Experimental Methods in

Physics
BITS Pilani V. Satya Narayana Murthy
Hyderabad Campus
Topics
Vacuum Technology
Basics
Rotary Pump
Characterization Techniques
Diffusion Pump
XRD
Turbo Molecular Pump
Electron Diffraction
Cryopump
Neutron Diffraction
Leak Detection
SPM

Thin film Deposition Resistivity Measurement

PVD, CVD Magnetic Measurements

Nucleation and Growth

Thickness Measurement

BITS Pilani, Hyderabad Campus

 Thin Film Deposition
BITS Pilani
Hyderabad Campus
Topics covered
 Physical vapor deposition (PVD)
Evaporation
Sputter Deposition
Pulsed Laser Deposition (PLD)
Molecular Beam Epitaxy (MBE)
 Nucleation and Growth
 Thickness Measurement

Text books
 Materials Science of Thin Films: Deposition and Structure, Milton Ohring
 Thin Film Phenomena, K L Chopra

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Introduction
What is a thin film?

Thin film is a solid or liquid object with one of its dimensions very much smaller
than the other two

Thin films have thickness in the range of few angstroms to micrometers

Properties of thin films strongly depends on

 Method of deposition

 Substrate material

 Substrate temperature

 Rate of deposition

 Background pressure
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Thin films are useful for the miniaturization of devices and have many

applications such as -

Magnetic thin films in the recording technology, read-write heads

Sensors

Solar cells

Reflective layers on CDs, etc

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 Fabrication of thin films
Thin Film Deposition

Vapor Phase Deposition Liquid – based deposition

Electrochemical
Physical Vapor Deposition Chemical Vapor Deposition Electroless
(PVD) (CVD) Spin coating, etc

Vacuum Evaporation

Sputter Deposition Atmospheric pressure CVD (APCVD)

Pulsed Laser Deposition (PLD) Low pressure CVD (LPCVD)

Molecular Beam Epitaxy (MBE), etc Plasma enhanced CVD (PECVD), etc

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Vacuum evaporation
Vacuum evaporation techniques -
 Thermal Evaporation
 Flash Evaporation
 Arc Evaporation
 Wire Exploding
 Induction Heating
 Electron Beam Evaporation

Three main steps –

(i) Vaporization of the material to be deposited

(ii) Transport of the vapor from source to substrate

(iii) Condensation of the vapor on the substrate

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Thermal Evaporation

Resistive heating technique Substrate

A vacuum 10-5 torr is required for the line of
sight deposition
vapors
Distance between the source and substrate is
10 - 50 cm
Boat

Evaporation Material

As the current through the boat increases, its temperature rises, melts the
evaporation material

Deposition rate is proportional to the mass transfer rate to the substrate

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 Dimpled foil
High melting point and very
low vapor pressure materials
Hairpin (tungsten, molybdenum and
tantalum) are used as boats
Wire helix

Wire basket

Disadvantages
Contamination from the boat material
Difficult to control the composition of alloys and compounds
Difficult to coat thick films
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Electron beam evaporation
Accelerating voltage 5 - 20 kV

Water cooled Cu crucibles are used

Any material can be evaporated

Rate of evaporation varies from angstroms to micrometers per second

Melt

Material
Electron beam

Crucible

Electron gun Accelerating electrode

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Advantages
Any material can be evaporated
No contamination
Deposition rate can be controlled

Disadvantages
Difficult to control the composition

Materials Science of Thin Films: Deposition and Structure, Milton Ohring

BITS Pilani, Hyderabad Campus

Sputter Deposition

 Ejection of atoms from the surface of a target by bombarding with ions

 Atoms are physically removed from the target
 When a charged particle hits the target surface ejection of –
Neutral atoms
Ions
& Electrons occurs
 The neutral atoms condense on the substrate in the form of thin film
 Ejection due to +ve ion bombardment → Cathodic sputtering

 Sputtering is a low temperature process

 Cooling is required for the target material

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 Ar atom Ar +

e-
e- Reflected ion
e-
Secondary
electron Ar + Sputtered atom

Target atoms

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Sputtering yield
The average number of atoms ejected from the target surface per incident
ion

