study revealed that CaP
biocompatibility of the NiTi substrate. Another study from 2018, con­ coatings have excellent in vivo biocompatibility since they greatly
ducted by Seifried et al., focused on coating NiTi sheets with thin films of stimulate the fibro integration process [110]. Chernozem and colleagues

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R. Garg et al. Advances in Colloid and Interface Science 330 (2024) 103203

proposed that аP-containing coatings can be deposited within TiO2 quality and human health [114]. Many of these species are created from
nanotubes using RF-magnetron sputtering of the HA target. The study the combustion of fossil fuels, and they have the potential to cause
found that only the HA coating on the NTs had a considerably higher H/ chronic respiratory and pulmonary illnesses, as well as cardiovascular
E and H3/E2 ratio than the NTs and Ti substrate [111]. Furthermore, and lung cancer [115]. Global environmental hazards are primarily
hybrid biocomposites based on TiO2 NTs and HA coating show promise caused by air pollution. It plays a role in the development of respiratory
for usage in bone tissue engineering. Because of their excellent biolog­ diseases, infectious diseases, acute toxic effects, malignancies, repro­
ical qualities, hydroxyapatite (HA) and calcium phosphate (CaP) coat­ ductive abnormalities, and allergies. According to the WHO, exposure to
ings have been widely used in biomedical applications. ambient air pollution causes approximately 4.2 million deaths per year.
The findings of the aforementioned studies on thin films synthesized Furthermore, air pollution harms the environment by interfering with
by the magnetron sputter-coated technique showed that films have good photosynthesis, transpiration, and respiration. They also contaminate
physicochemical properties, anticorrosion and excellent wear resis­ water and soil. They raise the acidity of drinking water and the levels of
tance, and excellent biological behavior. Apart from that, adequate heavy metals including lead, copper, zinc, and cadmium in the water
concentrations of Ag and Cu in thin films produce antibacterial activity [116]. Plumbing installations are destroyed by acidic water, which
and better cellular function, making them an essential biomedical film washes away numerous harmful compounds. They cause metals and
attribute. Moreover, limited studies on CCTO ceramic-based thin films building materials to corrode. Pollutants in the air also act as a catalyst
are available in the literature for its gas sensing application. Overall, it for climate change. The primary issue that must be addressed now is the
can be concluded from this section that each form of thin film has its successful decomposition/mineralization of air pollution. As a result, a
distinct properties dependent on its utilization. new and effective way of eliminating hazardous compounds from the
environment is required.
3. Thin film for environmental sustainability The use of thin film photocatalytic surfaces to clean the air was
explored in an innovative approach [117]. Contaminated air is directed
The sputtering process is governed by a principle in which a source over a photocatalytic surface that is exposed to light. On this surface,
material that is to be deposited onto a substrate is bombarded by ener­ pollutants that have adhered are broken down into compounds that are
getic ions [112]. Most often, these ions are from inert gases, like argon either non-harmful, devoid of odor, or less toxic. Consequently, the
(Ar+). The majority of magnetron sputtering applications use argon as pollutants that have been captured on the surface undergo a process of
their process gas of choice because of its enormous atomic mass, inert degradation, transforming into molecules that are either harmless, lack
reactivity, and reasonably inexpensive price. In a sputtering process, the odor, or are less hazardous, [117,118] TiO2 thin films put onto window
inert gas ions strike the target with such force that target atoms are glass are suitable for air filtration and self-cleaning applications. In a
removed (a technique known as sputtering), and these target atoms then similar study reported by [119] indoor/outdoor air pollution, volatile
consolidate on the substrate as a thin layer with a composition compa­ organic compounds (VOCs) degradation was carried out on sputtered
rable to that of the target material. Although the fundamental principle CuxO/TiO2 on polyester (PES) cloth under low-intensity visible light.
of operation appears to be straightforward, the actual mechanics Photoactive CuxO/TiO2 coatings were produced using magnetron sput­
involved in sputtering are rather complicated. Thin film deposition tering at different power levels and modes, including direct-current
sputtering in its different forms provides advantages such as film magnetron sputtering and High-Power Impulse magnetron sputtering.
adhesion strength and superior surface finish, high film adherence, and These coatings were then subjected to irradiation by low-intensity
good step or coverage. It is also possible to do simultaneous double-sided visible light. This illumination triggered a photocatalytic reaction in
coating with the right mechanical arrangement. This section will explore the sputtered photocatalysts, leading to the degradation of various
various applications of the sputtered-coated materials vis-à-vis envi­ VOCs. Simultaneously, the exposure to light hindered the growth of
ronmental sustainability, air purification, water treatment and adsorp­ bacteria. O’Keeffe et al. [120] proposed a technique for generating
tion, decontamination, and new directions and prospects. doped TiO2 films known for their efficacy in eliminating nitrogen di­
According to the United States Environmental Protection Agency (US oxide (NO2) from airflow, specifically when exposed to visible light.
EPA), sustainability encompasses the conscious effort to protect land, When compared to conventional commercial materials, these multi-
air, water, and ecosystem and utilize it to meet today’s needs without element doped TiO2 sheets have a surprising ability to remove NO2.
jeopardizing the future. It is described holistically as a decisive action to
harness the environmental resources in an economically viable manner 3.2. Photocatalytic degradation application
advantageous to human well-being and resultantly socially just in the
long run [113]. Sustainable development goals (SDGs) in terms of clean water and
Environmental sustainability is the obligation to conserve natural sanitation, life below water, sustainable cities and environment as well
resources and protect global ecosystems for current and future health as good health and well-being would be nebulous if a sustainable
and well-being. It is also possible to define it as “ensuring that human approach is not tailored towards wastewater treatment via an effective
civilization operates within ecological boundaries. It is critical to realize technique. Water has been identified as a life essential. However, studies
that humans have boundaries and understand where those boundaries have shown that 844 million people still lack access to clean water and
are to maintain sustainability. As a result of various environmental is­ the leading cause of death of children under age 5 could be attributed to
sues, there is a growing interest in the fabrication of thin films for diseases surrounding contaminated water. Hence without access to
environmental sustainability and application in remediation. Herein are clean water, life is at risk from preventable diseases (WHO & United
some of the studies carried out by various researchers on the application Nations International Children’s Emergency Fund (UNICEF), 2021)
of sputter-coated materials to environmental sustainability as related to [121]. Although various materials have been explored in the treatment
air purification and water treatment unraveled in the various sub- of water, the most widely used is activated carbon. However, this suffers
sections under environmental sustainability. some drawbacks based on its poor regeneration efficiency and diffi­
culties of separating it from the solution [122,123] This review, criti­
3.1. Purification of Air cally examined photocatalytic degradation as an effective water
treatment technique using sputter-coated thin film materials. Following
The World Health Organization (WHO) defines air pollution as the this section is the sputter thin film materials’ application in water
presence of both organic and inorganic chemical pollutants, as well as treatment via the photocatalytic degradation technique.
gaseous substances, pathogens, and particulate matter, in either outdoor
or indoor air. This contamination can have detrimental effects on air

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3.2.1. Wastewater remediation via photocatalytic degradation characterized by a band gap of 2.6 eV. Its properties encompass excep­
Photocatalytic degradation is a potentially sustainable remediation tional traits, including efficient absorption of solar radiation, notable
approach for reducing contaminants most especially the endocrine photostability, a relatively reduced indirect band gap, inert chemical
disruptive compounds among which dyes and other emerging contam­ behavior, lack of toxicity, remarkable thermal and acidic stability, and a
inants are categorized [124,125]. In today’s world, materials with high oxidation potential present in its valence band holes. Various
tunable qualities and flexible device construction are critical in the fields deposition methods are employed for generating WO3 films, including
of energy and the environment [126]. Based on the diverse features and template-assisted techniques, sol-gel processes, anodic oxidation, ther­
flexibility, photocatalysis has been identified as one of the few strategies mal evaporation, CVD, hydrothermal synthesis, reactive magnetron
for tackling energy and environmental challenges that could be flexible sputtering, and chemical spray pyrolysis. Given these attributes, WO3
for industrial-scale applications. Photocatalysis has been used in a va­ emerges as a promising material with potential applications in photo­
riety of applications, including pollutant degradation, water splitting, catalysis, photoelectrocatalysis, and electrocatalysis. Singh et al. inves­
CO2 and N2 reductions, and microbe inactivation [124,127]. The sput­ tigated nanostructured TiO2 thin films prepared by RF for photocatalytic
tering approach was used to create a variety of thin film photocatalysts degradation of MB.
suited for environmental cleanup. The synthesis of TiO2 thin films using RF magnetron sputtering was
Generally, sputter-coated thin film materials have found applications accompanied by thermal annealing. The modification in various pa­
for photocatalytic dye degradation. The usual procedure for photo­ rameters such as morphology, photocatalytic, and optical properties
catalytic degradation through the sputter-coated thin film materials through photocatalytic degradation based on the thickness of the films
involves the immersion of the thin films in the water contaminants like has been determined. The decrease in the particle size from 52 nm to 10
the dye solutions including Rhodamine-B (Rh–B), MB, etc. The mixture nm over the AFM studies through the increase in film thickness, where
within the glass tube was positioned in a dark environment to attain a the anatase phase of the TiO2 is confirmed through the Raman studies
state of equilibrium between adsorption and desorption. Following this which are embedded in the amorphous phase of TiO2. Fig. 5a(i-v) shows
is the light irradiation of the samples either using sunlight or artificial AFM images of the RF sputtered TiO2 thin film samples T2, T4, T8, and
light sources, and the samples have been subjected to withdrawal at T10 annealed at 600 ֩C, which reveal the presence of nanoparticles. The
period intervals of time, the UV-absorption data along with their pho­ T4 photocatalyst i.e., 40 nm thick TiO2 film tends to exhibit complete
tocatalytic efficiencies are majorly determined over this work. The methylene blue degradation (2.1 μM) in just 45 min which is majorly
degradation of pollutants occurs due to the presence of •OH, h+, •O2− , obtained due to its narrow bandgap and enhanced visible light absorp­
and e− radicals towards photocatalytic processes. The effect of the tion as shown in Fig. 5a(ii). The photocatalytic efficiency of the photo­
thickness, pressures of sputtering, time of sputter coating, temperature catalysts over 45 min of sunlight irradiation is shown in Fig. 5a(v). The
effect, scavenger effect, etc. is majorly considered in photocatalytic dye annealing over 600 ֩C leads to dewetting which leads to the formation of
degradation over sputter-coated thin film materials. Other operational nanoislands over the anisotropic shapes over the surface aggregation of
parameters of interest are the effects of reaction time, initial concen­ the TiO2 nanoparticles with its schematic illustration as shown in Fig. 5
tration, pH, and photocatalyst dosage. The following metallic oxide (b) [130].
nanoparticles developed via sputtering technique have found applica­ Subrahmanyam et al. demonstrated the deposition of the TiO2 over
tion in photocatalytic degradation of dyes and other emerging con­ the thin film layers through the sol-gel, DC sputtering is used for the
taminants which are categorized as endocrine disruptive compounds deposition of Ag particles over the TiO2 surface. Surface modification is
(EDC) among which dyes have been spotlighted: found to be a potential technique to achieve plasmonic-assisted sunlight-
Titanium dioxide nanoparticles (TiO2 NPs) are well-known as one of driven photocatalyst synthesis. The existence of the Ag particles over the
the most efficient photocatalysts in a variety of applications and have TiO2 surface is found to be in the metallic state, and the photocatalytic
also been investigated as a suspended powder in water remediation activity of the Ag-modified TiO2 thin film is comparatively higher than
[128]. Their use in thin films has recently been identified as a potential that of the unmodified surface. The degradation of the Rh–B, the
alternative to time-consuming filtration techniques [120]. TiO2 thin surface-modified Ag/TiO2 thin films deposited by DC magnetron sput­
films find extensive application in various domains such as environ­ tering over the 25 ◦ C, with the sol-gel, assisted TiO2 thin films and
mental remediation, self-cleaning technologies for surfaces like win­ annealed at 570 K in a vacuum. The comparison of the variation of the
dows, building exteriors, and textiles, water splitting processes, absorption ranges and the irradiation light source was majorly found to
antimicrobial functionalities, and biomedical applications. While there be the important aspects and their pH effect on the rate constants has
exist numerous approaches for fabricating TiO2 thin films, including been visualized. The Ag/TiO2 films tend to exhibit significantly
wet-chemical synthesis methods, CVD, and PVD, the latter techniques, enhanced photocatalytic efficiency, the deposition of the Ag over the
classified as PVD, offer advantages in terms of precise control over film TiO2 films will be for 15 s referred to as T2 resulting in 2.45 times su­
uniformity and thickness, as well as strong film adhesion. The photo­ perior efficiency in comparison to that of the pure TiO2 [131].
catalytic performance of the TiO2 layer to be deposited, on the other Sahu et al. demonstrated the nano thin film synthesis of the CuO
hand, is greatly influenced by the PVD process used. majorly deposited through the reactive DC magnetron sputtering tech­
When compared to other semiconductors, ZnO is a promising pro­ nique. The effect of substrate temperature variation over the photo­
spective photocatalyst due to its broad direct band gap (3.37 eV), catalytic, optical, morphological as well as structural properties of the
chemical stability, ease of production, low cost, substantial excitation material has been visualized. The decrease in the crystalline size of the
binding energy (60 meV), outstanding optical characteristics, and low CuO thin films is majorly observed over the increase in the substrate
toxicity [129]. Numerous techniques have been documented for crafting temperature. The fabricated CuO thin film nanostructures have worked
ZnO photoelectrodes, encompassing methods such as CVD, pulsed laser efficiently in the removal of MB and MO dye over 40 min in sunlight
deposition (PLD), chemical bath deposition, hydrothermal synthesis, illumination, as well as the reduction of the 4-NP (4-nitrophenol) in just
spray pyrolysis, RF sputtering, and sol-gel techniques. In a study by 15 min with an efficiency of 87% whereas the addition of cupric nitrate
Alfaro Cruz et al., ZnO films were generated through RF magnetron (CN) resulted in 55% and the addition of tertiary-butyl alcohol (TBA),
sputtering and subjected to annealing in air, argon, and nitrogen at­ decreases it to 7.6% and that of the addition of formic acid (HCOOH)
mospheres. Remarkably, the films annealed in air exhibited robust leads to 63%. This prominent decrease majorly determines that the
photocatalytic activity. This outcome could potentially be attributed to hydroxyl radicals highly affect the removal of the MB from water. The
the presence of noticeable oxygen deficiencies, which act as active sites, addition of the NaBH4 solution to the 4-NP leads to enhanced reduction,
thereby enhancing reaction efficiency. the smaller crystalline size of the material their improved utilization of
WO3 stands out as an n-type material active within the visible region, the sunlight, and the larger surface roughness leads to the efficient

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Fig. 5. (a) AFM images of the prepared TiO2 thin film samples (i) T2, (ii) T4, (iii) T8 and (iv) T10 showing the presence of nanoparticles, (v) Variation of pho­
tocatalytic efficiency of the thin film photocatalysts with sun light irradiation time, and (b) Schematic illustration demonstrating the photocatalytic methylene blue
degradation along with the efficiency and morphology [130]. (For interpretation of the references to color in this figure legend, the reader is referred to the web
version of this article.)

suppression of charge recombination, and the material possesses higher surface area of the sputtered films is determined over the magnitude of
stability and reusability towards the water purification kinetics [132]. ~50 m2g-1, and 64% degradation efficiency to CO2 in consideration of
Andriyanti et al. demonstrated the active sites as well as the most that of the reference TiO2 powder materials. This work majorly controls
stable semiconducting material-based TiO2 thin films majorly synthe­ the electrical, optical, structural, and morphological aspects of catalyst
sized through the DC sputtering technique over the stainless-steel sur­ preparation [134].
face. The improvement of the photocatalytic activity of the TiO2 thin Dustgeer et al. developed the Cu2O thin films that were deposited
films was found on the 10.5% weight loading of silver (Ag) nanoparticles through the DC magnetron sputtering along with the variation of the
over the TiO2 surface, the MB dye absorption efficiency of TiO2 and the substrate temperature ranging from 25 to 300 ◦ C, the Cu2O@200 ◦ C
subsequent TiO2-Ag is found to be 17.5% and 76.74% over the sunlight photocatalyst resulted in 100% photocatalytic degradation of MB dye
irradiation whereas that under UV light is 35% and 64.27% respectively from the wastewater. The surface roughness and the crystalline sizes,
within the deposition time of 2 min. The excess loading of Ag over the highly affect the efficiency, as shown in Fig. 6 (a-b). The pseudo-order
TiO2 thin films blocks the photon from activating TiO2, which inhibits as equations of first (0.95-0.96) and second (0.88-0.94) R2 values
well as reduces the % degradation of the dye [133]. Dumitriu. et al. majorly suggest the domination of the chemisorption mechanism for the
developed TiO2 thin films through the DC reactive sputtering technique, MB dye and their possible mechanism Fig. 6(c). The antibacterial ac­
which is majorly supported using different support materials such as tivity of these composite exhibited behavior against Escherichia coli,
glass, alumina, Si, and glass coating over the indium‑tin oxide substrate. which majorly creates a possibility towards its application leading to the
The degradation of the phenol dye and their respective photocatalytic touch screen appliances Fig. 6(d), leading to the introduction of the
properties, which is mineralized and obtained through the Ar-H2O auto-response methodology in reducing the rate of microbial contami­
mixture over the reactive gases. The catalytic efficiency across the given nation over the surfaces [135].

