ENSC-E131 NanoFabrication and NanoAnalysis

Thin Film deposition

Jiangdong (JD) Deng, Ph.D

Micro/Nano Fabrication Processes

Wafer
Preparation

Design

Design
Wafer Preparation
- Material Growth, cutting, polishing

Front-End
Processes

Thin Films

- LPCVD, MOCVD, MBE, ALD, wafer-bonding

(Photo)lithography

Metrology

Front-end Processes

Lithography (photo-, E-Beam, FIB)

Etch
- RIE, wet etching,

Cleaning
- Wet, plasma, O-zone

Ion
Implantation

Etch

- PVD, PECVD, ALD, LPCVD

Cleaning

Thin Films

Planarization

- Spin coating, CVD,

Test & Back End

Ion Implantation
Planarization
Test and Back-end
- Dicing/cleaver, Wire bonding, assembly

Metrology

Outline of
Thin Film Deposition
1. General characteristic and consideration of
thin film deposition
2. Physical Vapor Deposition (PVD)
Evaporation (Thermal & E-beam evaporation)
Sputtering (DC & RF sputtering)

3. Chemical Vapor Deposition (CVD)

Low-Pressure CVD (LPCVD)
Plasma-Enhanced CVD (PECVD)
Atomic Layer Deposition (ALD)

4. Other deposition Methods: Oxidization ,

10/12/2011

Jiangdong Deng

General Characteristics of Thin Film

Deposition

Conformality and Arrival Direction

Thicker deposition at outside corners
plugs gap at top before bottom is
completely full.

Directional arrival of depositing

species

Conformality and Surface Mobility

Low surface migration rate
may result in non-conformal
films and poor step coverage

High surface migration rate

results in conformal films.

Conformality is improved if surface mobility of the deposition species is

high. Surface mobility is enhanced by high temperature and ionic
bombardment, as in plasma processes, and is influenced by the
molecular species.

Film Design for Device fabrication

Choosing Right Film Deposition Methods
Suitable film properties/qualities for device and
process (design)
Step coverage, conformality, trench filling ability
Temperature required (process, device)
Deposition rate, throughput, cost, automation, etc.

Thin Film Deposition

Physical Vapor Deposition (PVD)
-Film is formed by atoms directly transported from source to the substrate
through gas phase
Evaporation (Thermal & E-beam evaporation)
Sputtering (DC & RF sputtering)

Reactive PVD
Chemical Vapor Deposition (CVD)

-Film is formed by chemical reaction on the surface of substrate

Low-Pressure CVD (LPCVD)

Plasma-Enhanced CVD (PECVD)
Atomic Layer Deposition (ALD)
Atmosphere-Pressure CVD (APCVD)
Metal-Organic CVD (MOCVD)
Other deposition Methods: Oxidization , Spin coating, Plating
10/12/2011

Jiangdong Deng

Evaporation
Crucible Load the source
material-to-be-deposited
(evaporant) into the container
(crucible)
Heat the source to high
temperature
Source material evaporates
Evaporantvapor transports to
and Impinges on the surface of
the substrate
Evaporant condenses on and is
adsorbed by the surface

Langmuire-Knudsen Relation

Uniformity on a Flat Surface

Uniform Coating

Thickness Deposition Rate vs. Source

Vapor Pressure

Deposition Rate vs. Source Temperature

Thermal Evaporation

Thermal Evaporator

Typical Boat/Crucible Material

E-beam Evaporation

E-Beam Evaporator

Comparison

Stoichiometrical Problem of Evaporation

Compound material breaks down at high temperature
Each component has different vapor pressure, therefore different deposition rate,
resulting in a film with different stoichiometry compared to the source

DC Diode Sputtering

Self-Sustained Discharge
Sheath
zone

Requirement for Self-Sustained Discharge

Deposition Rate vs. Chamber Pressure

DC Magnetron Sputtering

DC Magnetron Sputtering
Impact of Magnetic Field on Ions

DC Magnetron Sputtering
As a result

RF (Radio Frequency) Sputtering

RF (Radio Frequency) Sputtering

Comparison between Evaporation and

Sputtering

Chemical Vapor Deposition (CVD)