Sputtering yield depends on -

 Mass of the incident ions
 Energy of the incident ions
 Mass of the target atoms
 Structure and composition of the target
 Temperature of the target &
 Incident angle of ions

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Glow discharge – Townsend discharge

DC voltage 1 - 5 kV
Creates
current 1 - 10 mA/cm2
Glow Discharge
Ar pressure - 10-1 - 10-2 torr

 In Glow discharge, +ve ions strike the target

 The ejected electrons from the target (called secondary electrons)

collide with the gas atoms creates +ve ions – maintains the glow
discharge

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Cathode Anode

- +

I
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 Target
Cathode glow -ve glow +ve glow Anode glow

Cathode Anode

- +

Aston
dark space Cathode Faraday Anode
dark space dark space dark space

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 Aston dark space – very thin, contains low energy electrons and
high energy positive ions, each moving in opposite directions

 Cathode glow – De-excitation of +ve ions through neutralization,

length depends on the type of the gas and the pressure

 Cathode dark space – acceleration of the electrons and ions takes

place, most of the voltage is dropped across this
The thickness of the cathode dark space is inversly proportional to
the pressure

 -ve glow – fast moving electrons creates Ar+ ions

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Self sustained glow discharge

 Low Pd values
Electron – ion collisions are few and
the secondary electron yield is too
low to sustain the ionization

 High Pd values
Mean free path is small
Electrons do not acquire sufficient
energy to ionize the gas atoms,
discharge is quenched

 In between, at typically a few hundred to thousand volts the discharge is

self sustained

Materials Science of Thin Films: Deposition and Structure, Milton Ohring

BITS Pilani, Hyderabad Campus
If gas pressure is too low or separation of the substrate and target is too small
- the secondary electrons can not undergo sufficient collisions

If the pressure and separation are high –

the ions generated are slowed down by inelastic collisions and when they hit
the target and they will not have sufficient energy to release the secondary
electrons
Large spacing - the collision of the released atoms with the gas atoms
increases and the probability of reaching the substrate decreases

The optimum conditions for uniform deposition are obtained when the
distance is about twice the length of the Cathode dark space and a plain
cathode of size twice that of the substrate is used

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 Self sustained glow discharge can not be sustained at pressures lower
than 10 mtorr

 At high pressures, film contaminates by the inert gas by trapping of gas

atoms in the film

 Trapping of the gas atoms in the film can be lowered by depositing at

low pressures

 At low pressures adhesion is good because of high mean energy of the

sputtering particles

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Sputtering Techniques
 DC sputtering
 RF sputtering
 Magnetron sputtering → DC & RF
 Reactive sputtering

Materials Science of Thin

Films: Deposition and
Structure, Milton Ohring DC Sputtering RF Sputtering
Metals Insulators
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For sputtering at pressures lower than 10 mtorr –
there should be a source of electrons other than the secondary electrons
or
the ionizing efficiency of the available electrons should be increased

The ionizing efficiency can be increased by the application of magnetic

field – Magnetron sputtering

The magnetic field makes the electrons to travel large distances by

moving them in helical path around the magnetic field lines

Magnetron process pressure 0.2 - 0.6 mtorr

Cathode potential 300 – 700 V

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Planar magnetron
E X B drift path

Magnetic field lines

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Advantages
 Uniform thin films
 Good adhesion to the substrate
 Better reproducibility of the film
 Good stoichiometry
 Control of thickness

Disadvantages
 Sputtering rate is slow when compared with the evaporation technique
 Sputtering targets are expensive
 Target cooling is required

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Pulsed Laser Deposition (PLD)

 High energetic laser is used for deposition

 Ultra high vacuum 10-9 mbar is required
 Any material can be deposited

 Laser beam is focused by a quartz lens

 The targets are arranged at an angle of 45
to the focused laser beam
 Substrate is parallel to the target
 Target to substrate distance is 2 - 10 cm