Fig. 6. (a) AFM analysis of Cu2O@200 ◦ C, (b) Ra and Rqms surface roughness of single-phase Cu2O thin films over various temperatures, (c) Proposed photocatalytic
degradation mechanism of MB dye, and (d) Viability percentage loss of the single-phase Cu2O thin films with the variation of substrate temperatures, respec­
tively [135].

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Loh. et al., demonstrated the intercalation among the oxygen com­ superior surface roughness created through the deposition conditions
positions over the In2O3 thin films, their electronic as well as the ma­ leads to more adsorption states, and thereby improves the MB dye
terial characterization as shown in Fig. 7(a) which correlates the decomposition [137].
Rhodamine-B dye degradation over white light irradiation. The degra­ The same groups have further demonstrated the effect of the depo­
dation increases with an increase in indium content up to 4 times in sition conditions of TiO2-ZnO thin films over their consecutive photo­
comparison to that of the pre-introduced oxidizing material i.e., H2O2. catalytic activity is thoroughly determined, where the deposition of the
The increase in the oxygen vacancies has been thoroughly confirmed by samples through the DC reactive magnetron sputtering is carried out
the XPS studies which majorly correspond to the ionizing effects as using (Ti)90-(Zn)10 alloy target, which was further annealed at 500 ◦ C
demonstrated along with their Hall studies corresponding to the ionizing under air. The physical properties of the films are majorly based on the
effect as shown in Fig. 7. The crystal structure of the In64O64 sub-oxide O2/Ar gas ratios and the working pressures of the films. The superior dye
II is demonstrated in Fig. 7(a) which on the usage of black silicon sub­ degradation efficiency of 44% was observed with the sample deposited
strate material leads to anodic peak shift from -2000 mV to -15,000 mV over at 3 mTorr pressure and with an O2/Ar gas ratio of 10:90. The blue
respectively, and an increase in the dye degradation up to 60% on shift in the optical band-gap is majorly observed wherein the lower
baking at 250 ◦ C leads to higher photodegradation efficiency of 70% as electronic states are occupied over the conduction band over the doped
shown in Fig. 7(b), but don’t exhibit the activity of CO2 reduction due to semiconducting material, the increase in the pressure to 3 mTorr
the lack of OH-Ov vacancies coupled sites [136]. resulted in higher roughness and uniform dispersion over the semi­
The removal of hydrogen peroxide over the RhB-dye majorly leads to conductor surface [137]. Depicted in Table 2 are lists of various studies
an increase in the photodegradation efficiency. The synthesis and carried out on water treatment via photocatalytic degradation using
fabrication of Ag-Cu2O-CuO nanocomposite through the RF magnetron sputter-coated thin materials.
sputtering have been thoroughly investigated by Sahu et al. The
enhanced photocatalytic degradation efficiency is majorly obtained
from the Ag-Cu2O-CuO (T3) nanocomposite with higher Ag loading 3.3. Adsorption application
which possesses major charge transfer, better charge carrier separation
efficiency, exposed active sites, and extended light absorption as shown Adsorption is a phenomenon wherein substances (adsorbate) tran­
in Fig. 8a-d. The active radicals responsible for the superior activity and sition from a gas or liquid state to a compact phase, either solid or liquid,
their photocatalytic mechanism are thoroughly investigated, and their forming a thin monomolecular layer on the surface of another material
increased efficiency over various chemicals resulted in a maximum (substrate). [148]. Adsorption is effective with a very simple setup,
reduction over the TBA chemical which possesses •OH radicals as the making it technically possible, socially acceptable, and useful for
active radicals towards the MB degradation [132]. removing a wide range of toxins from wastewater. Previous studies have
The effect of sputtering power, the thickness of the films their demonstrated the effectiveness of the adsorption process for the uptake
sputtering working pressures over the adsorption powers, and the of a variety of pollutants and other emerging contaminants using acti­
consecutive photocatalytic activity of the MoO3 thin films over dye vated carbon [149], clay [150], zeolites [151], nanoparticles, and
degradation is majorly explained by Perez-Gonzalez. et al. The basic composite nanomaterials [123,152]. However, very few reports have
preparation of MoO3 thin films is majorly carried out through the sputter been documented on the use of sputter-coated thin film materials [153].
coating at room temperature through RF reactive magnetron sputtering Low starting cost, easy operation, and great efficiency are all inherent
which further leads to annelation over 500 ◦ C in air. The superior advantages of the adsorption technique over all other conventional
adsorption and photocatalytic efficiency are obtained over the W12 methods which have also served as compelling attractions for global
sample wherein the deposition at 60 W under a pressure of 12 mTorr researchers.
with a thickness of 400 nm for the methylene blue dye removal (53%) The process of adsorption can be categorized into two groups based
through adsorption and degradation parameters are shown in Fig. 9 on the specific adsorption forces involved: physical adsorption and
wherein the methylene blue dye degradation takes place over the dark chemical adsorption. Van der Waals forces interact between molecules
condition as shown in Fig. 9(a). The photoacoustic spectroscopy studies to cause physical adsorption, such as when activated carbon is used to
majorly confirm the adsorption of the MB dye over the catalytic surface adsorb gas. Physical adsorption generally occurs at lower temperatures,
as shown in Fig. 9(b), and their strong absorption with a hypsochromic displaying a rapid rate of adsorption, minimal heat generation, and
shift indicating their aggregation over the surface of MoO3 thin films lacking selectivity [123]. The molecular structure of the adsorbate re­
with α and β phases and their subsequent metachromatic effect over the mains largely unchanged due to weak intermolecular interactions. This
surface of the dye molecules. This study further determines that the results in low adsorption energy, rendering the adsorbed substance
relatively easy to detach [154]. Chemical adsorption however occurs as

Fig. 7. (a) Lattice parameters of In64O64 and their relaxation over the sub-oxide I and contracts the sub-oxide II. (b) The removal of hydrogen peroxide over the Rh-
dye majorly leads to an increase in the photodegradation efficiency [136].

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R. Garg et al. Advances in Colloid and Interface Science 330 (2024) 103203

Fig. 8. (a) Fabrication process of the photocatalyst, (b) band gap position of the Ag-Cu2O-CuO composites, (c) Photocatalytic degradation mechanism over the Ag-
Cu2O-CuO nanocomposite thin film, (d) bar diagram representing the photocatalytic degradation efficiency under various scavengers using thin film of Ag-Cu2O-CuO
nanocomposite [132].

Fig. 9. Adsorption and photocatalytic degradation of MB dye over the MoO3 film surface (a) dark conditions, (b) destruction of the dye over the MoO3 film sur­
face [137].

a result of chemical bonding. Chemical bonds are created and broken signposted in this section.
during the process of chemical adsorption. This kind of adsorption in­ Zhang [155] conducted a study focusing on the adsorption and
volves valence forces with a change in electronic state and the desorp­ photo-desorption of oxygen on the surface and crystallite interface of
tion would always require higher energy and alteration of chemical sputtered ZnO films. Oxygen adsorption was induced by an electric field
nature. Adsorption could involve different interfaces such as solid-gas, on the polycrystalline film with strong photoresponses obtained via UV
liquid-gas, solid-liquid, solid-solid, and liquid-liquid. Advantageously, light irradiation. To stabilize the surface structure of ZnO film, N2
in all the few studies on adsorption using sputter-coated thin film ma­ doping was carried which eventually enhanced the elimination of sur­
terials, they have found application in solid-liquid, solid-gas, and liquid- face adsorption. The study’s findings indicated that the conductivity of
liquid interfaces. the sputtered polycrystalline ZnO film is primarily influenced by surface
and inter-crystalline depletion barriers caused by ionized adsorbates.
3.3.1. Other related studies on adsorption This study is quite different from the general liquid-phase adsorption.
Although there are reports of applications of sputter-coated materials Boyd et al. [156] investigated protein adsorption using surface-MALDI-
in photocatalytic degradation, however, to the best of our knowledge, MS developed by a novel radio frequency magnetron sputtering method.
there are scanty and very few research works on liquid-phase and gas- The successful coating was confirmed by both the XRD and XPS ana­
phase adsorption using sputter-coated materials hence the need to lyses. The focus of the study was to utilize surface MALDI to detect and
close up the research gap in this area. Limited studies carried out by identify protein adsorbed to calcium phosphate/ TiO2 hybrid coatings
researchers on the application of sputtered-coated materials are surfaces from Fetal bovine serum (FBS) solution. The work was

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Table 2
Photocatalytic dye degradation of various sputter-coated thin film materials.
No Photocatalysts Adsorbate in the water Type Degradation efficiency Ref

1 T4 MB RF 2.1 μM in 45 min [130]

2 T2 RhB DC 8.04 x 1013cm-2s-1 [131]
3 CuO-D3 MB & MO DC 87% [132]
4 Ag-TiO2 RhB Sputtering 29.5% [138]
5 Ag-TiO2-80 nm MB DC 93% [133]
6 TiO2 – x Phenol transformation, DC 50 m2g− 1 [134]
7 Cu2O@200 ◦ C MB DC 100% [135]
8 CuO–TiO2/Rgo MO DC Complete degradation in 13 h [139]
9 In2O3@ Si substrate RhB DC 70% [136]
10 N-doped TiO2 (0.72% of N) C.I. Reactive Blue 19 Reactive magnetron 1st order rate constant-5.1 × 10-5 [140]
sputtering
11 TiO2 3-nitrobenezenesulfonic acid (3- RF 4.5 × 10-5 M h-1 [141]
NBSA)
12 ZnO- 200 nm 2-chlorophenol-pH -3, 112-W light RF 0.0056 min-1 [142]
13 Ag-TiO2 (TA-5) MB Atom beam Co-sputtering 63% [130]
14 Ag-TiO2-600 ◦ C MB Atom beam sputtering 80% [143]
15 Zn-TiO2-300 ◦ C Phenol red dye, 100 W, 60 min RF ~58% [144]
16 Ag/Ag2O-TiO2 RhB DC 65.2% [143]
17 MoO3 MB RF 53% [137]
18 TiO2 supported on stainless steel MB, RhB, MO, DC 18%, 17.2%, & 11.2% respectively [145]
after 1 h
19 BiVO4 RhB Pulsed-DC 29% for 7 h [146]
20 PVDF-HFP (polyvinylidene fluoride) MB Magnetron-sputter Coating 76% for 200 min [147]
hexafluoropropylene

investigated to mimic cell adhesion and detect common proteins. The typical adsorption of Pb(II) from synthetic wastewater using CuO
study was a good take-off for understanding the biocompatibility of hard nanoparticles synthesized by sputtering method. In this study, CuO was
tissue implants via the identification of major protein adsorbates. The synthesized by the reactive magnetron technique, and this showed
outcome of the study indicated that surface-MALDI-MS is an important improved properties compared to other CuO nanoparticles synthesized
tool for studying the dynamic nature of protein adsorption to bioceramic using other techniques, particularly in terms of surface properties.
coating and additional studies were recommended due to the complexity Typically, as depicted in Fig. 10(a-d), operational parameters investi­
of the system. gated were effects of pH, adsorbent dose, contact time, and initial metal
A notable study carried out on liquid-phase adsorption using sput­ ions concentration. Considering the operational parameter on the effect
tering material was reported by Verma et al. [157] who investigated the of pH, Verma and co-worker observed that the pH of the system affects

Fig. 10. Typical operational parameters on (a) effect of pH (b) Adsorbent dosage (c) contact time (d) initial concentration on adsorptive removal of Pb(II) and
adsorption capacity with sputter-coated CuO nanoparticles [157].

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R. Garg et al. Advances in Colloid and Interface Science 330 (2024) 103203

the chemistry of the adsorption process, and the best adsorption of Pb(II) factors are examined to determine the ideal circumstances needed for
was attained at a pH 6 with an increase in the percentage removal ef­ the highest percentage of removal of pollutants. The effects of pH,
ficiency from 11.4% to 76.50% and adsorption capacity increasing from contact time, temperature, and adsorbent dosage are the most often
13.2 mg/g to 95.62 mg/g. Consequently, the adsorbent dose affects the researched operating parameters.
availability of the binding sites for adsorption, and from their study, the Effect of pH: This operational factor majorly influences the chem­
percentage removal efficiency increased from 46.08% to 95.86% as the istry of the adsorption process, electrostatic competition, degree of
adsorbent dosage of CuO nanoparticles increased from 0.1 g/L to 2 g/L ionization, charge balance ratio, and the point of zero charge (pzc) of the
and maximally to 98.96% as the dose increased to 6 gL-1. From the effect adsorbent [123,161]. The pH adjustment is done using HCl and NaOH as
of contact time, as reported in Fig. 10c, a rapid adsorption process was most adsorption process is carried out at a pH that will not influence the
achieved at 60 min with 93.42% removal efficiency using CuO due to adsorbate precipitation [162]. The direct relationship between the pH
vacant site availability and the existence of a great concentration and pzc is on the condition that if the pH values are greater than pHpzc,
gradient between adsorbate-adsorbent phase, and eventually equilib­ the charges on the surface of the adsorbent will be considered positive
rium attained at 180 min with 96.22% Pb(II) removal. A large surface thus favoring the adsorption of anionic contaminants [163]. Cationic
area of CuO of 82.82 m2/g further enhanced its adsorptive capacity with contaminants will be more likely to be absorbed if the pH is greater than
99.73% removal efficiency reported at 10 ppm initial Pb(II) concen­ pHpzc, which indicates that the adsorbent’s surface is negatively
tration. The equilibrium data exhibited a more accurate fit with the charged [164,165]. In the study focused on Pb(II) adsorption onto CuO
Langmuir isotherm model, indicating a monolayer adsorption capacity synthesized through the sputtering technique, the adsorption capacity
of 37.027 mg/g, which surpassed the capacities reported in most pre­ exhibited an increase from 11.14% to 76.50%, and from 13.2 to 95.62
vious investigations. The kinetic data were most appropriately described mg/g, as the solution’s pH escalated from 2 to 6, respectively. The
by the Pseudo-second model, and the adsorption process was deter­ optimal pH condition was identified as 6, resulting in an adsorption
mined to be thermodynamically feasible. efficiency of 76.5% and a capacity of 95.625 mgg-1 [157].
Via the sputtering technique, Miao et al. [158] reported on an elec­ Effect of Adsorbent Dosage: In the sorption process, the adsorbent
trospun self-standing membrane for water remediation. In this study, dosage is also crucial [166]. Numerous agro-wastes have been physically
fibers made of hierarchical SiO2@-AlOOH (Boehmite) core/sheath using characterized, and it was shown that they contain mesopores and
electrospinning and hydrothermal reaction were created. The SiO2 fiber macropores that operate as adsorption sites [123,167]. If the adsorbent
membrane’s ability to adsorb organic dyes and microorganisms was concentration rises, more active sites for adsorption are said to be pre­
greatly enhanced by the uniform adsorption of -AlOOH (Boehmite) sent on the adsorbent. As a result, the adsorption capacity increases in
nanoplatelets on its surface. The resulting self-standing membrane direct proportion to the adsorbent dose [168]. In other instances,
demonstrated excellent flexibility and ease of handling and retrieval. though, increasing the adsorbent dose may result in a decrease in
This attribute positions it as a promising material for water treatment adsorption efficiency. This phenomenon can be attributed to the po­
applications, especially in comparison to traditional nanoparticle ad­ tential interference arising from interactions between the adsorbent and
sorbents. In a related work, Khraisheh et al., (2004) [159], described the the adsorbate, potentially leading to a reduction in active sites on the
use of raw and modified diatomite in the treatment of wastewater adsorbent’s surface [163]. To assess the influence of adsorbent dosage, a
containing heavy metals. The adsorbent surface area increased 2.4 times graph plotting adsorbent dose (in gL-1) against removal efficiency (in %)
after manganese oxide (0.38 mg/g) was applied to the diatomite surface. can be generated.
Diatomite has a better capacity than untreated diatomite to remove Effect of Contact Time: To accurately determine the moment of
Pb2+, Cu2+, and Cd2+ from water, according to equilibrium tests. equilibrium attainment during the sorption process, the influence of
Furthermore, the enhancement of Mn-adsorption diatomite’s capacity contact time stands as a pivotal operational parameter. It wields control
was achieved by minimizing the deposition of manganese oxides on its over the efficacy of the process, thereby impacting its economic viability
surface. To examine the influence of heterogeneity, modification, and [169,170]. Through the utilization of a UV–Vis spectrophotometer, al­
diatomite frustule variations on the adsorption process, electronic mi­ terations in residual pollutants are tracked and documented at varying
croscopy was employed. Two main types of diatomite were observed: time intervals until equilibrium is achieved, facilitating the elucidation
centric and pennate varieties. The scanning micrographs also revealed of the impact of contact time [171]. A shorter duration required to reach
the presence of the birnessite structure of manganese oxides, distin­ equilibrium signifies that pollutant molecules migrate from the bulk to
guished by its plate-like crystal arrangement. Notably, the treated the inner and outer surfaces of the adsorbents in a swift manner [172].
manganese-improved filtration characteristics of diatomite were sub­ An increased contact time, attributed to the presence of numerous
stantially improved, and the adsorption kinetics supported the effec­ available active sites on the adsorbent surface, bolsters the efficiency of
tiveness of the chemical treatment. adsorption [173]. A plot depicting percentage removal (%) against time
Similarly, in the realm of bio-based materials, researchers have (t) is generated to analyze the influence of contact time.
discovered the advantages of utilizing nano-porous aerogels for the Effect of Temperature: Given its vital role in pollutant adsorption
production of lightweight materials possessing high surface areas. A systems, the influence of temperature stands as a pivotal operational
particular study focused on adopting a top-down approach to create factor that is commonly investigated. This is attributed to the direct
aerogels. This involved coating delignified wood, also known as nano impact of solution temperature on the expansiveness of adsorbents, the
wood, with a chitosan-cyclodextrin co-polymer. The primary goal was to solid/liquid interface, and the mobility of ions [174]. This attribute of
alter the surface chemistry for potential application in water treatment, adsorption holds significance, as elevated temperatures often translate
particularly in capturing microcystin-LR. After the coating process, the to an augmentation of adsorption sites and thinner boundary layers
resulting nanowood structure displayed a porosity of 75%, an impres­ surrounding adsorbents [175]. To examine the influence of temperature
sive water swelling capacity of up to 339%, and an ability to adsorb on pollutant uptake, an initial concentration (mgL-1) versus percentage
microcystin-LR at a rate of 0.12 mg/g [160]. removal (%) plot can be employed. It’s worth noting that increasing
temperatures may diminish the effectiveness of adsorption due to a
3.3.2. Operational parameters for adsorption reduction in the adsorptive forces between active sites on the adsorbent
In studies involving the use of sputter-coated thin film for liquid- surface and pollutant species [168].
phase adsorption, relevant operational parameters affecting the
adsorption process as imperative to researchers were investigated 3.3.3. Isotherm, kinetics, and thermodynamics modeling of adsorption
among which are: the effect of pH, initial concentration, contact time, Relevance for data obtained in most adsorption studies is derived
adsorbent dosage, and temperature. In practice, several operational from the isotherm and kinetics and thermodynamics modeling. Table 4

