Physical Method

Thermal evaporation Sputtering Ion-plating

•Resistance heating •DC sputtering •Plasma ion

•Sublimation source •RF sputtering plating
•Cathodic arc ion
•Induction heating •Magnetron
plating
•e-beam deposition sputtering
•ICB technique
•Laser beam •Ion-beam
deposition sputtering
•Arc evaporation •ECR sputtering

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 What is Evaporation Method?
Thermal evaporation of source material and its transport to the
substrate within a high vacuum environment

heating

-2-
 Deposition by Evaporation

• Direct evaporation

• Reactive evaporation
Ti + C2H2 → TiC + H2
Ti + O2 → TiO2
Zn + O2 → ZnO

• Multisource evaporation

Two-source evaporation arrangement vapor pressure in pure metal

yielding variable film composition
≠ vapor pressure in compound

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Different types of Evaporation
Based on Hearing Sources

 Resistive Heating
Thermal Evaporation
 Inductive Heating

 Electron Beam Evaporation

 Arc Evaporation

 Laser Evaporation

-4-
 Thermal Evaporation?
A method of forming a thin film by evaporating a material by
heating using resistance of electric current flowing in a conductor
such as W, Mo, Ta, etc. to heat and evaporate the material and
form a thin film on a substrate

• Resistive Heating Evaporation

• Electron Beam Evaporation

-5-
 Thermal Evaporation?
 Resistive Heating
A method of forming a thin film by evaporating a material by heating using
resistance of electric current flowing in a conductor. W, Mo, Ta, etc. to heat
and evaporate the material

Spring Wire Wire baskets Dimpled Foil

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Electron Beam Evaporation

• Melts a materials using e-beam

• Fast deposition rate (5 nm/sec)

• Multiple deposition

• X-ray generation

• Poor step coverage.

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Source Feeding in Electron Beam Evaporation

Bulk feed Wire feed Rod feed

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 What is sputtering?

Sputtering Process

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 Sputtering System
substrate

plasma gas
target
gauge

DC/RF generator

DP/TMP Rotary pump

-10-
 Schematic of Sputtering Process

Cathode

Target

Sputtered Atoms
+ Ar+ +
Plasma

electrons +
Thin films
Substrate
Substrate holder

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 Sputtering on Alloys & Compounds
The composition of a sputtered film tends to be the same as that of the target,
Provided that :

1. The target is maintained sufficiently cool to avoid diffusion of the constituents.

2. The target does not decompose
3. Reactive contaminants are not present
4. The gas phase transport of the components is the same
5. The sticking coefficients for the components on the substrate are the same.

Think about deposition from Ni-Fe target of uniform 80:20 composition.

Sputtering yield SNi = 2.1 SFe = 1.4 High Low High Low
Yield Yield Yield Yield
material material material material
Sputtering ratio ; Ni : Fe = 80 x 2.1 : 20 x 1.4 = 86 : 14

86% of the atoms leaving the target would be Ni

compared with 80% in the target

72.7% Ni vs 27.3% Fe

target target

Before surface equilibrium After surface equilibrium

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Microstructure of Thin Films

Zone 1: (insufficient surface diffusion)

domed tops, voided boundaries

Zone T: fibrous grains

Zone 2: (surface diffusion dominant)

columnar grains

Zone 3: (bulk diffusion) equiaxed grains

Thornton, J.A. Ann. Rev. Mater. Sci. 1977. 7:239-60

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SEM images of TiN thin films on Si substrates
Films were prepared by sputtering method
50 W 50 W

power
300nm 300nm

200 W 200 W

300nm 300nm

2 mTorr 10 mTorr

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 Why RF Sputtering ?
DC methods can not be used to sputter Non-conducting targets
 Conducting Targets
The ions reaching the cathodes are supplied with electrons
from the cathode and are reduced to a netural normal atom
or molecule

 Insulating Targets
• Ions accumulate on the cathode surface because they
can not provide electrons to the ions that reach the
cathode
• When a lot of ions are accumulated, the surface of the
cathode becomes a positive potential, ions can no longer
come in, and the electric equilibrium state inside the
plasma is broken, so that the plasma disappears within a
few microseconds. ( t ≒ 1~10 μs )

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Why RF Sputtering ?
A RF sputtering system can be used to deposit
conducting, semiconducting, insulating coatings

Discharge circuit

Electrical Equivalent

Time dependence of V

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 Self DC Bias of RF Electrodes
AC glow discharge circuit

Schematic of a high frequency glow discharge circuit Voltage and target current waveforms

