Preparation and Characterization

Techniques for the Nanomaterial

• Nanomaterials - have one dimension on the nanoscale, i.e., between 0.1 and 100 nm

• As size of particle decreases disorderness in the material increases. As we enter to

nanometre region quantum confinement effect comes to play. Electronic properties
changes (these are seen when electron are confined)
• Greater the surface area greater number of active sites per unit area thereby increases rate
of catalysis reaction.
• Synthesis of nanomaterials:
• Physical: Mechanical(ball milling, melt mixing), Vapour(physical vapour deposition,
laser ablation)
• Chemical: colloidal route(sol-gel), micro emulsion route, co-precipitation
• Biological: green synthesis(use of micro organisms like fungi, plant extracts, enzymes
for nanoparticle synthesis),
• .Applications: Information technology(Internet, IT based systems), Energy(solar cells,
batteries, fuel cells),Medicine(drug delivery, medical tools, diagnostic tests, Imaging),
Consumer goods(food and beverages), textile industries
• Top down and bottom up approach
Methods for synthesis of nanoparticles
 Physical Vapor Deposition
• Physical Vapor Deposition (PVD) technology consist of the techniques of arc deposition, ion
plating, resistance evaporation, electron beam evaporation, sputtering and many others.
• It is used to deposit films and coatings or self-supported shapes such as sheet, foil, tubing, etc. The
thickness of the deposits can vary from angstroms to millimeters.
• The application of these techniques ranges over a wide variety of applications from decorative to
utilitarian over significant segments of the engineering, chemical, nuclear, microelectronics and
related industries.
• modern technology demands multiple and often conflicting sets of properties from engineering
materials, e.g. combination of two or more of the following – high temperature strength, impact
strength, specific optical, electrical or magnetic properties, wear resistance, fabric ability into
complex shapes, biocompatibility, cost, etc.
• A single or monolithic material cannot meet such demand in high technology applications. The
resultant solution is therefore a composite material, i.e., a core material and a coating each having
the requisite properties to fulfil the specifications.
Physical Vapor Deposition (PVD)
• Physical vapor deposition (PVD) refers to a family of
processes in which a material is converted to its vapor
phase in a vacuum chamber and condensed onto a
substrate surface as a thin film.
• PVD can be used to produce coatings of a wide variety of
materials:
 metals G alloys
 ceramics G glasses
 semiconductors G polymers
Physical Vapor Deposition (PVD)
• All PVD processes consist of the following steps:
 synthesis of coating vapor,
 vapor transport to the substrate,
 condensation of vapors onto the substrate
surface to form a thin film.
• These steps are carried out inside a vacuum chamber, so
evacuation of the chamber always precedes the PVD
process.
 Physical Vapor Deposition (PVD)
• Pressure Units:
 1 atm = 14.7 psia = 29.92 inches Hg
 = 760 mm Hg = 760 torr = 1.013 bar
 = 1.013 x 105 Pa
• 1 Pa = 1 N/m2 = 7.5 x 10-3 torr
• The degrees of vacuum and units is shown below:
Rough vacuum 1 bar to 1 mbar
• High vacuum 10-3to 10-6mbar
• Very high vacuum 10-6to 10-9mbar
• Ultra-high vacuum < 10-9mbar = vacuum in space
Physical Vapor Deposition (PVD)
• The two most common PVD processes are:
 evaporation
 sputtering
• We have already covered the basics of
evaporation.
• For evaporation, the background pressure in the
vacuum chamber is typically ~10-6 Torr (~10-4 Pa) or
lower.
• For sputtering, the background pressure in the
vacuum chamber is typically 10-3 to 10-2 Torr (~1
Pa).
 Evaporation

• In order to evaporate a material, it must be heated to a

temperature at which its vapor pressure is 10-3 Torr or
higher.
• E.g., aluminum must be heated to 1000°C or more.
Evaporation

• There are two common ways to heat the source

material :
 resistive heating
 electron-beam heating.
• Resistive heating uses electric current flow through a
tungsten filament to heat the source material.
• The source material can be placed directly on the
tungsten filament, or it can be put in a crucible that is
heated by the filament.
Resistive heating
Deposition of thin films from resistance heated evaporation sources was the first
practical thin film deposition technique. The resistance refractory metal source is the
heart of the evaporation system
Selection of a suitable source is the critical decision in designing a resistance
evaporation process. A source is selected to meet the following process requirements:
evaporant compatibility (many important evaporants dissolve all refractory metals to
some extend), capacity and power availability. In general, sources are made of
refractory metal (Mo, Ta, W) of three design classes: coils, boats and special purpose
designs
Electron beam gun heating
• is based in the heat produced by high energy electron beam bombardment
on the material to be deposited. The electron beam is generated by an
electron gun, which uses the thermionic emission of electrons produced by
an incandescent filament.
• Emitted electrons are accelerated by a high voltage potential (kilovolts). A
magnetic field is often applied to bend the electron trajectory, allowing the
electron gun to be positioned below the evaporation line.
• As electrons can be focalized, it is possible to obtain localized heating on the
material to evaporate, with a high density of evaporation power. This allows
controlling the evaporation rate, from low to very high values, and best of
all, the chance of depositing materials with high melting point (W, Ta, C,
 Evaporation
• Evaporation from a filament-heated crucible.