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depicts the most widely used adsorption models for the determination of radioactive substances either in municipal water or wastewater have
the quantity of the contaminants adsorbed, and the rate and mechanism caused stumbling blocks to the actualization of these goals. Therefore,
of the process. Also, the thermodynamics parameters help in actualizing the removal of radioactive substances from water requires the use of
the spontaneity, feasibility, nature, and energy involved in the seques­ reliable and efficient techniques for remediating radioisotopes [177].
tration process. Some equations can be used at equilibrium to quantify Conventional decontamination or treatment approaches encompass
the amount of substance attached to the surface given the concentration techniques such as ion exchange, chemical precipitation, thermal
in the fluid. Since temperature is one of the most significant environ­ evaporation, and the utilization of membranes either in isolation or in
mental elements affecting adsorption, these equations—of which the conjunction with other physicochemical methods to effectively elimi­
most well-known are the Langmuir and Freundlich equations—are nate radionuclides.
referred to as isotherms. Adsorption is effective with a very simple setup, Polyvinylidene fluoride (PVDF) membranes were synthesized using
making it technically possible, socially acceptable, and useful for phase inversion with the incorporation of CO2 as a non-solvent additive.
removing a wide range of toxins from wastewater [152]. Previous These membranes were employed for the dual purpose of desalinating
studies have demonstrated the effectiveness of the adsorption process and decontaminating modeled nuclear wastewater. The composition of
for the uptake of a variety of pollutants and other emerging contami­ the polymer (concentration) was varied across three levels (10%, 12.5%,
nants using activated carbon [149], clay [150], zeolites [151], nano­ and 15%), while the CO2 concentrations in the coagulation bath were
particles, and composite nanomaterials [123,153,154]. However, very adjusted at different levels during the phase inversion process. The most
few reports have been documented on the use of sputter-coated thin film effective membranes, as determined by the experiment, were selected
materials in liquid-phase adsorption. Low starting cost, easy operation, for desalinating saline aqueous solutions and decontaminating simu­
and great efficiency are all inherent advantages of the adsorption tech­ lated nuclear wastewater using a membrane distillation technique, with
nique over all other conventional methods which have also served as two configurations known as DCMD (Direct Contact Membrane Distil­
compelling attractions for global researchers. The rate and mechanism lation) and AGMD (Air Gap Membrane Distillation). All the chosen
of the adsorption process are established by the kinetic studies, the membranes exhibited high rejection rates coupled with acceptable
isotherm models help in describing the degree of towards adsorbent permeate fluxes, resulting in a practically infinite decontamination
surfaces, while the feasibility, and spontaneity, as well as the nature of factor. This innovative approach utilizes CO2 dissolved in water as a
the adsorption process, are established by the thermodynamics studies. coagulation medium during membrane fabrication, mitigating the po­
The use of adsorption kinetics, isotherm, and thermodynamics models tential negative environmental impact associated with the use of toxic
are mostly found in liquid phase adsorption. Typically, the study carried non-solvents in the coagulation bath. This method presents a positive
out by Verma et al. [157] revealed the application of these models. The utilization of carbon dioxide, contributing to the reduction of adverse
study found that the kinetic data were best fitted to Pseudo-second order environmental effects connected to membrane production, marking a
and the mechanism was pore diffusion governed. Also, the adsorption significant stride towards sustainability. [177].
process was thermodynamically feasible and spontaneous based on the In developed nations, graphite crucibles coated with yttria are
values of negative values of Gibb’s free energy while the heat content commonly employed as containers for molten refractory and radioactive
was an endothermic and positive degree of randomness of the system. metals such as uranium and plutonium. However, due to repeated
thermal cycles, the coated layer often sustains damage in the form of
3.4. Decontamination of chemicals cracking and peeling. Consequently, it becomes crucial to remove this
layer from the graphite surface to ensure the crucible’s reusability and to
In recent times, the use of thin films to decontaminate chemicals or facilitate the decontamination of radioactive waste. In this context, ul­
enhance the physicochemical characteristics of materials is ubiquitous. trasound was utilized as a non-destructive decontamination technique to
Generally, membranes from composites, organic or inorganic polymeric dissolve the coated graphite, thereby facilitating the recycling of the
materials have been fabricated into flat sheets or hollow fibers garnished graphite substrate. By identifying optimal conditions, including factors
with multilayered, asymmetric, symmetric, or cross-sectional structures. such as acid strength (8 M), temperature (45 ◦ C), frequency (30 kHz),
To date, several techniques have been used for fabricating films or and power density (8 W/cm2), researchers achieved the highest disso­
membranes, these are sol-gel processes, polymer phase separation, lution rate of graphite (52%) within 30 min. The introduction of an
interfacial reactions, stretching, and extrusion. The applications of oxidant (hydrogen peroxide) did not enhance the dissolution kinetics;
natural or synthesized sputter-coated films have taken a twist, especially instead, a notable escalation in the oxidation of the graphite substrate
in the food, water, pharmaceutical, medical, agricultural, and petro­ occurred, resulting in an unexpected weight gain despite surface
chemical industries [127,176]. erosion. The impact of ultrasound on the dissolution process was
The synthesis and development of photo-antimicrobial or light- discernible, manifesting a nearly threefold acceleration compared to
catalyzed films for decontamination of microbes in medical devices dissolution conducted under silent conditions. The dissolution rate was
and food substances is extremely significant due to several infections found to be slowest in the case of graphite with a density of 1.82 g/cm3,
and deaths caused by microbes one of the sputter-coated films, that is, primarily attributed to the contribution of pore size distribution in
chitosan/gelatin-based films containing pomegranate peel extract and containing the yttria particles. The dissolution process in nitric acid
curcumin at different concentrations (0.5–5.0 mg photosensitizer g− 1 exhibited kinetics governed by ash layer diffusion control. The study
solution) was developed to decontaminate microbial growth in medical conclusively demonstrated the effectiveness of ultrasound as an accel­
devices (endotracheal tubes and catheters) and food packaging. The erated decontamination method for graphite substrates, marking a sig­
effects of photobleaching were found to be 90% and demonstrated nificant advancement in the field [178].
marked therapy against the microbes. The chitosan/gelatin-based films To decontaminate seeds intended for edible sprout production and
significantly inhibited the growth of Staphylococcus aureus (to about 4 combat Listeria, chitosan (CS) coatings were employed, incorporating
log units) with the aid of 525 and 450 nm (50 J cm− 2) for pomegranate synergistic lysozyme-nisin (LYS-NIS) mixtures. Notably, the efficacy of
peel extract and curcumin respectively [176]. these coatings varied based on the molecular weight of chitosan used.
The goal of WHO is for mankind to live in good health and well-being Specifically, low molecular weight chitosan (LMW-CS) coatings exhibi­
(sustainable development goals III), enjoy clean water and sanitation ted the highest effectiveness against Listeria innocua, followed by me­
(sustainable development goals VI), and above all, have sustainable dium molecular weight chitosan (MMW-CS) and high molecular weight
cities and communities (sustainable development goals XI) where living chitosan (HMW-CS). Moreover, LMW-CS film combined with LYS-NIS
organisms can cohabitate without risk of contaminations, infections, demonstrated a nearly 1.5-fold greater reduction (~5 log) in the
and death. However, untreated contaminants or chemicals such as initial L. innocua load in broth culture over 6 days, in comparison to

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MMW-CS and HMW-CS films with LYS-NIS. SEM images of LMW-CS modifying the electrical structure can significantly improve photo­
films depicted the presence of heterogeneously distributed aggregates catalytic performance.
(Fig. 11 a-d). Furthermore, LMW-CS coating, along with LYS-NIS, ach­ In the realm of environmental remediation and sustainability, the
ieved substantial reductions in initial Listeria loads in mung beans, scope of photocatalytic environmental cleanup is primarily suited for
lentils, and wheat—amounting to 3.3, 3.4, and 4.1 log reductions, managing low-level pollutants. This is because the availability of UV
respectively. Importantly, these antimicrobial coatings exhibited no photons, present in both solar light and indoor illumination, is con­
significant impact on seed germination rates. However, the incorpora­ strained. While certain applications, such as outdoor self-cleaning, can
tion of LYS-NIS resulted in alterations in the films’ properties. This potentially leverage UV photons from solar radiation, the overall
included an increase in yellowness and opacity, accompanied by partial quantity of UV photons in solar light is often insufficient for robust
changes in mechanical and morphological attributes [179]. photocatalytic purification when compared to the abundance of con­
Catalysis is the method that alters the course of a chemical reaction taminants. Currently, photocatalysis serves more as a supplementary
to produce more products by employing suitable catalysts. More suc­ approach to biological remediation and other advanced oxidation pro­
cessful removal of many water contaminants will depend on the devel­ cesses, due to these limitations. Consequently, the trajectory of photo­
opment and usage of more stable, better, selective, and affordable catalytic environmental remediation is intricately linked to how
catalysts. Further studies could be done on how to effectively convert effectively photocatalysts can harness solar energy. The future of this
low-cost by-products from the industries and agro wastes into excellent field hinges on the capacity to maximize the utilization of solar energy
catalysts for more environmental cleanup applications. Additionally, for enhanced environmental cleansing. More so, there are very shanty
highly active transition metal oxides could also be developed for use as studies carried out on the application of sputtered-coated material for
water treatment catalysts. The recent strides made in thin film tech­ adsorption application most especially, the liquid-phase interface. These
nology have significantly expanded the horizon of industrial applica­ are promising areas to explore for future application. The photocatalytic
tions for metal oxide thin film photocatalysts. While materials like TiO2 environment and the respective advancement in the field of environ­
and ZnO have garnered extensive study and notable economic success, mental remediation, require utmost importance due to the low utiliza­
certain limitations such as wide band gaps and lower efficiency have tion or absorption of the sunlight by the photocatalyst. So, the major
prompted exploration into alternative metal oxides and metal sulfides. scope of research in the future aspects would be dealing with liquid-
The performance of thin film photocatalysts hinges on various factors phase interface junctions. The various potential applications include
including surface morphology, electronic structure, crystalline di­ membrane filtrations, disinfectants, desalination, removal of heavy
mensions, thickness, and the intricacies of the deposition process. The metals, air filters, antifouling coatings, selective separations, and water
thin film approach not only paves the way for innovation in immobili­ sensors. The suitability of sputter-coated thin films for these applications
zation technology but also demonstrates the potential to efficiently depends on factors such as film composition, structure, thickness, and
degrade contaminants on a large scale. As a result, this avenue holds surface properties. Tailoring these parameters can lead to optimized
promise for substantial advancements in the field of environmental materials that effectively address the challenges associated with water
remediation. Because photocatalysis is a surface event, thin film pho­ purification, air purification, and environmental remediation processes.
tocatalysts continue to struggle with efficiency due to lesser surface area As a result of various environmental issues, there is a growing in­
and reactive sites. As a result, widespread industrial use of thin film terest in the fabrication of thin films for environmental sustainability.
photocatalysts necessitates only minor adjustments and study. One Different sections of this review have addressed some of the studies
method for increasing the surface area of thin films is to add a small carried out by various researchers on the application of sputter-coated
amount of surfactant. Furthermore, using a variety of substrates and materials to environmental sustainability as related to air purification,

Fig. 11. SEM photographs of LMW-CS films (Magnification 500×; A: Control; B: 3.5 mg/cm2 LYS; C: 0.5 mg/cm2 NIS; D: 3.5 mg/cm2 LYS and 0.5 mg/cm2
NIS) [179].