Film Formation Steps

1. Diffusion across stagnant layer

2. Adsorption on surface
3. Surface reaction, migration, film formation

4. Desorption of by-products
5. Diffusion of products back into
gas stream

32

Types of CVD Reactions

Types of CVD Reactions

Types of CVD Reactions

Low Pressure CVD (LPCVD)

Plasma Enhanced CVD (PECVD)

What is ALD?
Atomic Layer Deposition
a.k.a. Molecular Layering (Rus.)Molecular Layer
Epitaxy, ALE (Atomic Layer Epitaxy)
ALG (Atomic Layer Growth), etc
Invented by Russian researchers in 1960s, independently
by Finns in 1970s.
Roy Gordon group in Harvard,
Micro- processing (IBM, Intel )
Solar Cell, and other applications

In essence, a pulsed form of thermal CVD

Growth is controlled by total available precursor on surface,
rather than precursor flux and reactivity, as in regular CVD.

What about ALD?

In ALD, reactants/precursors are introduced in
alternating pulses, rather than concurrently.
First precursor is pulsed into reactor, lands on
surfaces, and forms a "monolayer", which remains as
excess precursor is purged from reactor and pumped
away.
Second precursor is pulsed into reactor, lands on
surfaces, and reacts with first monolayer, to
completion, so that first monolayer is consumed.
Growth cycle is complete, leaving ~1 angstrom of
material. Cycle is repeatedseveral times.

ALD Cycle for Al2O3 Deposition

Tri-methyl
aluminum
Al(CH3)3(g)

Methyl group
(CH3)
H
H

Methane reaction
product (CH4)

Hydroxyl (OH)
from surface
adsorbed H2O

O
Substrate surface (e.g. Si)

In air H2O vapor is adsorbed on most surfaces, forming

a hydroxyl group. With silicon this forms: Si-O-H (s).
After placing the substrate in the reactor, Trimethyl
Aluminum (TMA) is pulsed into the reaction chamber.

Al

Reaction of
TMA with OH

H
H C
H

Al

C H

O
Substrate surface (e.g. Si)

Trimethyl Aluminum (TMA) reacts with the adsorbed

hydroxyl groups, producing methane as the reaction
product.

Trimethyl Aluminum (TMA) reacts with the adsorbed hydroxyl groups,

producing methane as the reaction product.
Al(CH3)3 (g) + : Si-O-H (s)

:Si-O-Al(CH3)2 (s) + CH4

ALD Cycle for Al2O3 Deposition

Methane reaction
product CH4

Excess TMA

H
H

Al
O

Substrate surface (e.g. Si)

Trimethyl Aluminum (TMA) reacts with the adsorbed hydroxyl groups,

until the surface is passivated. TMA does not react with itself, terminating
the reaction to one layer. This causes the perfect uniformity of ALD. The
excess TMA is pumped away with the methane reaction product.

ALD Cycle for Al2O3 Deposition

H2O
H

H
H

C
Al
O

After the TMA and methane reaction product is pumped away, water
vapor (H2O) is pulsed into the reaction chamber.

ALD Cycle for Al2O3 Deposition

Methane reaction product
New hydroxyl group
Methane reaction
product

O
Al

Oxygen bridges

Al

O
Al

H2O reacts with the dangling methyl groups on the new surface forming
aluminum-oxygen (AI-O) bridges and hydroxyl surface groups, waiting
for a new TMA pulse. Again, methane is the reaction product.

2 H2O (g) + :Si-O-Al(CH3)2 (s)

:Si-O-Al(OH)2 (s) + 2 CH4

ALD Cycle for Al2O3 Deposition

O
Al

O
Al

O
Al

The reaction product methane is pumped away. Excess H2O

vapor does not react with the hydroxyl surface groups, again
causing perfect passivation to one atomic layer.