Va : applied voltage
Vb Negative shift
C : capacitance of insulating target
Net current = 0
Vb : voltage of blocking capacitor

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 Magnetron Sputtering
A method of increasing the sputter yield by locating permanent magnets on the back
surface of the target and locally gathering electrons emitted from the target in a
magnetic field by forming a magnetic field to accelerate collision with Ar atoms

N S N

Cathode

Target

Sputtered Atoms
+ Ar+ +
Plasma

electrons +
Thin films
Substrate
Substrate holder

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Movement of electrons in E & B Fields

-19-
Pulsed Laser Deposition

-20-
Different Types of Chemical Method

Solution Plating CVD

Sol-gel Electroplating APCVD

Hydrothermal Electroless LPCVD

Solvothermal PECVD
Chemical Bath Deposition MOCVD

PCVD

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 Types of Plating
Plating: a surface covering in which a metal is
deposited on a conductive surface.

Electroplating: an ionic metal is supplied with

electrons to form a non-ionic coating on a
substrate.

Electroless plating: as chemical or auto-catalytic

plating, is a non-galvanic plating method that
involves several simultaneous reactions in an
aqueous solution, which occur without the use of
external electrical power.

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 Classification of Solution Methods
Electrodeposition

Bath-based Photochemical

SILAR Process
Non-Vacuum
Spray pyrolysis Ball-milling
Solution Methods Pure Solution Based
(sol-gel like process)
Hot-injection
Direct Liquid Particle Dispersed
Deposition (Ink/Slurry Formation)
Hydro/Solvo
thermal
Mixed Solution-Particle*
Microwave
assisted
*IBM-Champion Cell

-23- Lab.
 Classification of CVD

Parameters Types
Source Gases MICVD, MOCVD
Temperature Range Low, Medium, High
Deposition Pressure Atmospheric, Low Pressure
Reactor Geometry/Wall Temp. Hot Wall, Cold Wall
Energy Source Thermal, Plasma, Photon
Horizontal, Vertical, Barrel,
Reactor Continuous, Buried,
Rotational

-24- Lab.
 Classification of CVD

CVD

APCVD LPCVD
Pressure

Thermal Thermal Photon

Energy PECVD
CVD CVD CVD

Heating Hot Wall Cold Wall Hot Wall Cold Wall Hot Wall Cold Wall

Reactor Horizontal Continuous Horizontal Vertical Horizontal Barrael

Buried

-25- Lab.
 Schematic of CVD Process
A method of forming a nonvolatile solid thin film on a substrate by reacting gaseous
gases having components of the thin film to be formed on the substrate without
changing the properties of the substrate

α (Gas) + β (Gas) + … => A (Solid) + B (Gas) + …

5
1

3 기판
2 4

SiH4 Si H2(g)
-26-
Solution Deposition Method
Pb(CH3COO)23H2O Ti[(CH3)2-CHO]4

Mixing in a solvent (CH3OCH2CH2OH)

Spin-coating or dip-coating

amorphous phase
Decomposition (pyrolysis)
formation

crystalline phase
Crystallization (annealing)
formation

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Spin Coating Method

-28-
Hydro/Solvo-thormal Synthesis

• Soluble precursors
• Teflon lined vessel
• 80°C to 200°C
• Benefits
– Low cost
– Minimal waste
– Ease of production

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Chemical Bath Deposition

Zn source S source
(Zn acetate) (Thiourea)

substrate

substrate
Characterization
• XRD
• SEM
• XPS
• TEM
• UV-Vis

HotHeating 80ºC
plate and stirrier
60ºC
-30-
 Plating
Plating is a surface covering in which a metal is deposited on a conductive surface.

-31-
 Electroplating
Electroplating is a process that uses electric current to reduce dissolved metal
cations so that they form a thin coherent metal coating on an electrode

32
-32-
 Electrodeposition
Electrodeposition may refer to:
Electroplating, a process that uses electric current to reduce dissolved metal cations
so that they form a coherent metal coating on an electrode
Reaction at Cathode (Electrodeposition) Reaction at Anode

Cu2+ + In3+ + 2 HSeO3- + 10 H+ + 13 e- - + (Oxidation)

→ CuInSe2 + 6 H2O potentiostat H2O → ½ O2 + 2 H+ + 2 e-

e- e-
Reference Electrode

Cathode

Anode
Platinum Electrode
Working Electrode

Na+
Cu2+
HSeO3-
In3+
Cl-
Ga3+

H2O, H+ Electrolyte

33
-33-
Electroplating VS Electroless Plating

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