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R. Garg et al. Advances in Colloid and Interface Science 330 (2024) 103203

water treatment via photo-catalytic degradation, adsorption, and 4.1. Photoelectrochemical hydrogen generation
decontamination. Generally, from all the literature explored, TiO2 thin
films and the Cu2O-loaded thin films are found to be the most utilized The most predominant features of the photoelectrochemical
sputter-coated materials for photodegradation and they have unique hydrogen generation involve high surface area, and open porosity
properties towards the Ag loading over the materials as they play a resulting in the conversion of efficiency of the photocatalysts. The defect
major role in hindering the fast charge-recombination dynamics of the creation either through oxygen deficiency or physical defects over the
materials. From the adsorption approach, sputter-coated thin film ma­ electro-trapping layer can improve the highly negligible electron
terials have found application in solid-gas and liquid-solid interfaces transport [185–188]. The defect creations such as oxygen vacancies in
relating to gas and liquid phase adsorption. Typically, sputter-coated the photocatalysts are highly responsive over the photocatalytic appli­
materials have found effective applications in the adsorption of pro­ cations as shown in Table 5.
tein, gases, and endocrine disruptive heavy metal ions such as Pb(II). The high-quality hematite (α-Fe2O3) is majorly synthesized through
Among the excellent applications of sputter-coated thin film materials is RF-sputtering which is found to be one of the N-type semiconductor
the decontamination ability as found in their antimicrobial capacity and materials which favors the photoelectrochemical water splitting. The
inhibition of microbial growth in medical devices and food substances. limitations involve low efficiency, large-scale production, and high
This role has positioned sputter-coated thin films as bifunctional and recombination losses. Among other materials, CdO/α-Fe2O3 nanorods
efficient materials finding relevance in environmental sustainability and on annelation at 600 ֩C upon the 70 nm deposition of the Fe resulted in a
decontamination. superior photocurrent density of 1.2 mA/cm2 at 1.65 V vs RHE at 30 nm
cadmium the thickness of the best hematite (10-50 nm) of the cadmium
4. Thin films for energy and electronics deposited (CdO ~ 2 nm) over the α-Fe2O3 as shown in Fig. 12. The CdO-
modified photoanode demonstrated high dye removal of around 98% of
This section majorly affirms the sputter-coated thin-film photo­ MB in a short span of 40 min. The CdO deposited over the surface of the
catalysts over photocatalytic hydrogen generation [180–182], fuel cells, hematite acts as a co-catalyst in enhancing the hydrogen generation
energy perspectives, and a brief discussion on remaining issues with efficiency, where the reactive Cd2+ species, facilitates the electron
challenges over electron sputtering. Thin films possess diversified transfer as well as the electron-hole recombination dynamics [189].
compositions and morphological variations that would harness their The sustained development of the N-doped TiO2 through the reactive
desired applications favoring photocatalytic as well as energy conver­ RF magnetron sputtering studies over varied pressures along with a
sion applications revealing that sputter-coating is explored in catalysis, compositional variation of a dual reactive gas mixture of oxygen and
energy harvesting, photonics, etc. Sputter-coating over the nano­ nitrogen. The varying deposition parameters of the materials signifi­
particles enhances the surface area-to-volume ratio [183,184]. The cantly control the material’s bandgap alignments, and their consecutive
prominent advantages of heterogeneous catalysis result in high charge white or green light absorption in low-pressure Nitrogen-doped TiO2
separation over the reaction systems and the centrifugation. The unique thin films. The incorporation of nitrogen and the visible light absorption
features obtained through the catalytic supports include: (1) higher from the white light over the low-pressure conditions have improved
surface area, (2) high porosity, as well as full accessibility of the pores photoelectrochemical hydrogen generation around the pressure of ~3
over the individual nanoparticles on the thin films, (3) the deactivation mTorr under white light with a photocurrent density of 567 μA/cm2 and
of the catalytic active sites through the aggregation as well as the a nitrogen ratio of 25%. The photocatalytic degradation of N-methyl-2-
leaching under harsh conditions, (4) incorporation of the system over pyrrolidone (NMP) is found to be a cyclic structure containing the ni­
the continuous-flow kinetics, and (5) higher stability and flexibility of trogen species, a versatile solvent found in various applications in
the materials, developed and their recovery after the loading, these different fields. The highest photocatalytic activity over the TiO2 and N-
would support the enhancement of the selectivity, durability, thermal as TiO2 is majorly found at 14 mTorr, which is majorly due to the photo-
well as chemical stability, etc. bleaching, and the concentration of N-48%, 60% leads to a higher
Fuel cells are found to be another important aspect of the electro­ photocatalytic degradation of Nat > 1.8% [190].
chemical devices wherein the chemical energy is converted to electrical The fine-tuning of gold nanoparticles (Au NPs) over the titania
energy over the presence of the electrolytes. The basic chemistry behind nanotube arrays (TNTs) with an optimized diameter (7-25 nm) and high
the fuel cell involves the formation of the sandwich structure, with the surface area distribution over the TNTs loaded with the Au NPs. The Au
cathode and anode over the films incorporated over the electrolyte in NPs and their computational dynamics along with the experimental
the solution and the fuel cell technology. studies were demonstrated through the localized surface plasmonic
In electrocatalysis, oxidation takes place over the anodes whereas resonance (LSPR), wherein the higher efficiency of 0.750 mA/cm2, 86%
reduction occurs over the cathodic surface, and the electrons are in their photocurrent efficiency at 10 mA. The negative slope over the
transferred from the anode to the cathode and the transport of the Mott-Schottky analysis demonstrates a strong negative shift over their
protons takes place in the electrocatalytic solution. The demerits of the flat band potentials with an increased donor density in comparison to
commercialization of the fuel cells involve the sluggish kinetics in the that of the bare TNTs [191].
ORR over the cathodic interface. Adequate care must be taken in the The ordered templating of Ni nanoparticles blended with TiN (6 nm)
catalyst development and the plasmonic resonance creation, and the over the hexagonal pores and ordered structures through the impreg­
formation of active sites on the surfaces enhancing the energy conver­ nation over the Al2O3 and TiO2 materials carried out through the DR
sion efficiencies in the fuel cells. The plasmon-mediated electrocatalysts sputtering technique is found to be one of the prominent strategies over
majorly facilitate the oxidation of the fuels over the anodic sites wherein photoelectrochemical hydrogen generation. The as-synthesized TiN/
the coverage of the catalytic sites using the metal centers has been TiO2/Al2O3 photocatalyst determines the current-voltage relationship
mitigated. The development of various semiconducting materials over various light intensities, temperatures, and wavelengths, which are
involving 1D, 2D metal, and non-metal-based materials has been widely majorly utilized in the determination of electrode applications, with a
considered over sputter coating techniques to increase their surface comparison of Au coating over the surface and before towards hydrogen
area, charge separation properties, charge separation dynamics, and generation efficiency through sewage water splitting abolishing the
stability which would thrive towards their photocatalytic application usage of sacrificial electron donors. The QE efficiency is found to be
and energy harvesting ability. The 1D structures are highly ordered and 0.25%, and 0.34% over 400 mW.cm-2 for the photoelectrodes and their
majorly strive towards enhancing the charge transfer directionality, and effect on Au coating before and after loading, respectively. The
electron-hole separation with orthogonality favoring the enhanced ef­ consecutive activation energies are found to be 238.1 and 211.5 kJ-1.
ficiency in photocatalytic and photoelectrochemical aspects. mol-1 before and after the Au loading possesses high durability and cost-

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R. Garg et al. Advances in Colloid and Interface Science 330 (2024) 103203

Fig. 12. (a) Fabrication procedure of the materials, (b) Schematic representation of the dye degradation, and (c) Morphological as well as the elemental composition
of the Cd-Fe2O3 respectively [189].

effectiveness for industrial applications [192]. forward bias of V ≥ 0.43 [195].

The fabrication of TiO2 nanotubes over the flexible surface of the Fakhouri et al. and his co-workers have demonstrated the develop­
Kapton substrates at a variety of temperatures of RT and 300 ◦ C, and 1.5 ment of Nitrogen-doped TiO2 semiconducting material-based thin films
μm long as well as 80 nm diameter, and the anodization of Ti film using the reactive RF magnetron sputtering technique. The controlled
deposited through RF sputtering. These studies lead to a twofold in­ effect of loading the nitrogen levels over the TiO2 surface and their
crease in the rear pileup of Ti film over elevated temperatures other than photoinduced responses have been thoroughly monitored. This tech­
RT. The superior photocurrent efficiency of 18 μA/cm2 under AM 1.5 G nique is a simple procedure, involving a dual reactive gas mixture flow
using TiO2/Ti/Kapton. The variation of temperature, deposition time, of nitrogen and oxygen. The deposition technique highly favored their
and RF power lead to a ~ 8 cm2 larger area with strong adhesion [193]. significant control over their band gap energies to determine their
The creation of defects over the surface of WO3 thin films, wherein the photocurrent generation ability under white light irradiation over the
features such as physical defects, and their micronized holes, through RF visible range. The improved photocurrent generation of the nitrogen-
sputtering as well as atomic layer deposition. The creation of physical doped films over white light irradiation under low pressures has been
defects over the films enhances the resistance towards charge transfer thoroughly investigated. The variation of the deposition parameters
with a higher recombination rate inhibiting their photogeneration effi­ envisages that the photocurrent generation under visible light showed
ciency under annealed air. The variation of ALD and sputtered synthesis higher improvement over deposition pressures and varied based on their
reveals the higher efficiency of τD = 3.2 × 10-2 ms through the increased nitrogen incorporation over the TiO2 surface. The interstitial sites over
adsorption of the OH groups on the surface of thin films and their effi­ the nitrogen are more efficient towards the photocatalytic activity,
ciency [194]. wherein the substitutional sites (NI) are found to be more dominant with
The synthesis of the TiO2/BDD is majorly carried out using p-type a negative effect on the photocatalysis under UV light irradiation. The
semiconducting material of boron-doped diamond (BDD) along with the desired application is highly considered under deposition conditions
n-type TiO2 wherein the initial deposition of the BDD over Si substrate is with variations in the functionalities [190].
carried out through the microwave plasma chemical vapor deposition
(MPCVD) technique. The reactive RF sputtering is considered herein 4.2. Photocatalytic hydrogen generation
where the effect of sputtering pressure, time of coating, their working
pressures, Ar/O2 flow conditions, and temperatures of the substrates are The photocatalytic hydrogen generation procedure lies in the effi­
optimized. The RF sputtering over 90 min time leads to enhanced ac­ ciency of the photocatalyst, the excitation of electrons from the valence
tivity of 1.6 folds higher efficiency than other time intervals over 1.5 V, band of the semiconductor through the irradiation of light to the con­
with a remarkable ratio of the rectification value of 63,773 over 5 V. The duction band of the semiconductor, leading to the formation of holes
activity of higher efficiency is majorly ascribed to their p-n junction over the valence band, and the excess electrons leads to the water
formation and the injection of holes from BDD to TiO2 over an applied splitting and hydrogen generation through the protonation with

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R. Garg et al. Advances in Colloid and Interface Science 330 (2024) 103203

electrons [196,197]. The excess hole generation can be mitigated by the bandgap between 1.7 and 2.1 eV, reducing their bandgap values [202].
supply of electrons through the sacrificial agent, wherein the electron- The development of the Pt/Ti/TiO2 photoelectrode through the RF-
hole recombination takes place, for increased efficiency. The compara­ magnetron sputtering which was demonstrated by Chiarello et al.
tive studies of the photocatalytic hydrogen generation efficiency of the where the different deposition times ranging from 1 to 8 h have been
sputter-coated thin films are tabulated in Table 5. considered to determine their hydrogen as well as oxygen evolution
The development of the Cr or Fe-ion doped TiO2 thin films has been through the photocatalytic water splitting. The superior hydrogen gen­
majorly carried out using radio-frequency magnetron sputtering as well eration efficiency was majorly obtained through the 6 h- irradiation time
as the sol-gel methods for the photocatalytic hydrogen generation of the TiO2 through the deposition with their rutile polymorph, and the
application. Various parameters such as the dopant concentration, superior hydrogen generation efficiency is found to be 212.30 ± 0.03
dopant method, their uniform charge transfer from the metal dopant μmolh-1 with their photocatalytic conversion efficiency of 7.1-φexp, the
towards TiO2, and the various types of dopants and their systematic increase in hydrogen production rate would be parallel leads to the
modification over the TiO2 surface. The comparison of the materials redshift over the IPCE curves which leads to the absorption as well as the
prepared through sputter coating and the sol-gel methods demonstrates conversion efficiency on the extended proportion of incident light
that the thin films synthesized through the sputter coating resulted in a spectrum., the hydrogen generation, as well as the oxygen evolution
higher hydrogen generation efficiency of 15.5 μmolh-1 for Fe@TiO2 in efficiencies and their ratios, are slightly higher over their stoichiometric
comparison to that of the Cr@TiO2 (5.3 μmolh-1). This enhancement is values [203].
majorly obtained due to the electron-hole trapping ability of Fe ions and The preparation of sodium tantalate (NaTaO3) loaded onto
reduces the charge combination whereas Cr tends to possess the ability indium‑tin-oxide-coated substrates was achieved using a straightfor­
to trap one complete type of charge carrier [198]. ward screen-printing technique. Gold‑palladium (Au–Pd) sputtering
Demonstration and development of various ZnO-based thin films targets were employed in the process. Notably, the quantity of Au–Pd
with the effect of annelation and synthesis using the RF magnetron loading over the NaTaO3 material emerged as a critical determinant
sputtering technique is highly considered for photocatalytic hydrogen influencing the efficiency of these materials in the context of photo­
generation applications. The variation of annelation is majorly carried catalytic hydrogen generation [204].
out in different atmospheric conditions such as air, argon, and nitrogen. The synthesis of the TiO2 thin films through the RF magnetron
The ZnO films annealed in air at 400 ◦ C resulted in a superior hydrogen sputtering as well as the sol-gel technique and their comparison towards
generation rate of 76 μmol, where the percentage of oxygen deficiency the H2 and O2 generation through photocatalytic water splitting under
was majorly confirmed through the XPS analysis. The correlation be­ visible light. The development of the cell bias over the photo­
tween oxygen deficiency and hydrogen production is clearly where the electrochemical cell majorly involves the TiO2 films deposited over the
oxygen deficiencies act as the active sites which favor the reaction yield. ITO films as the anode and the Pt co-catalyst as the cathode material.
The deactivation of the ZnO samples and their photocatalytic applica­ The continuous generation of the gases leads to the eradication of the
tions is consecutively explained [199]. backward reaction and the studies revealed that the sputter-coating
The development of the Cr-doped-TiO2 thin films is majorly carried technique has resulted in a superior efficiency in comparison to that of
out with the variation in Cr concentrations such as 2, 5.5, and 9 wt%), the sol-gel technique due to the oxygen vacancies created over the TiO2
majorly synthesized using RF magnetron sputtering. The effective films by the energetic target ions over the deposition under Ar atmo­
doping of the Indium Tin Oxide (ITO)/Cr-doped-TiO2 (9 wt%) bilayers sphere. The open-circuit (Voc) over the sputter-coated material with a
with a thickness variation of thin films over the bilayers enhanced thickness of 30, and 50 nm possesses higher efficiency, which is majorly
photocurrent efficiency and a superior photocurrent efficiency of 24.4 due to the resistance over the contact of electrical contact layers which is
μmolh-1 which is two times higher in comparison to the pristine TiO2 a prior factor towards the loss of absorbed energy of photons. The
photocatalysts. The higher hydrogen generation of the Cr-doped TiO2 conductivity of the material is inversely proportional to the thickness of
multilayer film enhances the visible light absorption and decreases the ITO films, wherein the deposition of the TiO2 over the thinner ITO
charge-recombination dynamics which is majorly caused due to the towards the enhancement over electrical contact and reducing the en­
number of charge spaces over the ITO/TiO2 interfaces over the multi­ ergy loss caused through photon absorption favoring the better photo-
layer films [200]. The PbS/ZnO thin films are majorly designed through voltage [205].
RF magnetron sputtering, the chemical bath deposition over the glass The thermal treatment of the NiCu nanoparticles and their surface
substrate, and the n-type ZnO thin film. The PbS/ZnO thin film resulted diffusion with the Ni and Cu sputtered layers leads to a nanotube sur­
in a higher hydrogen generation efficiency of 7.38 μmol⋅cm-2 h-1 in face. The work function, composition, co-catalytic ability, and the
comparison to that of PbS and ZnO which are 3.35 μmol⋅cm-2 h-1 and dewetted-alloyed co-catalytic nanoparticles with the equimolar quantity
2.45 μmol⋅cm-2 h-1 respectively. The ellipsometric representative models of the Ni and Cu amounts. The suitable temperatures over the thermal
of PbS/ZnO thin films, majorly determine the thickness as well as the treatment can lead to surface diffusion and dewetting i.e., the splitting
bandgap energies of the materials. The basic PbS/ZnO interface layer into the NiCu NPs which includes controlled size, and spacing over the
majorly determines the superficial roughness by a two-phase system TiO2 surfaces of the nanotubes. 5Ni5Cu-TiO2 photocatalyst resulted in
determined by Bruggeman’s effective medium approximation (EMA) the superior hydrogen generation efficiency of 6.04 μL h-1 cm-2 on light
[201]. irradiation with an AQY ~ 0.043%. Herein, the NiCu alloyed nano­
The development of the TiO2 nanorods through the hydrothermal particles act as co-catalysts towards the TiO2 which is a noble metal-free
method over the seed layer through the deposition by the DC sputtering photocatalyst towards photocatalytic hydrogen evolution as shown in
as demonstrated by Cruz et al. The studies revealed that the TiO2 seeds Fig. 13 [206].
are oriented over the anatase phase and the TiO2 nanorods in the rutile The deposition of the Cu and Pt clusters over the TiO2 powders
phase. The profilometer has been used to analyze the thickness of the through the pulsed DC magnetron sputtering with the variation of
film for the seed layer which is 310 nm and that of the TiO2 nanorods to temperature and deposition time during the Cu/Pt sputtering technique.
be ~400 nm. The photocatalytic hydrogen generation efficiency of 38 The photocatalytic activity of the composite possessing the Pt clusters in
μmol is found for TiO2 seeds and 132 μmol for TiO2 nanorods. This comparison to that of the pristine TiO2, and their plasma compositions
orientation highly influences the midgap states by increasing their over the Cu sputtering on the surface would affect or alter the photo­
contribution below their conduction bands towards the valence band, catalytic activity of the materials, wherein the Cu is deposited over the
which favors the enhanced photocatalytic activity. The higher activity of Ar-atmosphere as co-catalyst to inculcate the photoactivity of the ma­
the TiO2 nanorods was majorly due to the contribution to the rutile terial in comparison to that of the Cu sputtering under Ar/O2 atmo­
phase and their Ti3+ species contribution towards the redshift in the sphere. The additive effect of the Cu cluster and Pt deposition as the two

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R. Garg et al. Advances in Colloid and Interface Science 330 (2024) 103203

shaking frequency of the highly ordered powdered samples during metal

sputtering [207].