ALD Cycle for Al2O3 Deposition

H

Al
O

Al
O

Al
O

O
O
O

Al
O

Al

O
O

O O

Al
O

Al
O

Al

Al

One TMA and one H2O vapor pulse form one cycle. Here three cycles are
shown, with approximately 1 Angstrom per cycle. Each cycle including
pulsing and pumping takes, e.g. 3 sec.
Two reaction steps
in each cycle:

Al(CH3)3 (g) + :Al-O-H (s)

2 H2O (g) + :O-Al(CH3)2 (s)

:Al-O-Al(CH3)2 (s) + CH4

:Al-O-Al(OH)2 (s) + 2 CH4

ALD film control

Self-saturation process:
Film growth during a cycle is controlled by the total
reactant present rather than a flux of reactant,
depends on sufficient precursor to cover area of interest,
temperature sufficient to allow reaction to proceed,
time sufficient for each layer to react to completion.
No process MFCs, no tuning networks, no pressure
controllers, no sophisticated power supplies, no process
cooling, etc.

Exceedingly high conformality, aspect ratios from

100s to 100,000 demonstrated.
Excellent uniformity over 8" sample, 1%
Very Slow. (~6 /min)

Lining and Filling Holes by ALD

Aspect
Ratio
~50:1

ALD films
Oxides
Al2O3, HfO2, SiO2, LaO2, TiO2

Metals and pure elements

Pt, Cu, Si, Ge, Sb.

Nitrides.
Rare-Earth Oxides.

Nano-Coaxial Cable or Transistor

Conducting tungsten nitride (WN) concentrically around
insulating aluminum oxide (Al2O3) concentrically around
a conducting carbon nanotube.
WN

Al2O3 Carbon

Al2O3

WN

Oxidation of Silicon
SiO2 film growth is a key process step in manufacturing
all Si devices
Thick (- 1m) oxides are used for field oxides (isolate devices from
one another )
Thin gate oxides (-100 ) control MOS devices
Sacrificial layers are grown and removed to clean up surfaces

SiO2 film can be deposited through PVD or CVD

methods. However,
Deposited oxides tend to possess low densities and large numbers of
defect sites.
Not suitable for use as gate dielectrics for MOS transistors,
(but still acceptable for use as insulating layers between multiple
conductor layers, or as protective overcoats).

Silicon Dioxide Structure

Quartz
Density: 2.65 g/cm3

Amorphous
Density: 2.21 g/cm3

(c)

(a) Basic structural unit of silicon dioxide (tetrahedron); (b) two dimensional
representation of a quartz crystal lattice; (c) two dimensional representation of
the amorphous structure of silicon dioxide
51

The simplest method of producing an oxide layer

consists of heating a silicon wafer in an oxidizing
atmosphere.

 Dry oxide - Pure dry oxygen is employed

Disadvantage
- Dry oxide grows very slowly.
Advantage
- Oxide layers are very uniform.
- Relatively few defects exist at the oxide-silicon
interface (These defects interfere with the proper
operation of semiconductor devices)
- It has especially low surface state charges and thus make
ideal dielectrics for MOS transistors.

 Wet oxide - In the same way as dry oxides, but steam

is injected
Disadvantage
- Hydrogen atoms liberated by the decomposition of the
water molecules produce imperfections that may
degrade the oxide quality.
Advantage
- Wet oxide grows fast.
- Useful to grow a thick layer of field oxide

Comparison of Typical Thin Film

Deposition Technology

Properties of PECVD Silicon Nitride

and LPCVD Nitride
Property
Si/N ration
Density
Refractive index
Dielectric strength
Bulk resistivity
Surface resistivity
Step coverage
Thermal stability
H2O permeability
49% HF etch rate

LPCVD
0.75
2.8 3.1 g/cm3
2.0 2.1
1x107 V/cm
> 1015 - 1017 ohms/cm
>1013 ohms/cm
Fair
Excellent
Zero
8 nm/min

PECVD
0.8 1.0
2.5 2.8 g/cm3
2.0 2.1
6x106 V/cm
1015 ohms/cm
~ 1013 ohms/cm
Conformal
Variable > 400C
Low-none
150 300 nm/min

56

References
Stephen Campbell, The Science and Engineering of
Microelectronic Fabrication, Oxford Univ. Press, 1996
Silicon Processing for the VLSI Era, Vol. 1: Process
Technology by Stanley Wolf and Richard N. Tauber
Erli Chen, lecture notes for Applied Physics 298r, 2004