Nanomaterials deposition

techniques

Thermal evaporation
 Learning Outcomes
 LO1: To have a scientific understanding of processing/deposition
techniques, such as: electrochemical, evaporation, sputtering,
chemical vapor deposition.
 LO2: Ability to apply the knowledge and practical skills in the analysis
and solution of mechanical engineering problems.
 LO3: An in-depth understanding of the ranges of properties and
characteristics exhibited by the materials.
 LO4: To equip the students with skills necessary to carry out
research in advanced and emerging materials
 LO5: Have an in-depth understanding of the principles and a
knowledge of the capabilities of the different types of analysis
covered in the module.
Thin film deposition methods
Thin film deposition - Vapor deposition methods
The deposition process of a thin film can be
divided into three basic steps:

Step 1. Production of the appropriate atomic,

molecular or ionic species that are suppose to
form the thin film on the substrate

Step 2. Transport of these species from the source

to the substrate, through a medium

Step 3. Deposition/Condensation on substrate/

Adsorption of the particles on the substrate and
Thin film formation
 http://pubs.rsc.org/en/content/chapterhtml/2014/bk9781849736381-00001?isbn=978-1-84973-638-1

Thin film deposition

Step 1. Production of the appropriate atomic, molecular
or ionic species

Physical processes:
Evaporation/sublimation from a source Figure 3
Sputtering from a target CVD chemical vapour deposition

Figure 2 Sputtering
Figure 1- Thermal evaporation https://en.wikipedia.org/wiki/Sputter_deposition
 Steps in film formation
Thin films go through several distinct stages during growth,
each affecting the quality of thin film and hence it’s physical
properties.
1. Adsorption
2. Nucleation
3. Island formation
4. Coalescence
5. Continuous film

http://www.tf.uni-kiel.de
 Classification of SURFACE COATING
techniques:

1.Physical Vapour Deposition

2. Chemical Vapour Deposition (CVD)
3. Combination processes
1.Physical Vapour Deposition - evaporation of target
material either by thermal or athermal process
 Physical process (evaporation or collisional impact) by which
source atoms or molecules enter the gas phase
 A reduced pressure environment/vacuum through which the atoms or
molecules are transport to the substrate
 No chemical reactions in the gas phase and at the substrate surface

Evaporation
Sputtering

Need good vacuum for thin film growth!

1.Physical Vapour Deposition - evaporation of target
material either by thermal or athermal process

Evaporation

Sputtering

Need good vacuum for

thin film growth!
 2. Chemical Vapour Deposition (CVD)

 The gas phase of target material undergoes chemical reaction

during deposition process.
 Chemically reacted materials at the substrate surface form thin film
of product materials

Chemical Vapour Deposition (CVD)

3. Combination processes:
1. Reactive sputtering – material in gas phase reacts with oxygen,
nitrogen etc. to form oxide or nitrite film
Physical Vapour Deposition
(PVD)
Thermal Evaporation

http://physics.taskermilward.org.uk/KS4/core/html/evaporation.htm
 Thermal evaporation
Definition and brief history of thermal evaporation

Evaporation – process & steps

Evaporation – process theory

Technical description of various types of evaporation

source

Evaporation - Transport of particles to substrate

Evaporation - How to achieve uniform deposition ?

Evaporation – current limitation

 Definition and brief history of thermal
evaporation
Thermal Evaporation process involves evaporation of the source
material inside a high vacuum chamber, and then condensation of the
evaporated particles on a substrate
Michael Faraday is credited with the first experiments of thermal evaporation in
the early 1800’s
1857 - Evaporated metal wires in inert atmosphere and made a metallic thin
film
1887 – Nahrwold discovered that Joule heating may be used to evaporate the
source material to form a thin film
1935 – Carl Zeiss Company patterned an anti-reflective coating technology
based on vapour deposition
Today - Thermal evaporation is a common method of thin film ( few angstrom
to several micrometers ) deposition.
 Evaporation – process & steps

The material is heated in a vacuum

chamber until its surface atoms have
sufficient energy to leave the surface. The Step 3
vacuum allows vapor particles to travel
directly to the substrate, where they
condense back to a solid state and form a
Step2
film.