4.3. Photocatalytic CO2 reduction

The process of photocatalytic CO2 reduction exhibits the potential

for utilization in the realm of CO2 photoreduction to produce useful
chemical fuels. This phenomenon transpires when the coexistence of
CO2 within an aqueous solution instigates the reduction of CO2
[208,209], facilitated by the photogenerated gaps in electron structures
(holes) and hydrogen entities. The resultant products encompass CH4,
carbon monoxide (CO), methanol (CH3OH), HCOOH, and formaldehyde
(CH2O) [210,211]. These chemical entities hold the promise of serving
as viable substitutions for conventional fossil fuels. Moreover, the inte­
Fig. 13. Effect of dewetting of the alloys over the thin films and their respective gration of cocatalysts and sacrificial agents constitutes a detrimental
hydrogen evolution efficiency [206]. approach aimed at amplifying the efficacy of CO2 photoreduction, and
some of the reports are tabulated in Table 3 using thin films.
metals over the TiO2 enhanced activity under the sputtering of the Cu The synthesis and CuO thin films through DC sputtering over the
cluster in the absence of the oxygen centers. The application of pulsed- variation of deposition time such as 10, 20, and 30 min with the
DC magnetron sputtering as a technique yields improved efficiency in modification in thickness such as 60, 120, and 180 nm as demonstrated
modifying photocatalytic powders with customized metal nanoparticles by Cruz et al. Here the determination of the photocatalytic hydrogen
within a relatively brief period. This process induces structural alter­ generation as well as the CO2 photoreduction over the simulated sun­
ations in the initial materials. The increase in the homogeneity of the light conditions. The superior hydrogen efficiency is majorly obtained as
metal clusters will optimize the operational parameters through the 24 μmol over the 120 nm thickness of CuO thin films and a CH3OH
lowering of the sputtering power under varied deposition times, with the generation of 1536 μmol/g, CH2O of 450 μmol/g, whereas the low
thickness i.e., 10-CuO resulted in enhanced CH2O generation of 6816

Table 3
Summary of a few adsorption applications using sputter-coated thin film material.
Adsorption and mechanism Adsorbent and Adsorbate Experimental Conditions Findings Ref.

Gas-Solid interface involving Adsorbent: Nickel Nanoarrays: Rapid Adsorption Rate and [212]
Chemisorption mechanism Titanium‑zirconium‑vanadium (Ti-Zr- Varying synthesis parameters Adsorption Capacity Nanoarray-supported
V) Ti-Zr-V Films: Ti-Zr-V films exhibit greater capacity than
Adsorbate: H2 Sputter-deposition technique films on silicon substrates.
Protein Adsorption onto ZrCuX thin Adsorbent: ZrCuX BSA Solution Preparation: 100 μg/mL ZrCu-coated Ti6Al4V substrates show [213]
film, involving chemisorption BSA in PBS at pH 7.4. increased protein adsorption, notably with
X = [Ca, Mo, Mg, Si, Sr] Protein Deposition: 100 μL droplet, Mo, Sr, and Mg additives.
30-min (min) incubation, ethanol Study of protein adsorption and immersion.
Adsorbate: Protein rinse, N2 drying.
Wash: PBS wash, distilled water
treatment, N2 drying.
Liquid-Solid interface for liquid phase Adsorbent: MoO3 Batch adsorption at Adsorption increased with higher sputtering [137]
adsorption Initial MB conc = 10 ppm, power and thicker samples.
Adsorbate: MB Contact time = 1200 min (20h), MoO3 films exhibited the most effective
adsorption.
Liquid-solid interface in a Liquid Adsorbent: CuO Solution pH: 6 Conformed to a pseudo-second-order model [157]
phase adsorption involving Contact Duration: 3 h Maximum adsorption capacity (Qmax) was
Physisorption mechanism. Adsorbate: Pb(II) ions Adsorbent Dose: 2 g/L 37.027 mg/g.
Targeted Removal: Pb(II) ions Adsorption process endothermic nature.
Initial Concentration: 50 mg/L
Photocatalytic Degradation Adsorbent: ZnO doped with Cd Thin Films: ZnO and cadmium-doped Achieved 49.6% degradation efficiency for [214]
ZnO ZnO films.
Photocatalytic Reactivity: Demonstrated enhanced degradation
Degradation of MB molecules
Activation Source: UV light
irradiation
Hydrogen Gas Adsorption Adsorbent: Zr-Co-RE compounds Loose, porous, columnar-like Superior adsorption capacity and enhanced [215]
structure stability in pumping speed.
RE: rare earth elements. Limited lateral diffusion of Zr and Co
atoms
Absorbate: H2 gas Obstructive effect from non-
perpendicular sputtering
Amorphous or nanocrystalline
framework in Zr-Co-RE films
Gas-phase adsorption of N2 to TiN. Adsorbent: TiN 2-in. diameter planar circular DC Increasing flow rate leads to saturation of [216]
Chemisorption mechanism magnetron target adsorption.
involved Adsorbate: N2 gas Target: Titanium (99.995% purity)
Beamline: 10-6 mbar
Processing chamber: ~33 × 10-3 mbar
Argon: 10.4 sccm
Nitrogen: Up to 2 sccm (modulated
flow)

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R. Garg et al. Advances in Colloid and Interface Science 330 (2024) 103203

Table 4
Isotherm, kinetics and thermodynamics model [217,218].
Models Mathematical Plot axis Slope Intercept Evaluated Description
Expression Parameters

Isotherms
Langmuir Ce Ce Ce/Qe Vs 1 1 Qmax &KL Qe: Equilibrium adsorption quantity (mg/g), Ce: Equilibrium concentration (mg/
= +
Qe Qmax Ce Qmax Qmax KL L), Co: Initial concentration (mg/L), KL: Langmuir adsorption constant (L/mg),
1 and Qmax: Maximum adsorption capacity (mg/g).[217]
Qmax KL
1
RL =
1 + K L CO
Freundlich logQe = logKF + Log Qe vs 1 KF 1 Qe: Equilibrium adsorption quantity (mg/g), Ce: Equilibrium concentration (mg/
1 log Ce nF nF 1
logCe L), KF: Freundlich constant (adsorption capacity), and : Adsorption intensity
nF & KF nF
factor (Freundlich model).
Temkin Qe = βlnAT + Qe vs ln Ce β BlnAT AT & β AT: Temkin equilibrium binding constant (L/mg), β: Temkin constant related to
βlnCe heat capacity, estimated as RT/b, R: Molar gas constant (8.314 J/mol/K), T:
Absolute temperature measured in Kelvin (K).
D-R ln Qe = − βε2 + ln ln Qe vs ε2 − β ln Qmax β and Qmax β: Dubinin-Radushkevich constant,
Qmax Qe: Quantity of adsorbate adsorbed at equilibrium, Qmax: Monolayer maximum
1 adsorption capacity (mg/g), E: Energy of adsorption determining the process
E = √̅̅̅̅̅̅
2β mechanism.

Kinetics Models
Pseudo first ℓn(qe − qt ) = ln(qe-qt) k1 ln qe qe & k 1 qe and qt: Quantities adsorbed at equilibrium and at time (t), respectively.
order ℓnqe − k1 t Vs t k1: pseudo-first-order rate constant
Pseudo second t 1 t t/ Vs t 1 1 qe & k 2 k2 is pseudo-second-order rate constant, while other parameters remain as earlier
= + qe /qe
order qt k1 q2e qe k1 q2e defined.
Elovich 1 1 qt Vs ln t 1/β 1 α, β ∝ is the initial rate of adsorption in (mg/g-min);
qt = lnt + ln(αβ) ln(αβ)
β β β β denotes the desorption constant in gmg-1
Fractional ℓog (qt ) = log(k) + log (qt) vs v k v, k k: the fractional power constant factor, v: positive constant, specifically equal to 1
Power vlog(t) log (t)
Intraparticle qt = KIPD t
12
/
+C qt VS t1/2 KIPD C KIPD, C KIPD: intraparticle diffusion rate constant in mg.g-1 min-0.5, while C signifies the
diffusion intercept that denotes the adsorbent thickness.

Thermodynamics
Gibbs Free ΔG◦ = − RTlnKd ΔG◦ ΔG◦ is Gibbs free energy, Kd Equilibrium constant from Langmuir.
Energy
Van’t Hoff Plot ΔS0 ΔH0 ln KC ΔHo ΔSo ΔHo, ΔSo ΔSo: standard entropy (kJ/mol K);
ln KC = +
R RT versus 1/T KC = Qe/Ce, denoted as equilibrium constant at various temperature; ΔHo:
standard enthalpy quantified in kJ/mol K.
Arrhenius Ea ln k2 Ea A A, Ea, Ea: Activation energy for adsorption process (kJ/mol), k2: Pseudo-second-order
ln k2 = lnA -
Equation RT versus 1/ rate constant (gmg-1 min-1), kL as Langmuir constant evaluated from various
T, thermodynamics parameters could also be used in place of k2; A: Arrhenius factor

μmol/g. The refractive index studies reveal that the 10-CuO possesses oxidation of H2O, CO2−
3 and HCO3 thereby contributing to O2 genera­
−

increased value over the range of 550-900 nm whereas the 20-CuO and tion prevention [221].
30-CuO reduced over the visible region. The ellipsometry results suggest
that the 20-CuO thin film was revealed to possess the highest light ab­
4.4. Fuel cells
sorption over the UV-to-IR region and a lower refractive index along
with a higher extinction coefficient [219].
4.4.1. Overview sputter-coated thin films for fuel cells
The generation of mixed-phase TiO2 nanomaterials, characterized by
The advancement of thin-film fuel cells (TFFC) is crucial given their
elevated interfacial charge densities and heightened active sites, is pri­
extensive utilization across electric power generation, electric vehicles,
marily accomplished using DC magnetron sputtering. The incorporation
and portable devices, owing to their energy conversion efficiency and
of bundles of anatase-rutile phase-based nano-columns gives rise to two
impressive power densities. The focus on commercialization has become
distinct types of interfaces: one existing between the bundles and the
paramount within both research communities and industries, aimed at
other between the nanocolumns. The sputtering of the films over the
enhancing cost-efficiency per kW of power generation [222,223]. Cur­
lower angle in comparison to that of the pristine materials results in
rent efforts in cost optimization encompass various factors, including
superior activity under UV irradiation. The photoreduction of CO2 is
minimizing electrocatalyst loading variations, streamlining cell design,
carried out using isopropanol which is utilized as the additional scav­
and refining synthesis/manufacturing protocols. Material selection for
enger, wherein the superior efficiency was majorly obtained under 45%
fuel cells is guided by specific criteria: the anodic surface must facilitate
volume of the CO2 concentration, and an elevated temperature of
gas flow, serve as a catalyst for fuel oxidation, and exhibit both elec­
~80 ◦ C leading to ~12% of CO2 conversion to CH4 generation [220].
tronic and ionic conductivity [224]. Thin film electrolytic systems offer
The modification in the surface density, crystallinity, and their
high-performance efficiency at low temperatures, a trait even observed
amorphous, quasi-amorphous coating over the TiO2 by the DC magne­
in traditional electrolytes like yttria-stabilized zirconia. Additionally,
tron sputtering leads to incredibly low densities. The effectiveness of the
thin film technology finds application in barrier-layered deposition on
TiO2 coating is notably influenced by the catalyst’s area and density
the electrode–electrolyte interface, Chromium protective oxide layers,
parameters. Among the samples, the highest efficiency is achieved with
and functionally graded electrodes for interconnectors [225].
the GF3 sample, characterized by an extended surface area and a density
Solid oxide fuel cells play a pivotal role in efficiently converting
of approximately 1 g/m2. The presence of peroxo and peroxocarbonate
chemical energy into electrical energy and generating heat across a
species on the TiO2 surface plays a significant role in inhibiting the
spectrum of fuels, such as hydrogen and natural gases. In this process,

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R. Garg et al. Advances in Colloid and Interface Science 330 (2024) 103203

Table 5 zirconia (SSZ), or bismuth vanadium copper oxide (BIMEVOX),

Photoelectrochemical water splitting efficiency, Photocatalytic hydrogen gen­ lanthanum strontium gallium manganite (LSGM) [234,235]. Among the
eration, and CO2 reduction of various sputter-coated thin film materials. highly conductive electrolytes, CGO has become more and more popu­
No Photocatalyst Type Efficiency Ref. lar, [236] as phase stability and delayed degradation, are the demerits
Photocurrent efficiency
during SOFC operation in YSZ, LSGM, SSZ, and BIMEVOX materials.
1 CdO/α-Fe2O3- RF 1.2 mA/cm2 at 1.65 V vs [189] CGO is also termed a “mixed ionic-electronic conductor” with conduc­
600 ◦ C-30 nm RHE tivity over ionic as well as electronic levels under low-pressure levels of
2 N-doped TiO2- ~ Sputtering 567 μA/cm2 and a nitrogen [190] oxygen, and temperatures <800 ◦ C [237–239]. As a result, these are
3mTorr ratio of 25%
primarily used intermediates for low-temperature SOFC operation
3 Au NPs@TNTs Sputtering 0.750 mA/cm2, 86% in [191]
their photocurrent where ionic conductivity prevails. YSZ and CGO are the thin film elec­
efficiency at 10 mA trolytes that have received the most attention. In terms of thin film
4 TiN/TiO2/Al2O3 DC 0.25%, and 0.34% over quality, it has been discovered for both sputtered materials that, PLD
400 mW.cm-2 [192] and CVD can produce columnar thin films that can predominantly grow
5 TiO2 nanotubes on RF 18 μA/cm2 under AM 1.5 G [193]
Kapton-300 ◦ C
epitaxially over the substrate, and on the other hand, PSD, and spin
6 WO3 RF τD = 3.2 × 10-2 ms [194] coating leads to the formation of noncolumnar microstructures as
7 TiO2/BDD Reactive rectification factor of [195] demonstrated in Fig. 14(c, d).
Sputtering 63,773 at 5 V Anode thin films can be employed in solid oxide fuel cells to study
the mechanisms behind electrode reactions. Most of the standard anodes
Photocatalytic hydrogen generation have complicated microstructures with three interpenetrating Ni, YSZ
8 Fe@TiO2 Sputtering 15.5 μmolh-1 [198] (or CGO), and gas phase networks (e.g., a porous Ni-YSZ [CGO] cermet).
9 Cr@TiO2 Sputtering 5.3 μmolh-1 [198]
Additionally, it is challenging to isolate all processes that make up the
10 ZnO films-400 ◦ C Sputtering 76 μmol [199]
11 Cr-doped-TiO2-6 RF 24.4 μmolh-1 [200] anodic reaction mechanism. To unravel anodic reactions, numerous
bilayer groups have studied model electrodes composed of thin films with well-
12 PbS/ZnO thin film RF 7.38 μmol⋅cm-2 h-1 [201] defined geometry using experiments or simulations. Besides, these thin
13 TiO2 nanorods DC 132 μmol [202]
film electrodes, the studies of Ni point [240–243] and Ni-paste [244]
14 20-CuO sputtering 24 μmol [219]
15 TiO2 film-6 h RF 212.30 ± 0.03 μmolh-1 [202]
and their subsequent approaches grieved due to contacting, non-
16 Au-Pd/NaTaO3 sputtering 3305 μmolg-1 [204] reproducibility, and scaling issues.
17 TiO2 Magnetron 12.5 ± 0.1 μmolh-1 [205] Similar to anodes, a significant portion of research concerning thin
sputtering film cathodes revolves around model cathodes to dissect the mecha­
18 5Ni5Cu-TiO2 Plasma 6.04 μL h-1 cm-2 [206]
nisms underpinning cathode reactions. In contemporary applications,
sputtering
cathodes are primarily designed for low (600 ◦ C) and intermediate
operating temperatures. These cathodes often comprise mixed ionic-
CO2 Reduction
19 10-CuO (120 nm) DC CH3OH- 1536 μmolg-1, [219]
electronic conducting perovskite materials (ABO3), in which the A
CH2O- 6816 μmolg-1, 450 sites (typically rare earth elements such as lanthanum) and B sites
μmolg-1 (transition metals) can be manipulated to tailor the material’s charac­
20 TiO2 DC 12%- CO2 conversion to [220] teristics. Most of the compositions are composed of Strontium and
methane (CH4)-6.5 nmol
lanthanum as LaxSr1− xBO3±δ [245]. Due to identical ionic radii, the Sr2+
21 Cu/Rut-TiO2 DC 2.35 μmolgcath-1 [221]
cations in those compounds occupy the La3+ sites. The replacement of
Sr2+ by La3+ leads to the level formation of a completely ionized
depicted in Fig. 14a, hydrogen gas is fed into the anodic compartment, acceptor wherein the charges are formed by the holes over the valence
where it undergoes oxidation, releasing electrons that flow through the bands. Therefore, LaxSr1− xBO3±δ perovskites are found to be the
external circuit [224]. strongly doped p-type semiconductor [246–248]. Typical materials are
the well-known LSM, LSCF, and BSCF [249].
4.5. Cell components of fuel cells
4.6. Applications on fuel cells
The current electrolyte technology ranges from 10 to 200 μm
thickness, mainly via thick film or powder processing. To enhance fuel In a recent study, the La0.5Sr0.5Co0.95Nb0.05O3-δ (LSCNO) perovskite
cell efficiency and reduce costs, a shift to thin film techniques (~100- was employed as an electrode material in symmetric solid oxide fuel
1000 nm thick) operating at lower temperatures (~500 ◦ C) is pursued. cells. The investigation aimed to explore the oxygen reduction reaction
Thin films offer benefits such as reduced ohmic loss, lower sintering at moderate temperatures through the construction of thin-film LSCNO
temperatures (>1000 ◦ C), and controlled nanocrystalline microstruc­ electrodes within symmetric solid oxide fuel cells. The oxygen ion
tures, enhancing conductivity. However, nanocrystalline materials diffusion coefficient of LSCNO was observed to be 1.407 × 10-8 cm2/s at
[226–228] may exhibit unconventional electrical properties and ther­ 973 K, a magnitude higher than that of La0.5Sr0.5CoO3-δ - (7.751 × 10-9
mal stabilities [229–232] due to increased grain boundary concentra­ cm2/s). This improvement in oxygen ion diffusion was attributed to the
tion. Considerations must address stresses from thermal expansion structural stability conferred by Nb doping, which enhanced oxygen
disparities or deposition processes, influencing electrical conduction anion mobility. To delve into the rate-limiting mechanism governing
[233]. sluggish oxygen transport kinetics, thin films of 80 nm and 40 nm were
The basic characteristics and the electrical conductivity of the deposited on a gadolinium-doped ceria electrolyte substrate using RF
microstructure materials are thoroughly demonstrated, whereas in the magnetron sputtering. The emergence of increased resistance along the
thin films fuel cells with sputter-coated thin film electrolytes are thickness indicated bulk diffusion as the rate-limiting step influencing
considered. YSZ is widely considered as the stabilized material and is oxygen ion diffusion, as depicted in Fig. 15(a-d). The electrochemical
highly utilized over fuel cell applications, as it possesses properties of performance of a thin-film symmetric solid oxide fuel cell utilizing air on
ionic conductivity or acts as the ionic conductors for ~1000 ◦ C and is the cathode and H2 fuel on the anode was evaluated. This setup achieved
considered majorly for SOFCs as shown in Fig. 14b. But it predominantly a peak power density of 390 mW cm-2 at 1.02 V, as depicted in Fig. 15(e,
has a lower electrical conductivity index in comparison to that of the f) [250].
other microcrystalline electrolytes such as CGO, scandia-stabilized Reisner et al. used carbonaceous protective layers and thin films,