Materials Science of Thin Films: Deposition and Structure, Milton Ohring

BITS Pilani, Hyderabad Campus
 Mostly used lasers are
 Solid state NdYAG laser – 1064 nm
Pulse energy ~ 2J and pulse repetition rate; 30 Hz
 Gas excimer laser – ArF (193 nm), KrF (248 nm), XeCl (308 nm)
Energy ~ 500 mJ and pulse repetition rate above 100 Hz
 PLD is also called as pulsed laser ablation (PLA)
 Ablation – Localized evaporation of a material
 The absorbed beam energy is converted into thermal, chemical and
mechanical energy causing electronic excitation and ablation target material
 The plume formed by evaporants contain energetic neutral atoms,,
molecules, ions, electrons, atom clusters, micron sized particulates and
molten droplets, etc

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Laser pulse

Motion of solid – liquid

Melting
interface

Plume formation

Absorption of incident radiation by

plume and plasma formation
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High ablation rate – 0.01 nm per pulse
Stoichiometry is maintained → The fast and strong heating of the target
makes all the target components evaporate at the same time

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Advantages
 Source is outside the chamber
 Concentrated energy beam maintains the stoichiometry
 Reactive gases can be used
 Any material can be deposited

Disadvantages
 Expensive
 Small area deposition – highly directional plume
 Splashing of microscopic particles → rapid expansion of gas trapped under the
target, a rough target surface whose mechanically weak projections are prone to
fracturing during thermal shocks and superheating of subsurface layers before
surface atoms vaporize
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 Molecular Beam Epitaxy
(MBE)
 Epitaxy: Growth of single crystal film
 2 types –
Film
 Homoepitaxy: Film and the substrate are same material
Si on Si
Substrate

 Heteroepitaxy: Film and the substrate are different materials

AlAs on GaAs; Fe on GaAs

Film Film

Relaxation
Strained

Substrate Substrate

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 MBE: Growth of epitaxial layers in the molecular flow regime
 Single crystal film growth technique
 Controlled evaporation
 Deposition is done in ultrahigh vacuum 10-10 torr
 To reach the ultrahigh vacuum
chamber is baked at 200 C for 24 h
 Load lock is used for loading the
substrates

Basics of MBE – Fernando Rinaldi

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 Heating sources  3 types
 (i) Effusion cell, (ii) electron beam gun
& (iii) gas source
 Effusion cell or evaporation cell or
Knudsen cell: An isothermal cavity
containing a hole through which the
evaporant exits
 Ebeam gun for high melting point
materials

 Gas source for depositing P, H, O films, etc

 Multiple sources are used for different materials Basics of MBE –
Fernando Rinaldi
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 The reaction of one or more evaporated beams of atoms or molecules
on a heated crystalline substrate gives the epitaxial film
 For growing clean epilayer the surface diffusion incorporation time must
be less than the monolayer deposition time
 Growth rate: 1m/h
 Crystal defects can be avoided because of the slow growth rate
 In addition to ultrahigh vacuum system and growth techniques MBE also
contains the in situ structural and chemical characterization techniques
 Reflection high energy electron
diffraction (RHEED) – Gives
the information about the
monolayers
Basics of MBE – Fernando Rinaldi
BITS Pilani, Hyderabad Campus
Effusion cell
Pyrolitic boron nitride crucibles (up to 1400C)
 The rate of gas emission from the walls is small
Molybdenum and Tantalum  shutters and heaters

The science and engineering of microelectronic fabrication – Campbell

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Advantages
 Single crystalline films can be grown
 Purity of the films is very high and defects are less
 Insitu thickness measurement and structural characterization
 Evaporation rate of materials can be controlled for getting the composition
 Mainly useful in semiconductor industry
 Substrate temperature is not too high

Disadvantages
 Long time process
 Expensive
 Sensitive effusion cells
 Need ultrahigh vacuum
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Nucleation and Growth

Thin films are formed by the condensation of atoms from the vapor phase of
material
Vapor to solid transformation is the birth stage of thin film