Evaporation steps:
1. Source material is evaporated Step 1
2. Transport of particles to substrate
3. Condensation of particles on substrate/ Vapours of the
material that reach the substrate surface are deposited
 Evaporation – physical fundamentals
Evaporation mechanism

Evaporation - the target material is heated up until the interatomic

bonds between atoms on the surface are breaking down and sufficiently
high vapour pressure is attained.
The probability of evaporation of atoms on the surface of matter
depends on:
1. bond-breaking energy Еλ,
2. evaporation rate
http://www.chem4kids.com/files/matter_evap.html
Evaporation rate the number of atoms of matter evaporating
per unit area in a second); is defined by:

The matter is stationary on

Nu - the concentration of atoms in solid material, a macroscopic scale—we
N2/3 = 1015 cm-2 – the concentration of atoms at the surface, know there is thermal
ν - the frequency of vibration the atoms in the lattice (atoms- oscilators), motion of the atoms and
Еλ - bond-breaking energy, molecules at any
kТu – a value that proportional to the average kinetic energy of the atoms temperature above
of the material. absolute zero

For a surface atom the transition into the gas phase is possible if:
kinetic energy of individual atoms on the surface >> the bond-
breaking energy Еλ,
Assumption: all surface atoms have the same binding energy and can
change into the gas phase with the same probability
As the temperature of the source material is increased, the
material typically goes through the solid, liquid, and gas
phases.
https://www.chem.purdue.edu/
gchelp/liquids/vpress.html

The vapour pressure that develops over a

liquid or by sublimation of a solid material,
is a function of temperature.
If both phases solid and vapour states
exist side by side in a closed chamber at
the same temperature, the equilibrium
pressure is called the vapour pressure or
the saturation vapour pressure.

Equilibrium of two phases strongly depend

on both the pressure and temperature
Pressure-Temperature diagram.
Evaporation is based on the concept that there exists a finite
“vapour pressure” above any material.

Equilibrium state - number of atoms leaving the

solid and/or liquid surface = atoms from the gaseous phase
condense
evaporation rate = condensation rate

The vapour pressure is one of the dominant physical parameters

for evaporation

Ideal gas law can describe the behavior of the gases under
vacuum/low pressure
PV= NkT = RT
P – pressure; V - volume ; T – temperature
N- Avogadro’s number
K – Boltzman constant
R ideal gas constant https://slideplayer.com/slide/8080458/
Clausius – Clapeyron relationship describe the connection between
temperature and vapour pressure for
both solid-vapour and liquid vapour phases:
𝑑𝑃 ∆ 𝑄𝐷
= (1)
Where: 𝑑𝑇 𝑇 (𝑉 𝑔 −𝑉 𝑠)
P saturation vapour pressure
T temperature of the evaporation material - phase transition temperature
QD heat of vaporization
Vg and Vs the volumes of the gas and solid phase
Vg>>Vs ; volume of vapor typically in order of magnitude larger than a solid or liquid
phase. 𝑑𝑃
If the gas is assumed ideal: =𝑑𝑙𝑛𝑃 ( 𝑑𝑒𝑟𝑖𝑣𝑎𝑡𝑖𝑣𝑒𝑜𝑓 𝑙𝑛𝑃 )
𝑃
PV = RT where we consider =
𝑑𝑇
𝑇
2
=− 𝑑
1
𝑇 ( )
B integration constant
A constant depending on the heat of vaporization and on evaporation material
Vapour pressure of selected elements
 too fast evaporation - the vapour pressure over the source is too large, vapour
particles collide with each other.
Large number of collisions at the substrate surface, a part returns to the
evaporation source.
 too high temperature of evaporation source creates vapour bubbles. The
evaporation material is ejected by splashing out of the evaporation source,
which arrives partially on the substrate, which leads to film damage.

Influence of the vapour

delivery surface of real small
surface evaporators on the
vapour stream density
distribution

a convex surface can be
formed, if the molten
evaporation material has a
high surface tension and the
crucible is not wetted.
By using an electron beam a
very high vapour pressure
over the melt can be
developed so that the vapour
delivery surface is deformed.
A concave vapour delivery
surface leads to a stronger
decrease of the vapour
stream density dispersion

If the distribution of
the vapour stream is
constrained by cold
parts of the crucible
wall, then the
influence on the
vapour stream
density distribution is
called a chimney
effect.
Technical description of various types of
evaporation source
 http://www.chegg.com/homework-help/consider-air-
Evaporation - Resistive heating composed-nitrogen-molecules-n2-concentration-n-chapter-
1-problem-11-solution-9780072957914-exc

Resistive heating is a simple electrical resistive

heat element, or filament.