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R. Garg et al. Advances in Colloid and Interface Science 330 (2024) 103203

Fig. 14. (a) Schematic illustration of single solid oxide fuel cell, (b) Ionic conductivity of different microcrystalline electrolyte materials; Cross-sectional microscopic
images of ceria gadolinia oxide (CGO) (c) deposited by PLD and (d) deposited by PSD [224].

Fig. 15. Electrochemical Impedance Spectroscopy (EIS) spectra of symmetric cell developed using (a) brush painting, (b) 80 nm thin film, (c) with 40 nm thin film,
(d) Arrhenius plot of LSCNO symmetric cells, (e) Polarization resistance, and (f) I–V and I–P curve of symmetric cell [250].

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R. Garg et al. Advances in Colloid and Interface Science 330 (2024) 103203

flexible substrates to develop through fabricating lightweight artificial harvesting >95% over the front side, Jr-Hau et al. employed a strategy
leaves. In comparison, the Co-based catalysts and their photocathodes of decoupling towards electrolysis and light harvesting. (Fig. 16 a and b)
demonstrated that CO2 reduction attained superior CO:H2 selectivity = The electrochemical reactions occur over the back end in the PEC cells in
~7.2 under low (0.1 sun) irradiation than those with lead halide continuation with the carrier separation. The electrocatalysts (Pt for the
perovskite photocathodes, attained an H2 activity of 4266 μmol/g h-1 hydrogen evolution reaction (HER) side and Ni for the oxygen evolution
through platinum catalyst. Unassisted solar-to-fuel efficiency of the reaction (OER) side) were deposited using sputter-coated deposition on
perovskite-BiVO4 PEC devices was 0.58% for hydrogen and 0.053% for opposite edges of electrons and holes collection bars, creating a photo­
carbon dioxide, respectively. The scalability of 100 cm2 stand-alone cathode and a photoanode, respectively, as depicted in Fig. 16c. Sub­
artificial leaves, which maintained almost similar stability (of about sequently, the working electrode was affixed to an aluminum foil
24 h) to their 1.7 cm2 counterparts, provides an example of their po­ through tin soldering and linked to the working electrode. The resulting
tential for scaling. Additionally, on outdoor testing on the river, light­ silicon BBJ-PEC half-cell design effectively minimizes optical, electrical,
weight reactors aided gas collection while bubbles created during and catalytic losses (as low as 6.11, 1.76, and 1.67 mA cm2, respec­
operation allowed devices with a surface area of 30-100 mg cm-2 to float tively), yielding a notable current density of 40.51 mA cm2 for hydrogen
[251]. evolution, as illustrated in Fig. 16d. Furthermore, by integrating three
However, due to the unstable nature of submerged light absorbers, BBJ-PEC cells into a single module using a monolithic fabrication
Reisner et al. developed Photoelectrochemical (PEC) devices for direct approach, unassisted solar water splitting is achieved. This configura­
solar fuel synthesis. The oxide-based architecture and the formation of tion demonstrates a sun-to‑hydrogen conversion efficiency of 15.62%
BiOI absorbers of light are found to be robust in combination with the and an impressive hydrogen production rate of 240 g cm2/h [253].
encapsulants made of graphite paste, they produced photocathodes with The lowering of charge-extraction barriers as well as the pathway
an operational H2 evolution activity in a timeframe of weeks. The next towards the n- and p-type photoelectrodes in electrolytes possessing
step was to create integrated electrodes with photocathode capability by appropriate redox reaction, Wilson et al. disclose a design with band
coupling BiOI PV cells to a Pt electrocatalyst. To achieve this, conductive alignment. On the backside of the photoelectrodes, reactive sputter
graphite epoxy (GE) paste was used to encase the functioning ITO|NiOx| deposition was used to produce the carbon at room temperature. A
BiOI|ZnO|Cr|Ag pixels before a 5 nm Pt film was sputtered on top. As a quartz crystal microbalance installed within the chamber was used to
result, PEC tandem devices with multiple-pixel BiOI photocathodes, and calibrate the deposition rate (QCM). Furthermore, a reactive sputtering
BiVO4 photoanodes are stable for ~240 h over water-splitting, whereas process with a homemade metallic mask was used to deposit a ring-
the devices developed with Cu92In8 alloy show that syngas may be shaped Au layer at room temperature on the light-illuminated surface.
produced from CO2 without the need for additional assistance [252]. Pt, C, and TiO2 were among the conducting layers that were placed onto
The back-buried junction (BBJ) PEC cell design majorly allows light degenerately doped n+-Si substrates for the electrochemical experiment

Fig. 16. (a) Schematic illustration of BBJ–PEC Cell, (b) Cross-section as well as optical properties of cell, (c) the schematic setup of the interdigitated dopant pattern,
(d) Time-resolved saturated current density [253].

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R. Garg et al. Advances in Colloid and Interface Science 330 (2024) 103203

in the dark as shown in Fig. 17a-d respectively. At 400 ◦ C, or normal

temperature, the carbon was sputtered. To avoid silicon oxidation dur­
ing the following preparation of the TiO2 through the reactive sputtering
stage at 400 ◦ C. Based on their findings, they created a single-photon
photo charging method for redox flow cells that has a solar-to-
chemical conversion efficiency of over 9.4%. Along with these results,
we offer design guidelines for concurrent optimization, which could
result in improved conversion efficiency in future solar rechargeable
redox flow cell advancements [254].
With the use of inverted metamorphic epitaxy along with transparent
graded buffer leads to the bandgap alignment over each junction to be
separately adjusted, Deutsch et al. established very effective, submerged
water-splitting electrodes. By employing a buried p-n junction, voltage
losses on electrolyte contact are minimized by 0.55 V in comparison to
conventional, uniformly p-doped photocathodes. GaInP/GaInAs tandem
absorbers leads to advancement in benchmark, on-sun spectral correc­
tions and validation over incident photon-to-current efficiency, deliv­
ering 16% hydrogen generation efficiency, a 60% increase over the Fig. 18. Schematic and systematic configuration of SRFC, using the redox
traditional, high-efficiency tandem III-V device [255]. Furthermore, to couples such as Br-3/Br- and AQDS/AQDSH2 [256].
carry out the in-situ conversion of solar energy and their consecutive
storage, Li et al. have proposed efficient solar rechargeable flow cells 8.1- 6.7, and increase by 27% over the visible when thinly doped Si is
(SRFC) subjected to dual‑silicon photoelectrochemical cell along with paired with it on the waveguide. After shutting off photo-illumination,
quinone/bromine redox flow battery. The 5-nm thick carbon coating is the In2O3-x(OH)y system permits CO synthesis at a rate for two hours,
sprayed over the TiO2/Ti/n+p-Si electrode to maintain and develop C/ increasing yield by 44-62% over thermal alone yield. Through outdoor
TiO2/Ti/n+p-Si as shown in Fig. 18. The developed device leads to an solar concentrator testing, the usefulness of persistent photocatalysis
energy conversion efficiency of around ~5.9%, and a photon-electricity was established. The CO yield increased by 19% over a day-only period
conversion efficiency of ~3.2% on the usage of narrow bandgap towards after a day-and-night cycle [257].
the effective collection of photons and induced redox coupling towards According to John et al., power generation through the modules of
rapid charge injection through the interfaces. The suggested SRFC has a cadmium telluride (CdTe) photovoltaic is the most affordable electricity
discharge capacity of 730mAhl-1 and can self-photo charge to 0.8 [256]. over the solar business and is currently more affordable than sources
According to the idea of light maximization, Nazir P. Kherani’s that rely on fossil fuels in many parts of the world. The substrates were
research group suggested a counterintuitive method for distributing made of a 3 mm soda lime glass-coated fluorine-doped tin oxide layer
light intensity below the electronic photo-saturation limit. The devel­ that was ~400 nm thick and served as conducting oxide. Following the
opment of the photo-intensity induced hydroxide groups leads to the fabrication of the buffer/window layer for the devices, 100 nm of
coating of defect-engineered In2O3-x(OH)y which majorly operated MgZnO was coated with conducting oxides using a magnetron sputter­
under the saturation point and gaseous environment of H2 + CO2. The ing process. This is because selenium alloying into the CdTe absorber
reverse gas phase water shift in the solar catalysts over the optical recently resulted in efficiency advances that have increased cell effi­
waveguide with a ratio of 2.2. The optical pathlengths and the disper­ ciency from 19.5% to 22.1%. Although the band gap of the absorber
sion lengthens leading to the weak absorption of the green as well as material is known to be reduced by the addition of selenium, increasing
yellow wavelengths, leading to the production rate of CO with a factor of the cell short-circuit current as a result, this effect is not sufficient to

Fig. 17. (a) Band alignments in electrolyte of bare c-Si electrode, (b) TiO2, (c) Pt, and (d) Pt/TiO2 [254].

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R. Garg et al. Advances in Colloid and Interface Science 330 (2024) 103203

account for the gain in performance. Here, they demonstrated selenium light range adsorption would be a prominent aspect which would be an
enables increased luminescence efficiency along with longer diffusion important aspect for future researchers in developing various new
lengths on alloyed material, depicting the passivation of the selenium strategies for formulating the design parameters towards the develop­
with key flaws over the majority of the absorber layer, using cathode ment of the catalysts for the next-generation devices for the energy
luminescence as well as secondary ion mass spectrometry. The perfor­ harvesting and storage applications.
mance of the selenium-alloyed CdTe devices is explained by the The shapes and sizes of the metal nanoparticles are majorly fabri­
passivation effect, which also offers a way to increase efficiency and cated through the in-situ route over the surface of the nanofibers making
bring down the price of solar electricity even more [258]. the parameters more strenuous in uncovering the structural properties
The strongest platinum group metal-free catalyst, according to Xile and their consecutive relationship leads to improved catalytic perfor­
et al., is a Ni-based hydrogen oxidation reaction catalyst with an mance of the materials. In continuation, tremendous efforts need to be
exchanged normalized current density of around 70 A cm-2. The catalyst implemented towards the usage of catalytic materials possessing well-
is composed of Ni nanoparticles encapsulated in carbon support doped defined nanostructures with controlled size, facet types, and shapes,
with nitrogen. The electrical interaction among Ni nanoparticles with their comprehensive understanding of the electrochemical processes,
support results in binding energies of hydrogen as well as hydroxide and their characteristic effects over the photocatalytic surfaces. Various
moieties, which are majorly attributed to enhanced catalytic activity, new technologies and subsequent catalysts would furnish applications
based on H2 chemisorption data and X-ray and ultraviolet photoelectron and provide new knowledge in excelling in the field of research. Upon
spectroscopy. The Ni-based hydrogen oxidation reaction catalyst used in the considerable understanding of the photocatalytic applications and
this platinum group metal-free hydroxide exchange membrane fuel cell the storage of energy using fuel cells technology is highly considered and
produces a peak density of 488 mW cm-2 [259]. possesses many industrials as well as the research orientation. The
To increase efficiency and tunability, Suleyman et al. created development of stable materials possessing controlled size, pore size,
photonic-based functional integrations for cutting-edge optoelectronic etc. would make the thin films utilized over energy generation over the
devices. This study reported the key outcomes of practical and theo­ industries due to their wide range of light absorption, they can be uti­
retical evaluation of optical as well as electrical evaluation when a one- lized in other potential applications such as Solar cells, gas sensors, CH4
dimensional photonic crystal with a functional design was integrated production, HCOOH generation. Various research and development ef­
into CdTe solar cells. Re-harvesting is made better by raising absorbance forts are ongoing to optimize their performance and unlock their po­
because the photonic band gap created by (MgF2/MoO3)N 1D-PC re­ tential in industries over energy-related applications.
duces the transparency of the CdS/CdTe heterojunction-based solar cell.
The photocurrent density and period number at the 850 nm resonance 5. Thin films for biomedical applications
wavelength significantly affect the inquiry. The photonic band gap re­
gion’s reflectance is sufficient for photon harvesting for four cycles Over the last decade, there has been a tremendous increase in the
before saturation sets in. The photovoltaic performances of SCs pos­ need for innovative thin film materials for biomedical applications such
sessing both with as well as without 1D-PC generated at optimal levels as dental wires, orthopedic implants, orthopedic artificial joints, bone
are compared and analyzed. Apart from short-circuit current density and plates, interventional treatment, cardiovascular stents, pacemakers,
maximum current density varying from 15.86 to 17.23 mA cm-2 and heart valves, and other surgical devices [48,105,261]. The materials
13.08-15.41 mA cm-2, the open-circuit voltage remains constant. The used in the biomedical field should be nontoxic, inert to the body’s
conclusion revolves around the fact that FF, as well as the power con­ environment, highly resistant to corrosion and wear, lightweight, have
version efficiency, increased from 55.27 to 63.35% with enhanced ef­ high strength, inhibit bacterial adherence, biocompatible, and not
ficiency of 15.91%, from 8.26 to 10.47%, and improvement of 21.10% induce any allergic reactions in the body [52,104]. Moreover, the sur­
when the 1D-PC is integrated into the structure [260]. face, mechanical, and biological properties of these materials have a
Significant progress has been achieved in utilizing sputter-coated vital role in cell adherence, and as a result, can impact cell proliferation
materials as photocatalysts for energy applications. The technique en­ and differentiation [262–264]. For biomedical implants and stents,
ables the production of catalytic supports for metal nanoparticles, various alloys such as stainless steel, cobalt‑chromium alloys, magne­
benefiting energy harvesting, conversion, and storage. Critical factors sium alloys commercially pure Ti and Ti-6Al-4 V alloys are extensively
affecting efficiency include pressure, coating time, enhancing surface employed [47,265]. However, the major issue with these implant ma­
parameters, active sites, and electron-hole recombination dynamics. terials is their biocompatibility and highly corrosive behavior [263]. To
Fabrication of photocatalysts or nanoparticles with desired photo­ overcome the aforementioned issues, various thin film coating materials
stability and chemical properties is crucial. Sputter coating is highly have been investigated for the improvement and development of
efficient in developing electrocatalysts with photocatalytic applications biomedical devices and applied for orthopedic and dental implants,
for clean fuel generation. However, achieving high conversion efficiency tissue regeneration, and coronary stents. Furthermore, sputter-coated
requires a thorough investigation of particle sizes, active site formation, thin films have also been reported for cancer treatment by incorpo­
and structural properties. Flexible parameters like density, pattern, and rating drugs into thin films for controlled release.
deposition of electrocatalysts via sputter coating are vital. Future
research should focus on cathode/anode selection, electrolytic solutions, 5.1. Orthopedic implants
and nanostructure control for next-gen energy devices. Efforts must
emphasize well-defined nanostructures, understanding electrochemical Implants are artificial or natural materials designed to replace the
processes, and optimizing catalytic surfaces. These advancements hold broken and non-functional parts of the human body. The implants are
promise for various applications including solar cells, gas sensors, projected to sustain at least 15 to 20 years in older patients and >20
methane production, and formic acid generation, driving ongoing years in younger ones. They serve as a channel for interaction with the
research and development in energy-related industries. surrounding cells and tissues once implanted in the body. Therefore, the
The particle sizes and their active site formation need to be thor­ selection of material is a critical step in developing appropriate ortho­
oughly investigated to improve the structure and the chemical stability pedic implants. The implant material should possess superior properties
properties over the catalytic surface. The flexibility and the elasticity such as low density, good corrosion, and wear resistance, strong
parameters would also cover the density, pattern, and deposition of the bonding, similar elastic modulus to natural bone, biocompatibility,
electrocatalyst over the thin films using the sputter coating technique. durability, and good antibacterial activity to avoid infections [93,266].
The cathode and anode selection along with the electrolytic solution The enduring stability of these implants hinges on a robust connection
suitable for the consistent material with major active sites and visible between bone cells and the implant, referred to as osseointegration