TEM images of Ag films nucleation and growth

Materials Science of Thin Films: Deposition and Structure, Milton Ohring

BITS Pilani, Hyderabad Campus
Nucleation
 The crystalline nature and the microstructure of thin film depends on the
nucleation
 How the nucleation starts?
 How the vapor atoms condense?
 Condensation is determined by the vapor atoms interaction with the impinged
surface  get adsorbed by the surface
 Vapor atom or impinging atom or adatom
 The impinging atom is attracted by the instantaneous dipole moments of the
target surface
 If the KE of the vapor atom is not too high it looses its velocity component
normal to the surface
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Adsorption reactions on solid
surface

 Two types of adsorptions depending on the strength of the atomic

interactions
(i) Physisorption  Physical
Adatom retains its identity by forming van der Waals bond to the substrate
atoms
(ii) Chemisorption  Chemical
Adatom changes its identity by forming ionic or covalent bond with the substrate
atoms
Adsorption energies or adsorption heats are EP = 0.25 eV & EC = 1 – 10 eV

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Physisorbed particles
achieve equilibrium farther
from the surface than
chemisorbed particles
The adatom is chemically
adsorbed with the release of
heat of condensation →
nucleation starts
It interacts with the other
adatoms and forms a stable Equilibrium between the adsorption and
cluster desorption process gives the condensation
Materials Science of Thin Films: Deposition and Structure, Milton Ohring
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Nucleation theories
(i) Capillary or Droplet theory
(ii) Statistical or Atomistic theory

(i) Capillary theory or Droplet theory

This theory is based on the total free energy of formation of cluster of
adatoms
Nuclei are formed by the collision of adatoms on the substrate surface
Atoms at surfaces are more energetic than atoms with in the bulk
The excess energy at the surface of a material than compared with the bulk
gives the surface energy

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The free energy increases until a critical size, r* is reached
Cluster small than r* are unstable
Larger ones gives the stable deposits
Total free energy, G

G*

r*
Radius, r

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Let the critical nucleus is
cap shaped
The total free energy is

G = a1r2fv + a2r2(fs - sv) + a3r3 GV

a1r2 = curved surface area

a2r2 = project circular area on the substrate
a3r3 = volume area
Thermodynamically stable nucleus is formed if (dG/dr)r=r* = 0
This gives the critical nucleus size and the critical free energy
Materials Science of Thin Films: Deposition and Structure, Milton Ohring
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Growth of the film
3 growth modes
(i) Island or Vomer – Weber mode
(ii) Layer or Frank – Van der Merwe mode
(iii) Island - layer or Stranski – Krastanov mode

Materials Science of Thin Films: Deposition and Structure, Milton Ohring

BITS Pilani, Hyderabad Campus
Growth modes can be
understand using Young’s
equation
At equilibrium
sv = fs + fv cos
(i) Island growth
 >0
and sv < fs + fv

Surface tension or energy of the film exceeds that of the substrate

Ex: metal deposition on ceramics or semiconductor substrates

Materials Science of Thin Films: Deposition and Structure, Milton Ohring

BITS Pilani, Hyderabad Campus
(ii) Layer growth
 0
and sv  fs + fv
Ex: homoepitaxy → interface between the film and the substrate essentially
vanishes fs = 0

(iii) Island – layer growth

Initially sv > fs + fv
Film – substrate lattice mismatch creates the strains in the growing film
Strain energy dominates the fv
The release of this energy at the deposit intermediate layer interface may
trigger the island formation

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 Thickness measurement
techniques

Properties of thin films depends on the

thickness

Thickness measuring techniques can be

divided into several groups –
 Balance methods
 Mechanical methods
 Optical methods
 Electrical methods

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Balance methods
Microbalance method
This method depends on the determination of the mass of the film
The balance must be sufficiently sensitive (10-8 g/m2)
m = tA
Disadvantage: Density of the coating may be different from bulk because of
porosity or implanted ions

Quartz crystal oscillator method

Based on the change in the resonance frequency of the quartz crystal
oscillator
Resonance frequency  1/thickness of the crystal
t = 0.1 nm to 100 m; rate = 0.01 nm/s to 100 nm/s

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BITS Pilani, Hyderabad Campus
Mechanical method
Stylus profilometer
Step is required
A diamond stylus (10 m) is pulled along the surface
The step height is measured using a pickup system
t = 5 nm to 10 m