Low melting point materials (gold, aluminium

(6600C), etc. ) can be easily evaporated by heating
the filament/crucible.
Tungsten (34200C) or Mo (26200C) filaments
The power required to achieve
the sufficient temperature in the holder by
Joule heating is given by:
P = I2 R
Q= I2Rt 𝐿
𝑅=𝜌 L length;
T = time 𝐴 A cross-sectional area of the
I = current material
R = resistance of the holder ; ρ electrical resistivity
http://www.mdcvacuum.com/MDCMain.aspx
 Evaporation - Resistive heating
There are numerous different physical configurations of these filaments
 boats - essentially thin sheet metal pieces of suitable high temperature
metals (such as tungsten) used for powder form materials
filament source offers the safety of low voltage, although very high
current is required, usually several hundred amps.

https://www.tedpella.com/vacuum_html/vacuum-evaporation-
sources.htm
 Evaporation - Electron beam evaporation
High melting point materials such as Ti (16680C) can be evaporated
locally with an Incident electron beam.

E-beam evap.
1. Electrons are emitted from a small and very hot filament
2. The electron beam is magnetically directed to the target/source material.
3. Electrons are smashed into a crucible containing the source material
4. Constant flow of electrons into material heats it until evaporation takes place
5. Electron bombardment heats very effectively allowing deposition of very high
temperature materials http://www.wikiwand.com/en/Electron_beam_physical_vapor_deposition
 Resistive heating E-beam

Simple, robust, and in More complex, but extremely

widespread use
Use Ta or Mo filaments to
heat evaporation source
Contamination from heated
boat/crucible
versatile
X-rays can be generated by
high voltage electron beam
Less contamination, less
heating to wafer (as only
small source area heated to
very high T)

Most compounds/alloys decompose during melting. Each

component has different vapour pressure, therefore
different deposition rate, resulting in a film with different
stoichiometry compared to the source.
 2. Transport of particles to substrate
Vacuum & atmospheric pressure

Step2

Atmospheric Pressure comes from molecules of oxygen,

nitrogen, and other gases present in air.

In vacuum systems, we remove the atmospheric gases

in an enclosed area.

Vacuum is a reduced air pressure environment.

Fewer molecules of gas result in lower pressure.

http://www.omtexclasses.com/2015/06/what-is-composition-of-air.html
 line of sight
very directional
evaporation rate = condensation rate
High vacuum increases the mean free path of the vaporized atom which enables the
movement in a straight line without the gas-to-gas collision towards the
substrate.

http://edge.rit.edu/edge/P14651/public/Miscellaneous
 2. Transport of particles to substrate
The evaporated atoms should have to compete with the residual gas atoms
Residual gas conditions:
1. The ration between residual gas and evaporated atoms should be small
2. The evaporated particles should move on straight lines
Mean free path – average distance between two collisions

http://hyperphysics.phy-astr.gsu.edu/hbase/kinetic/menfre.html
http://www.iestechsales.com/blog-0/bid/64236/High-Vacuum-Conductance-Part-1-Bigger-is-Better
 2. Transport of particles to substrate
Why Use Vacuum for Thin Films Deposition?
1.To increase the Mean Free Path
Vacuum in the chamber mean that free path of atoms in the chamber is
greater than the distance between the source and the substrate. High
vacuum is required to minimize collisions of source atoms with background
species.

2. To Remove Active and Reactive constituents

Thin film purity:
- low number of molecules of potential contaminants
– reduce or eliminate impurities incorporated during processing

Film quality and vacuum system pressure are inseparably connected.

Purity and Uniformity are the main elements in determining a film’s quality.
 3. Condensation of particles on substrate
From atom to thin film

1. Adsorption
2. Nucleation
3. Island formation
4. Coalescence
5.Thin film

The morphology is influenced by:

Substrate temperature
Deposition rate
Desorption
Bulk and surface diffusion
……….finally the thin film fully cover the substrate.
 http://slideplayer.com/slide/5677023/
Purity and Uniformity are the
main elements in determining 3. Condensation of particles on substrate
a film’s quality. How to achieve uniform deposition ?
Evaporation is a parallel processing method where it is possible to
place several substrates on the sample holder to deposit films
simultaneously
Thin thickness controlled by:
1. Evaporation flux
2. Evaporation time

Thickness uniformity is mainly influenced by the deposition

geometry. The 3 key factors are:
1. Characteristics of the evaporation source (point or surface
source)
2. position substrate inside the vacuum chamber
3. orientation of the substrate inside the vacuum chamber
1.Characteristics of the evaporation source (point or surface
source)
Point Source Surface Source

Deposition is function of: Deposition is function of:

Distance between point source and substrate Distance between point source and substrate
Geometric orientation of the substrate Geometric orientation of the substrate /
θ = 0 uniform coat emission (vapour strem) angle
 How to achieve uniform deposition ?
3. orientation of the substrate inside the vacuum chamber

2. position substrate inside

the vacuum chamber

l=h l = 2h
Micro and nano Fabrication, Tools and Processes,
d = thickness Hans H.Gatzen, Volker Saile, Jung Leuthold
d0 = maximum thickness at the substrate’s centre l=0
Less freedom of pattern/features current limitation !