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R. Garg et al. Advances in Colloid and Interface Science 330 (2024) 103203

[267,268]. After implantation, the first issue is protein adsorption on the cytotoxicity, and hemocompatibility, thereby viable option for
implant surface. The interface between the implant and the proteins acts numerous implant medical devices.
as a mediator of a good proliferation of the cells [269] Therefore, the In the most recent study, Lukose and his colleagues developed thin
adsorption of protein on the material surface determines processes like films of TiO2 and gold oxide on Ti6Al4V and glass substrates, and they
cell growth, differentiation, and extra-cellular matrix formation compared the impact of in-situ substrate heating and ex-situ post-
[266,270]. Another significant factor to consider while choosing an deposition heat treatment on the evolution of mechanical properties and
implant material is its affinity for bacteria and plaque. To date for biocompatibility performance in Ti–Au films (Fig. 19a(i)). The
orthopedic-related implantation ceramics/bioceramics, polymers, and maximum hardness of 8.8 GPa, 11.9 GPa, and 12.3 GPa was achieved as
metals have been employed. In another study, Das and his team [271] grown, in situ, and after ex-situ heat treatment [277]. Fig. 19a(ii) reveals
also investigated that the coating of hydroxyapatite on medical grade that all Ti–Au thin films were found to be extremely biocompatible and
UNS S31254 stainless steel possesses desirable surface properties for did not hurt L929 murine fibroblast cells. However, after a long 168-h
orthopedic implant applications. The desired level of crystallinity and extraction time, the cell survival levels in Au-rich thin films (S0.53 and
uniformity in the coatings was successfully achieved through post- S0.70) were slightly reduced (20%). However, according to ISO 10993-5
deposition annealing. AFM confirmed the surface roughness of the (2009), samples are only deemed cytotoxic when they result in a
coatings, which is conducive to enhanced cell growth and proliferation. decrease in cell viability of <30%; as a result, these are noncytotoxic and
Furthermore, the coatings exhibited superior adhesion strength, regarded as biocompatible. The hardness performance >12 GPa and
remarkable antibacterial properties, and notable bioactivity. However, excellent biocompatible coating were found to be suitable for next-
the coatings of ceramic and polymer materials do not possess the generation lifetime orthopedic implants. The above studies revealed
appropriate properties for implantation [272]. that the nanocrystalline multilayer composite coatings have attracted
Therefore, metallic implants made of titanium, Ta, chromium, co­ the attention of researchers owing to improved mechanical properties,
balt, and stainless steel have been investigated for orthopedic implants tribological performance, and excellent biocompatibility.
for several years owing to their fascinating properties and load-bearing
capacity [266,273,274]. Brohede et al. [275] developed the crystalline 5.2. Tissue regeneration
TiO2 coating on pure Ti substrate using the DC magnetron sputtering
technique. The coatings were found to be bioactive in-vitro by the for­ Regeneration is the process of renewal and growth of new tissues by
mation of a hydroxylapatite layer on the crystalline TiO2 coating after replacing damaged tissues and organs. Tissue regeneration is based on
immersion in phosphate buffer solution for one week at 37 ◦ C. The the fabrication of functional scaffolds that are as near to the native
scratch test revealed an adhesive strength value of 1 GPa between the extracellular matrix (ECM) as feasible in terms of chemical composition,
coating and the substrate, which is more than the adhesion strength architecture, and other features [278]. ECM plays an important role in
value (34.5 MPa) recommended for a medical implant coating under many cell functions including cell adhesion, migration, proliferation,
ASTM F 1044-99. The findings revealed that this approach can create cell-to-cell interactions, and growth regulation [279,280]. Tissue
safer permanent implants such as reconstructive devices, dental im­ regeneration relies heavily on the design and manufacture of high-
plants, or spinal implants. Rahmati and his coworkers reported that performance film materials with mechanical robustness, biocompati­
using Ta2O5 coating on Ti-6Al-4 V alloy has increased adhesion from bility, durability, and antibacterial activity [281,282]. Here we briefly
0.713 N to 1.907 N by annealing and optimizing deposition parameters introduced sputter-coated thin materials used for regeneration, their
[274]. They also found that higher treatment temperatures (500 ◦ C) properties, and examples of the architecture of native tissue for optimal
improved adhesion strength by enabling Ta2O5 to penetrate deeper into repair or regeneration Thian and his team investigated the in vitro
the substrate. However, the study uncovered that inadequate bonding biocompatibility of Si-doped hydroxyapatite (Si-HA) coatings in an
strength could potentially trigger premature detachment of the coating acellular simulated body fluid [283]. The finding suggests that Si-HA
from the substrate during operation. This could lead to implant rejec­ coatings can generate carbonate-containing apatite layers. This layer
tion, adverse effects on adjacent tissues, and even potential implant promotes the adhesion, growth, and formation of new bone by osteo­
failure. Several critical coating properties, including coefficient of fric­ blasts, resulting in a mechanically strong link at the material/bone
tion, adhesion strength, surface hardness, and surface roughness, can be contact. As a result, Si-HA coatings might be a promising alternative for
detrimentally impacted by various factors, such as temperature, DC bias hard tissue replacement.
voltage, nitrogen flow rate, and DC power. One specific investigation Researchers are interested in carbon-based coatings to increase
demonstrated that the implementation of a multilayer coating involving corrosion resistance, biocompatibility, hemocompatibility, and physical
titanium, TiN, and hydroxyapatite on a Ti-6Al-4 V substrate resulted in and biological qualities. Furthermore, Qi et al., stated that sputter-
heightened surface hardness. This outcome was achieved using specific coated DLC/HA coatings on the Ti6Al4V substrate had outstanding
parameters: a DC power of 300 W, temperature set at 150 ◦ C, substrate corrosion resistance, which they attribute to the absence of micropores
DC bias voltage of 50 V, and a nitrogen flow rate of 5%. and defects within the HA coatings [56]. The incorporation of a DLC
The findings indicated that the incorporation of Ti/TiN interfacial transition interlayer yielded significant enhancements in nano hardness
thin films between the hydroxyapatite (HA) layer and the substrate led (10.4 GPa), adhesion strength (26.5 N), and corrosion resistance (icorr,
to a noteworthy enhancement in adhesion strength, with an increase of 6.34 × 10− 9 A⋅cm-2; Ecorr, − 46 mV)) within the DLC/HA coating.
44.57%. To bolster both the bonding and wear resistance properties of Additionally, when compared to a single-layer HA, the substantial
the material, a graded nano‑titanium nitride (TiN) coating was exam­ thickness of the DLC transition layer led to a reduction in the production
ined over a Ti-6Al-4 V biomaterial substrate, as highlighted in the study of hazardous metal ions by over 20%. The morphological analysis using
by Cui et al. [276]. Their investigations revealed that the graded coat­ SEM displayed in Fig. 19b(i) demonstrates the response of the DLC/HA
ing’s compositions and microstructures underwent gradual alterations coating when submerged in an SBF solution for varying durations. These
along the direction of film growth. This deliberate modification images confirm discernible fluctuations in calcium ion concentration,
contributed to an improvement in adhesion force to the substrate. The revealing the emergence of dispersed microcrystalline clusters on the
adhesion strength of the coating to the substrate determines the service coated surface. Notably, the quantity of these clusters exhibited a
life. The resistance to fracture and plastic deformation has enhanced consistent increase with the prolonged duration of immersion, as
because of the combination of TiN compound and Ti4N3-x transitional depicted in Fig. 19b(i)). The XRD spectra obtained after immersion
phase. The increase in hardness, toughness, and surface roughness was revealed the appearance of new broad peaks of carbonated HA, indi­
primarily responsible for the low friction and great wear resistance. The cating the formation of tiny crystalline bone-like apatite on the coated
nano-TiN coating has also shown high biocompatibility in in-vitro surface (Fig. 19b(ii-iii)). As a result, the development of bone-like

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R. Garg et al. Advances in Colloid and Interface Science 330 (2024) 103203

Fig. 19. (a) (i) The impact of both in-situ and ex-situ post-deposition heat-treatment on the mechanical properties; (ii) Evaluation of cytotoxic effects on L929 cells
using thin films of Ti(1-x)Au(x) [277] (b) (i-iii) Investigation of morphologies, load, and XRD spectra of the DLC/HA coating following immersion in SBF solution [56]
(c) (i) Assessment of viability and proliferation; (ii) Visualization through LM (Light Microscopy); (iii) SEM images showcasing osteoblast-like cells after 2 and 12 h of
culture on a-C and Ca/a-C films [79].

apatite increased the surface biological activity of HA, which is helpful In recent times, thin films based on titanium (Ti) have emerged as a
to cell adhesion, proliferation, growth, and bone tissue regeneration. Liu highly promising category of nano-engineered surfaces, offering an
and his colleagues developed bioactive calcium/amorphous-C compos­ impressive blend of high mechanical strength and biocompatibility. A
ite films (Ca/a-C) with varying Ca concentrations on Ti alloy substrates, study conducted by Rashid and colleagues unveiled the connection be­
which were implanted in rabbits to imitate bone tissue applications as tween the antibacterial activity of TiCu(Ag) thin films and the release of
seen in Fig. 19c(i-ii). The light micrographs (LM) and SEM images. Ag and Cu ions into the surrounding environment. The presence of silver
Fig. 19c(iii) demonstrates that osteoblast-like cells spread and prolifer­ ions was observed to disrupt bacterial cell walls by generating reactive
ated considerably better on the Ca/a-C-coated Ti alloys than on the a-C- oxygen species (ROS), ultimately leading to bacterial cell demise.
coated alloys, and they exhibit a disc-shaped morphology with cellular Conversely, lower concentrations of copper (Cu) were found to be vital
protrusions. The results showed that the cells adhered closely to the for bacteria metabolism, while elevated concentrations hindered cell
surface of the Ca/a-C films, indicating increased cell proliferation and growth and even resulted in cell death. This positions Cu as a promising
viability. Thus, the implantation investigation demonstrated that Ca/a- candidate for the development of antibacterial titanium alloys [262].
C-coated Ti alloys have excellent in vivo biocompatibility and bio- TiCu(Ag) thin films have showcased notable biocompatibility, as
tribological qualities and are the best bone tissue substitute. In a demonstrated by the favorable adhesion and proliferation of the MRC-5
similar study, multifunctional Cu/a-C:H thin films over the Ti-6Al-4 V cell line of human fibroblasts. Human fibroblasts play a pivotal role in
alloy have been fabricated. The results showed that Cu/a-C:H-coated generating and depositing ECM components, facilitating interactions
titanium implants have inhibited bacterial growth effectively [281]. between epithelial and mesenchymal cells, and offering three-
Furthermore, the films encouraged angiogenesis, osteogenesis, and host dimensional support for the settlement and mobility of other cell
response regulation, enhancing the success rate of implants. types. This significantly contributes to the architecture of specific

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R. Garg et al. Advances in Colloid and Interface Science 330 (2024) 103203

organs. Importantly, fibroblast cells exhibit heightened levels of fibro­ titanium and its alloys titanium–6aluminum-4vanadium (Ti-6AI-4 V),
nectin and fibrin, enabling swift and secure attachment to the titanium cobalt‑chromium‑molybdenum-based alloy, iron‑chromium‑nickel-
substrate. Furthermore, the resilience of TiCu(Ag) thin films to trypsin- based alloy, niobium based oxide, nitride, and carbide) [285–287], ce­
mediated cell detachment underscores their exceptional biocompati­ ramics (Al, titanium and zirconium oxide, bioglass and biodegradable
bility. These multifunctional thin films, characterized by outstanding ceramics) [283,288,289], polymers and their composites have been
biocompatibility and antibacterial properties, hold substantial promise extensively used for dental implantology [290]. Metallic implants such
for utilization in tissue engineering applications. as titanium and its alloys are used as implantable material owing to their
excellent corrosion resistance and load-bearing capacity.
Banakh et al., employed magnetron sputtering to deposit titanium
5.3. Dental implantology oxynitride coatings onto a metallic Ti target [286]. The results showed
that all coatings were far more bioactive than bare Ti surfaces as 1.2-1.4
A dental implant is a screw-like prosthetic tooth root that is times increase in cell proliferation was observed. However, bare metals
implanted into the jawbone at the location of a missing tooth. Dental deteriorate with time, and tiny wear debris produced by titanium alloys’
implants are subjected to load and fatigue cycles so they must have good poor tribological performance causes a toxicological response in the
mechanical properties which can only be obtained by using metallic body [276,291]. The properties of implant materials are further
materials [284]. The materials such as metals and alloys (stainless steels,

Fig. 20. (a) (i) Schematic representation of a dental screw in its initial state (left side) and a dental implant coated with Bioactive Glass (BG) (middle), followed by
post-deposition thermal treatment at 630 ◦ C for 3 h in an air environment (right side) (ii) Procedure illustrating the implantation and extraction of Alpha-Bio® DFI
dental screws, biofunctionalized through RF-MS, featuring bioglass coatings [288] (b) (i) Depiction of wear patterns, (ii) Potentiodynamic polarization and EIS
curves, (iii) SEM images of cultured cells, and (iv) Quantitative PCR analysis of cells cultured on the films composed of Nb [287].