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Electrical methods

Resistance method
The film acts as one arm of bridge circuit
Resistance of the film depends on the thickness

Capacitance method
For insulating layers

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Optical methods
Applicable to both opaque and transparent films
 Interferometry
 Ellipsometry

Interferometry
 Multiple beam interferometry
 Light impinges normal to the film surface
 Interference of light from air/film interface and film/substrate interface occurs
 Instrumentation depends on the transparency of the film

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 Sharp step is required
 Optical reflectance of
the film and substrate
must be very high
 Al or Ag is evaporated to
get high reflectance
 Thickness,
t = */(2*Fringe spacing)

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Ellipsometry
Useful to measure thickness and optical properties of dielectric materials
The change in the polarization state of the light is used to measure the
properties
The light is reflected at non-normal incidence from a film surface
The name ellipsometry comes  the light becomes elliptically polarized after
passing through the medium
Two types
Multiple angle of incidence
Multiple wavelength or spectroscopic ellipsometry

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
E p  Eˆ p exp[i (t  )]


Es  Eˆ s exp(it )

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 Reflection coefficient

 - amplitude ratio between p and s

polarizations
 - phase difference that develops
between p and s components after
reflection
When film is present on the substrate similar
type of reflection coefficient equation holds
but it is more complex

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Advantages
Film thickness determinations are not limited by the wavelength of the light
because it does not rely on interference effects
Non-destructive technique
Fast measurement
Thickness other optical properties can be measured
Highly sensitive

Disadvantages
Not good for materials with low absorption coefficient
Data analysis is complex

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Film thickness uniformity
Deposition geometry
 Explains the orientation and placement of substrates
 Source-substrate geometry influences the film uniformity
Evaporation from a point source
Consider a spherical source of surface area Ae
Particles are evaporated from a small region of area dAe
Total evaporated mass is

Mass of dMs falls on the substrate of area dAs

dAc = dAs cos
dMs : Me = dAc : 4r2

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 dMs/Me = dAc/4r2
 Mass deposited per unit area of the substrate is dMs / dAs = Me cos /
4r2
 The deposition depends on the geometric orientation of the substrate
 It varies as the inverse square of the source-substrate distance
 At  = 0, substrate tangent to the surface of the receiving sphere is
coated uniformly irrespective of the placement
 Film thickness, d = dMs /  dAs

 Substrate placed tangent to the surface of the receiving sphere will be

coated uniformly irrespective of the placement ( = 0)

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Surface source
It is a superposition of many point sources
The mass deposited per unit area is

 = evaporation emission angle

 = deposition or receiving angle

Film thickness depends on  and 

Measurement of angular distribution of film thickness shows that thickness
variation, d cosn
n is a number, determines the geometry of the lobe shaped vapor cloud and the
angular distribution of evaporant flux from source

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n is large, the vapor flux is highly directed
Physically n is related to the evaporation crucible geometry
Decrease in melt depth increases the n

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Film thickness uniformity

Uniformity is a problem -
 If there are many components to be deposited
 Substrate surface area is large
 Substrate is curved

Point source
dMs / dAs = Me cos / 4r2

Thickest deposition occurs at l = 0,

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Surface source

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BITS Pilani, Hyderabad Campus
Source substrate geometry for multiple sources

Super position of solutions for two individual surface sources gives the thickness
uniformity

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By locating surface evaporant source and the substrate on the surface of a
sphere gives uniform thin films

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Substrate cleaning procedure

Glass Substrates (ITO Coated)

1. Rinse: 18.2 M DI water
2. Ultrasonic bath: 60 min, 45 C
3. Rinse: 18.2 M DI water
Rinse: Acetone
Rinse: IPA
Rinse: 18.2 M DI water
4. Dry: N2 blow gun
5. Dehydrate: Oven, 15 min, ~125 C

Silicon Substrates (SiO2 Coated)

1. Rinse: 18.2 M DI water
a. Rinse: Acetone
b. Rinse: IPA
c. Rinse: 18.2 M DI water
2. Dry: N2 blow gun
3. Dehydrate: Oven, 15 min, ~125 C

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