Pattern Description:
Four, 1mm wide tracks with a length of 22mm. The
tracks are on a 4mm pitch. 1mm squares are also
included for alignment purposes
Coverage on steps and trenches current limitation !

Line of sight deposition means atoms travel in a straight line, generally bottom to
up vertical line, results in a poor step coverage

The Materials Science of Thin films” M.Ohring,

Micro and nano Fabrication, Tools and Processes,
Hans H.Gatzen, Volker Saile, Jung Leuthold
 Applications: Optical Reflecting coatings
 the metal reflects the light very well – about 95% for most metals
 metals are both opaque and reflective

100 nm
thickness layer

https://www.olympus-lifescience.com/fr/microscope-
http://www.4college.co.uk/a/Cd/spect.php resource/primer/lightandcolor/mirrorsintro/
 Thin film coatings
Application Material  
Optical coatings Dielectric oxides SiO2; Ta2O5; Nb2O5
Metal carbides GeC
Micromechanical devices Ferroelectric oxides Fe
Metallization metals W,
Erosion protection Metals  
Adhesion layer Metals Ti
Corrosion resistant coatings Metal carbides Ti, Ta
V carbide
Corrosion protection Metals Cr, Ti
Metal carbides Cr7C3; Cr3C2
Wear resistant coatings Metals/metal nitrides Mo, TiN
Metal carbides Cr7C3; Cr3C2
Friction reduction coatings metal nitrides TiN
Decorative coatings metal nitrides TiN
Hard coatings for machine tools / tool coatings metal nitrides ZrH, HfN
Metal carbides WC, W2C; W3C
Hard coatings for cuttings and milling Metal carbides TiC
Oxidation resistant coating for composites; Metal carbides HfC
coatings for superalloys
Protective coatings Metal carbides Ta and Nb carbide
 2. Transport of particles to substrate
Mean free path – average distance between two collisions

Mean free path: length of

the path divided by the
number of collisions.

number of collisions can be

estimated from the number of gas
molecules that were in that volume
n is number of moles of gas
𝑛𝑁𝐴 𝑛𝑁𝐴 𝑁𝐴𝑃
𝑛𝑣 = = =
𝑉 𝑛𝑅𝑇 𝑅𝑇
𝑃
PV= NkT = nRT
Ideal gas law 𝑅𝑇
𝜆
𝑁𝐴 𝑃
http://hyperphysics.phy-astr.gsu.edu/hbase/Kinetic/menfre.html
 Influence of background vacuum pressure
The chamber is evacuated to a pressure of 10-6 to 10-7 Torr

1 atm =1,013,250 dyne/cm2=14.7 lb/in2 (psi)

1 atm=760 mm Hg=760 Torr=1013 mbar
1 bar = 106 dyne/cm2=0.98692 atm=105 Pa http://www.schoolphysics.co.uk/age16-19/Electricity%20and%20magnetism/
Current%20electricity/text/Electricity_in_gases/index.html
1 Pa=1 N/mm2(ISO, SI unit)=133 Torr
 Reading material

1. An introduction to Physics and Technology of Thin films, A. Wagendristel ,

Y. Wang; 530.4175 WAG

2. Materials Science of thin films, Milton Ohring 621.38152 OHR

3. Micro and nano Fabrication, Tools and Processes,

Hans H.Gatzen, Volker Saile, Jung Leuthold

4. Handbook of Thin film Technology

Hartmut Frey , Hamid R.Khan, Springer – Verlag Berlin, 2015

5. Thin film Structures in Energy Applications, Suresh Babu, Krishna Moorthy,

Springer International Publishing, Switzerland, 2015

6. Chapter 9 Thin film deposition - http://ece.uwaterloo.ca/~bcui/

 Please Read

Sputtering
Chemical Vapour Deposition

Books
for next lecture
“The Materials Science of Thin films” M.Ohring,

“ An introduction to Physics and Technology of thin Films”

by A.Wagendristel & Y. Wang