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R. Garg et al. Advances in Colloid and Interface Science 330 (2024) 103203

improved by coating them with bioactive and osteoinductive (osteoin­ alloy has been frequently employed for stents because of its outstanding
ductive materials can stimulate the growth of new bone.) thin films. shape memory effect, super-elastic nature, and biocompatibility. How­
Popa and his team deposited bioactive bioglass coatings (BG) over real ever, fast dissolution of Ni ions from the surface has been demonstrated
Ti dental implant fixtures by radio-frequency magnetron sputtering in literature, which has been shown to produce toxicity, carcinogenicity,
technique as shown in Fig. 20 a(i). Further Fig. 20 a(ii) shows the sur­ and immunological sensitization. As a result, numerous attempts have
gical steps: incising the mucosa and periosteum, trepanning the cortical been undertaken to change the surfaces of NiTi- SMA to increase
bone, drilling to appropriate depths, tapping screw threads, and corrosion resistance and biocompatibility. Habijan et al. studied the
manually inserting the implants under controlled force. The combined feasibility of using magnetron sputtering to directly produce NiTi thin
SEM/electron dispersive X-ray spectroscopy studies found no evidence film stents [294]. Figs. 21a and b illustrate the process of depositing NiTi
of BG deformation from the surface of the Ti dental screws, supporting films onto cylindrical glass substrates, which possess dimensions
their excellent bonding strength. Biocompatibility tests revealed that measuring 113 mm and a thickness of 6.5 μm. This technique involved
human dental pulp stem cells may adhere to and proliferate on BG films. the utilization of three-dimensional (3D) lithography followed by wet
An ideal dental implant coating must possess high resistance to corro­ etching to fabricate NiTi tubes intended for vascular stents.
sion, acceptable strength, good biocompatibility, cell proliferation, and The specimens were then examined for biocompatibility in human
a highly protective interface between the bone cell and implant to mesenchymal stem cells (hMSC). The presence of green fluorescence on
ensure long-term stability [286]. the NiTi stent surface after a week of cell growth indicates the survival
Ceramic materials such as hydroxyapatite (HA; Ca10(PO4)6(OH)2] is and cytokine release of hMSC, and hence excellent biocompatibility
one of the most extensively used as a coating material on metallic alloys (Fig. 21c). In another study by Part et al., [101] deposited tantalum (Ta)
because it has chemical similarities to the components of bones and coatings on NiTi alloy substrates using DC magnetron sputtering. The
teeth and enhances the connections between the bone cell and implant results showed that a 5 m thick Ta coating on nano-roughened NiTi
alloy [285,292]. Surmeneva et al., utilized RF magnetron sputtering to improved bonding strength and mechanical stability. In vitro, cell
deposit nanostructured low-crystallinity HA coatings with thicknesses of adhesion and MTS assays further showed that the implanted Ta has a
170, 250, and 440 nm on acid-etched titanium substrates [60]. Using unique ability to enhance endothelial cell attachment and proliferation.
primary dental pulp stem cells and NCTC murine fibroblasts, they Furthermore, the in vitro biocompatibility of the Ta-coated NiTi sub­
investigated the in vitro cellular behavior of uncoated titanium sub­ strate was considerably improved due to the inhibition of Ni ion release
strates and deposited CaP thin films. The study indicated considerable and the formation of a permanent Ta oxide layer. In their recent study,
cell proliferation and matrix formation across the whole CaP coated Soltanalipour and Khalil-Allafi focused on investigating the in vitro
surface in contrast to uncoated titanium. Nanostructured HA coatings of corrosion resistance of novel amorphous Ta/TaxOy multilayer coatings
varying thicknesses displayed cell attachment to the surface, prolifer­ applied to self-expanding nitinol stents [50]. The coatings are smooth
ated, and formed mineralized nodules on the surface, with minimal and consistent, with no voids, cavities, or fractures. At 200 ◦ C, the Ta/
toxicity. Nowadays, researchers have paid more attention to sputter- TaxOy thin films exhibit good in-vitro corrosion resistance. According to
coated niobium (Nb) based coatings over metallic substrates for dental ICP-OES measurement, coated samples contain no nickel ions and have
implants [285,287]. Because of its outstanding biocompatibility and high radiopacity and biocompatibility.
anti-corrosion qualities, Nb has significant promise for dental applica­ Furthermore, wetting angles have a significant impact on corrosion
tions. Xu and his colleagues used magnetron sputtering to deposit Nb- properties. As illustrated in Fig. 21d, coated surfaces with a higher
based films on stainless steel disc substrates, including pure niobium contact angle demonstrated superior corrosion resistance as compared
(Nb), NbO, niobium nitride (NbN), and niobium carbide films (NbC) to uncoated surfaces. To enhance the radiopacity of Fe-Mn-C alloys
[287]. AFM images showed that NbC films have a higher wear resis­ incorporating radiopaque elements like tungsten, Ravanbakhsh et al.
tance. The potentiodynamic polarization curves and EIS data revealed employed the deposition of micrometric coatings of W-Fe-Mn-C alloy
that the NbC films have higher corrosion resistance (Fig. 20b (ii)). SEM onto Si wafers and Fe-foils [295]. In their study, a sputtering power of
images revealed cellular reorganization and cytoskeletal changes in 400 W was utilized on the Fe-13Mn-1.2C target, while on the W target,
bone marrow mesenchymal stem cells cultured on Nb-based films, with three distinct powers (100 W, 200 W, and 400 W) were employed and
distinct actin fiber patterns observed, notably absent in NbN film denoted as P100, P200, and P400, respectively. Among these variations,
(Fig. 20b(iii)). Furthermore, reverse transcription-polymerase chain sample P200 (comprising Fe-13Mn-1.2C at 400 W and W at 200 W)
reaction (RT-PCR) was used to assess the influence of the Nb-based films exhibited the most uniform morphology, the lowest roughness (RMS =
on the expression of osteogenic genes in cells (Fig. 20b (iv)). It was 3.9 ± 0.4 nm), a high corrosion rate (59.68 ± 1.21 μm/year), and
observed that the NbC film can promote the gene expression of Col–I, notable radiopacity (~6%). These attributes position sample P200 as a
Runx-2, OPN and OCN compared to the Nb, NbO and NbN films promising candidate for the development of innovative radiopaque
resulting in a higher osteogenic potential. Thus, the findings showed degradable coatings for biodegradable Fe-Mn-based stents. Further­
that NbC film may stimulate cellular attachment, mineralization, and more, it was shown that nitric oxide (NO) molecules play a significant
osteogenic differentiation, and has the potential to be used to modify the role in the modulating cellular response to biomaterials [269,293].
surface of dental implants. Surovtseva et al. [269] claimed that NiTi coated with TiO2 and titanium
oxynitride (TiOxNy) at a 3:1 N2:O2 ratio enhanced the biocompatibility
5.4. Coronary stents and hemocompatibility of vascular stents, potentially by directly
releasing NO (Fig. 21e). The endothelial cells were most compatible
Cardiovascular disease is the leading cause of death that occurs due with the abraded materials, and the endothelial cells’ efficient spreading
to blockage of blood vessels that completely impede blood flow. The led to high cell viability (76–94%), which more strongly encouraged
stents are tiny expandable mesh tubes that are used to widen blood adherence (Fig. 21f). However, sputtering NiTi magnetrons without N2
vessels and restore blood flow in the event of a vascular obstruction or with a low N2 concentration did not improve cytocompatibility.
[50,293]. When a stent is inserted in the body, its surface comes in Overall, it can be concluded from previous reports that the deposition of
contact with blood, causing protein adsorption and cell adhesion. coatings over NiTi alloy was found to be promising in enhancing the
Therefore, the performance of stents in the body mainly depends on the biocompatibility of NiTi-based stents. The results of earlier in­
physiochemical composition, mechanical properties, and biocompati­ vestigations indicate that NiTi is a well-known alloy in the medical
bility of the materials used in their fabrication [263]. For the stents sector that could be employed in orthodontic applications, a variety of
mainly corrosion-resistant metals such as Nitinol, 316 L steel, and cobalt medical equipment, and temporary or permanent vascular implants.
chromium (Co–Cr) alloy have been extensively employed [263]. NiTi

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R. Garg et al. Advances in Colloid and Interface Science 330 (2024) 103203

Fig. 21. (a) Cylindrical NiTi films are deposited both radially and axially. (b) Optical micrograph displaying thin film stents made of NiTi and (c) Fluorescence
micrograph revealing the growth of human mesenchymal stem cells (hMSCs) on the NiTi surface [294] (d) Wetting behavior comparison between uncoated NiTi
substrate and Ta/TaxOy coated samples [50] (e,f) Presentation of Nitric oxide (NO) production by EA.hy926 cells and cell viability after a six-day cultivation period.
This data corresponds to TiOx and TiOxNy coatings on both abraded and non-abraded NiTi samples [269].

5.5. Other biomedical applications the literature that mainly focus on the antibacterial, mechanical, and
biocompatibility aspects of functional coatings. Jin et al. discovered that
5.5.1. Antibacterial implant coatings the application of TiN coating alters the surface characteristics of NiTi-
One of the severe problems with implant coverings is infection at the SMA, resulting in increased roughness and improved wettability. These
surgical site. Therefore, to avoid infections, the biocompatibility and modifications contribute to enhanced fibroblast adherence and prolif­
antibacterial activity of sputter-coated thin films were improved. Wu eration. The outstanding biocompatibility demonstrated by this
and his team reported that by producing Ag and Ta co-doped amorphous approach indicates the promising potential for utilizing TiN-coated NiTi
calcium phosphate (ACP) coating films on Ti substrates via RF magne­ orthodontic archwires [261]. In 2017, Liu and his coworkers [299]
tron sputtering, the antibacterial activities were improved [296]. showed that in comparison to uncoated wires, composite archwires
Moreover, the results revealed that the addition of Ta has effectively (CAW) coated with N-doped TiO2 had the best antibacterial activity
suppressed the dissolution of ACP coating films and thus can be used as against Streptococcus mutans. The basic metals in this investigation were
coating material for biomedical devices. The gold nanoparticles coupled Ti-44.73% NiTi SMA wire, Fe-18Cr-8Ni (SS), and pure Cu. The study
with collagen molecules exhibited excellent antibacterial activity, and found that N-doped TiO2 films showed much greater anticorrosion
antioxidant function, which can be used in biological environments such ability than TiO2 films in artificial saliva, indicating that they had strong
as exposed skin wounds [297]. In a recent study, ZrC and TiC transi­ potential in practical dental therapies. A recent investigation achieved
tional metal carbides were applied to stainless steel (SS) 316 L to in­ the successful fabrication of Al-SiO2 coatings with robust binding forces
crease its bio-corrosion and antibacterial properties [46]. In an artificial on NiTi and SS archwires through the process of Physical Vapor Depo­
blood plasma solution, the coated surfaces had higher anti-corrosion sition with Metal Silicate (PVDMS) [105]. It was found that the Al-SiO2
capabilities. Strong passive oxide layers formed on ceramic carbide- coating has no noticeable cytotoxicity and that its physicochemical
coated surfaces may improve the antibacterial and corrosion resis­ characteristics significantly improve the aesthetics of the archwires.
tance properties over uncoated SS substrates. These materials are
promising for protective coatings in biomedical implants since they 5.5.3. Cancer treatment
showed highly mineralized osteoblast-like cells (Ca precipitation) on Sputter-coated thin films can also be employed in cancer treatment
coatings of TiC and ZrC on biomedical grade SS. by utilizing their capacity to encapsulate and release anticancer drugs in
a controllable manner. In the most recent study with the aid of
5.5.2. Orthodontic appliances magnetron sputtering, Coon et al. achieved a successful breakthrough by
Orthodontic appliances, brackets, and archwires are subjected to an creating micropatterned nickel titanium thin films that were infused
adverse environment that includes saliva flow, food, temperature, and with human chimeric antigen receptor (CAR)-T cells. These modified
appliance force resulting in wear and corrosion [105,298]. To achieve cells were specifically designed to target solid tumors, presenting a
the highest level of corrosion resistance, the material used to make the promising avenue for treatment [300]. The study demonstrated that the
orthodontic archwire is crucial. Several studies have been published in functionalized nitinol thin films housing T cells remain durable over

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R. Garg et al. Advances in Colloid and Interface Science 330 (2024) 103203

time without degradation. Notably, in a mouse model with incurable improving biocompatibility. However, meeting strict safety and efficacy
ovarian cancer, the cell-loaded nitinol thin films exhibited strong standards is crucial. Recent research focuses on surface modifications of
adhesion to the implantation site, facilitated rapid T cell multiplication, metallic biomaterials through coatings, aiming to alter material prop­
delivered a concentrated population of T cells directly to the tumor, and erties. This study examines mechanical, thermal, corrosion, and bio­
significantly extended animal survival. logical attributes of coatings, including hard coatings, TFMGs, DLC, and
Overall, the versatility and controllable drug-release capabilities of bioceramic coatings, each with distinct characteristics. Innovative
sputter-coated thin films open new possibilities for innovative biomed­ coating methods are needed to merge benefits and mitigate drawbacks,
ical applications. As ongoing research and advancements in thin film enhancing biocompatibility and minimizing degradation. This fosters
technology continue, these coatings demonstrate immense potential in safer and more effective biomaterials for medical use. Additionally,
revolutionizing diagnostics, orthodontic treatments, and cancer thera­ sputter-coated thin films show promise in revolutionizing cancer ther­
pies. This can substantially enhance disease management and contribute apy, offering new solutions in cancer treatment. In conclusion, the
positively to public health outcomes. extensive applications and advantages of sputter-coated thin films
across various fields highlight their significant contributions to tech­
6. Conclusion nological advancements and the potential for future innovations.

Magnetron sputtering, in particular, stands out among these methods 7. Future directions
owing to its capability to deposit a wide range of thin film materials.
However, the selection of these materials depends on the specific re­ • Exploring multifunctional thin films offers new possibilities for
quirements of the device or applications. The widely used materials diverse applications. For instance, combining electrical conductivity
mainly include metal and metal oxide-based, carbon-based, and metal with self-healing properties enhances material reliability. Addition­
nitride-based. Metal and metal oxide-based materials exhibit remark­ ally, integrating photonic-based devices with plasmonic elements,
able conductivity and semiconducting properties, making them essential waveguides, or microfluidic channels creates multi-modal devices
in the development of electronic devices, sensors, and photovoltaic cells. for manipulating light, heat, and chemical reactions simultaneously.
While carbon-based films, such as graphene and DLC, have exceptional These innovations are crucial for integrated photonics, lab-on-chip
properties, producing them on a large scale can be challenging. Metal devices, and advanced sensors.
nitride-based films are gaining popularity for their unique physical, • Improving the stability of thin films at high temperatures is crucial
chemical, mechanical, and optical properties. Among them, TiN is one of for applications in aerospace, energy, and other high-temperature
the most well-known metal nitrides for its properties, including excel­ environments. Research efforts can be focused on understanding
lent biological properties that make it suitable for orthopedic implant the underlying mechanisms of degradation at elevated temperatures
materials. and developing thin film materials with better oxidation resistance
The applications of thin films in air purification, water treatment, and mechanical properties under extreme conditions. This may
and adsorption underscore their potential to contribute to a cleaner and involve optimizing deposition, introducing protective coatings, or
healthier environment. Sputter-coating photocatalytic materials exploring advanced heat-resistant materials.
enhance the surface area-to-volume ratio, crucial for heterogeneous • Future research can target the development of thin film materials
catalysis. This facilitates high charge separation over reaction systems, with improved flexibility and transparency to meet the requirements
improving efficiency. The increased surface area and porosity enable full of flexible displays, wearable devices, and transparent conductive
pore accessibility, deactivating catalytic sites through aggregation and electrodes.
leaching, even under harsh conditions. The review suggests that the use • As environmental concerns continue to grow, researchers can work
of thin film photocatalysts has great potential for industrial applications towards developing thin film materials using sustainable and eco-
in the removal of organic pollutants from wastewater, but further friendly approaches. Additionally, exploring recyclable materials
research is needed to optimize their efficiency and enhance their surface or investigating the use of biodegradable thin films for certain ap­
area. plications can contribute to reducing environmental impacts.
Defects in the electron trapping layer, like oxygen deficiency or • Thin films play a crucial role in biomedical applications, such as
physical ones, can impede electron transport but are generally negli­ implants, drug delivery systems, and biosensors. Future research can
gible. Oxygen vacancies, the major defects created by photocatalysts, focus on improving the biocompatibility, corrosion resistance, and
play a crucial role in photocatalytic applications. Various materials, antibacterial properties of thin films to enhance their performance
including 1D and 2D metal-based and non-metal-based ones, are and safety in medical settings. Moreover, research can explore
commonly sputter-coated to enhance surface area, charge transfer dy­ innovative ways to engineer thin film surfaces for controlled drug
namics, and stability. Highly ordered 1D structures aim to improve release or targeted therapies.
charge transfer and electron-hole separation, thus enhancing efficiency • Thin film materials with excellent gas sensing and photocatalytic
in photocatalytic and photoelectrochemical processes. properties have a significant impact on environmental monitoring
Furthermore, the integration of sputter-coated thin films in fuel cell and clean energy generation.
technologies presents a promising path forward in advancing the field of • For advanced energy applications, the development of multifunc­
energy conversion and sustainable power generation. The studies also tional materials that encompass enhanced photonic band gap struc­
revealed that the fabrication of metal nanoparticles on nanofibers tures, tailored sputter-coated materials, and efficient
through the in-situ route presents challenges in understanding structural electrochemical catalysts can be a very effective study.
properties and their relationship, which ultimately impacts catalytic • To advance the field of sputter-coated thin films, researchers should
performance. Therefore, in the future researchers need to focus on adopt a comprehensive approach that explores both their synergistic
selecting suitable cathodes, anodes, and electrolytic solutions to create effects and antimicrobial applications. Understanding how these thin
consistent materials with significant active sites and visible light range films can be combined with other treatment methods, such as
adsorption. ozonation, Fenton-like reactions, or biodegradation processes, will
The biomedical field has also gained significant benefits from help enhance pollutant removal efficiency while minimizing envi­
biocompatible thin films produced through the sputter coating tech­ ronmental impacts.
nique. This advancement has notably enhanced the performance of • To enable mass manufacturing of sputter-coated thin films for
medical devices and improved patient outcomes. These films offer practical implementation, process optimization, and reducing ex­
tailored properties, corrosion resistance, and controlled drug delivery, penses solutions should be investigated. The commercial viability of

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