Silicon Wafer

Aluminum Film

Aluminum Vapor
Evaporation
• In electron-beam (e-beam) evaporation systems, a high
intensity beam of electrons, with energy up to 15 keV, is
focused on the source material.
• Electron bombardment heats the source material to the
temperature required for evaporation.
• Heating can be restricted to the source material itself . Þ
The surroundings stay cool.
• Because pressure is so low in the vacuum chamber, in
evaporation the source material travels in a straight line
from the source to the substrate Þ shadowing
Physical Vapor Deposition (PVD)
• The mean free path, l of atoms or molecules in a chamber
at pressure P is given by

kT

2 Pd 2

• T is the absolute temperature, k is Boltzmann’s constant,

and d is the diameter of the gas atoms or molecules
• The mean free path is the average distance between
collisions in the chamber.
• The rate of formation of a surface layer is determined by the
impinging molecules ø:= P/(2ømkT)1/2(molecules/cm2sec)
where m is the mass of the molecule
Physical Vapor Deposition (PVD)
• At room temperature and for a typical atom/molecule
diameter of 4 Å, the previous equation becomes
3
5.8  10
 ( m)
P
• The pressure P is in pascals (Pa).
• 1 Pa = 1 N/m2 = 7.5 ´ 10-3 Torr
• What is the mean free path for typical evaporation and
sputtering conditions?
• Advantages
• High-purity films can be deposited from high-purity source material. Source of
material to be vaporized may be a solid in any form and purity.
• The line-of-sight trajectory and "limited-area sources" allow the use of masks to
define areas of deposition on the substrate and shutters between the source and
substrate to prevent deposition when not desired.
• Deposition rate monitoring and control are relatively easy.
• It is the least expensive of the PVD processes.
• Disadvantages of vacuum evaporation:
• Many compounds and alloy compositions can only be deposited with difficulty
• Line-of-sight and limited-area sources result in poor surface coverage on complex
surfaces unless there is proper fixturing and movement.
• Few processing variables are available for film property control.
• Source material use may be low.
• Large-volume vacuum chambers are generally required to keep an appreciable
distance between the hot source and the substrate.
Sputtering
• Sputtering involves a target or source material being
bombarded by high energy particles, ejecting atoms of
this material which are subsequently deposited onto a
substrate to form thin film layers.
• In sputtering, the source material is usually in the form of
a sheet or plate, called a target.
• Sputtering is achieved by bombarding the target with
energetic ions, typically Ar+.
• Atoms on the surface of the target are dislodged by this
bombardment and fly off .
• These atoms then impinge on the substrate, resulting in
deposition of a thin film.
 Chemical Vapor Deposition
• Chemical Vapor Deposition (CVD) is the formation of a
solid material (insulator, metal, or semiconductor) from
the reaction of source gases (or vaporized liquids).

• The solid material is usually in the form of coating (a “thin

film”) 20-5000nm thick (200-50,000Å or 0.02-5mm).
 CVD of Zinc Oxide (ZnO)
• A simple Chemical Vapor Deposition system for the
preparation of thin film coatings of ZnO on a substrate
(e.g., a Si or GaAs wafer) is shown:

Air

N2 + H2O +
Zn(OOCCH3)2 Wafer Exhaust

Furnace
 Chemical Vapor Deposition
• Materials deposited by CVD are usually amorphous or
polycrystalline.

• If a “clean” crystalline substrate is used, it can

sometimes act as a seed, resulting in a single crystal
deposited layer.

• A crystalline layer deposited on a crystalline substrate is

called an epitaxial layer.
 Chemical Vapor Deposition
• Examples in microelectronics -- insulators (dielectrics)

• Silica (SiO2) deposition (400-500ºC)

SiH4 + O2 ® SiO2 + 2H2

• Silicon Nitride (Si3N4) deposition (700-800ºC)

3SiH4 + 4NH3 ® Si3N4 + 12H2
LPCVD Systems