ALD Theory and Process

Precursor Requirements
Deposition Advantages
Comparison to CVD Process
Applications

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 What is ALD?
ALD (Atomic Layer Deposition)
Deposition method by which precursor
gases or vapors are alternately pulsed on
to the substrate surface.
Precursor gases introduced on to the
substrate surface will chemisorb or
surface reaction takes place at the surface
Surface reactions on ALD are
complementarity and self-limiting
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 ALD Example Cycle for Al2O3 Deposition
Tri-methyl Methyl group
aluminum (CH3)
Al(CH3)3(g)

Al
H
C Hydroxyl (OH)
H from surface
adsorbed H2O
H

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
After placing the substrate in the reactor, Trimethyl Aluminum (TMA) is pulsed into the
reaction chamber 3
 ALD Cycle for Al2O3
Methane reaction
product CH4

H
Reaction of
TMA with OH H C
H
H H H

H C C H
H
Al

Substrate surface (e.g. Si)

Trimethyl Aluminum (TMA) reacts with the adsorbed hydroxyl

groups, producing methane as the reaction products

Al(CH3)3 (g) + : Si-O-H (s) :Si-O-Al(CH3)2 (s) + CH4

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 ALD Cycle for Al2O3

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. 5
 ALD Cycle for Al2O3

After the TMA and methane reaction product is

pumped away, water vapor (H2O) is pulsed into the
reaction chamber. 6
 ALD Cycle for Al2O3

H2O reacts with the dangling methyl groups on the new surface
forming Aluminum-oxygen (Al-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
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 ALD Cycle for Al2O3

The reaction product methane is pumped away. Excess

H2O vapor does not react with the hydroxyl surface group,
again causing perfect passivation to one atomic layer.
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 ALD Cycle for Al2O3

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

2 H2O (g) + :O-Al(CH3)2 (s) :Al-O-Al(OH)2 (s) + 2 CH4 9
 ALD Precursor Requirements
Must be volatile and thermally stable
Preferably liquids and gases
Should Chemisorb onto the surface or rapidly
react with surface and react aggressively with
each other
-Short saturation time, good deposition
rate, no gas phase reactions
Should not self-decompose
- Affect thickness, uniformity
Should not etch, dissolute into film or substrate

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 Deposition Advantages
Alternating reactant exposure creates unique
properties of deposited coatings:
Thickness is determined simply by number of deposition cycles

Precursors are saturatively chemisorbed stochiometric films

with large area uniformity and 3D conformality

Intrinsic deposition uniformity

Low temperature deposition possible

Gentle deposition process for sensitive substrate

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 Comparison of ALD and CVD
ALD
Highly reactive precursors
Precursors react separately on
the substrate
Precursors must not
decompose at process
temperature
Uniformity ensured by the
saturation mechanism
Thickness control by counting
the number of reaction cycles
Surplus precursor dosing
acceptable
CVD
Less reactive precursors
Precursors react at the same
time on the substrate
Precursors can decompose at
process temperature
Uniformity requires uniform
flux of reactant and
temperature
Thickness control by precise
process control and monitoring
Precursor dosing important
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 ALD Applications summary
Piezoelectric layers (ZnO, AlN, ZnS)
High-k dielectrics (Al2O3, HfO2, ZrO2, Ta2O5, La2O3,) Transparent Electrical Conductors (ZnO:Al, ITO)
for transistor gates and DRAM capacitors in Si,
GaAs, Heterostructures, compound
semiconductors, Mesfets, III-V Semiconductor UV blocking layers (ZnO, TiO2)
materials, organic transistors, graphene,
graphite, nanotubes, nanowires, molecular OLED passivation (Al2O3)
electronics,
Solid Lubricant layers (WS2, )
Conductive gate electrodes (Ir, Pt, Ru, TiN, )
Photonic crystals (ZnO, ZnS:Mn, TiO2, Ta2N5, )
Metal interconnects and liners (Cu, WN, TaN, coatings inside porous alumina, inverted opals
WNC, Ru, Ir)
Metallic diffusion barrier layers for copper Anti-reflection and optical filters (Al2O3, ZnS, SnO2,
interconnects and semiconductor vias for Ta2O5)
transistor gate and memory cell applications,
DRAM capacitors, Passivation layers Fabry-Perot, Rugate, Flip-Flop optical filters

Catalytic materials (Pt, Ir, Co, TiO2, V2O5) Electroluminescent devices (SrS:Cu, ZnS:Mn, ZnS:Tb,
Coatings inside filters, membranes, catalysts (thin SrS:Ce)
economical Pt for automobile catalytic
converters), fuel cells ion exchange coatings Processing layers (Al2O3, ZrO2,
Etch barriers, ion diffusion barriers, fill layers for magnetic
Nanostructures (all materials)
read heads
Conformal deposition around and inside
nanostructures
and MEMS Optical applications (AlTiO, SnO2, ZnO)
Photonics, Nanophotonics, Solar cells, integrated optics,
Biomedical coatings: (TiN, ZrN, CrN, TiAlN, AlTiN) optical coatings, lasers, variable dielectric constant
Biocompatible materials for in-vivo medical devices nanolaminates
and instruments
Sensors (SnO2, Ta2O5, )
ALD metals (Ru, Pd, Ir, Pt, Rh, Co, Cu, Fe, Ni) 13
Gas sensors, pH sensors,
 References
Cambridge NanoTech Inc., Cambridge, MA 02139 USA
www.cambridgenanotech.com/.../ Atomic%20Layer
%20Deposition%20tutorial%20Cambridge%20NanoTech
%20Inc.pdf
www.mne.umd.edu/.../465_spring_2003/465_
spr2003_final_project_results/ALD-finalpres-465-
spr2003.pdf
ICKNOWLEDGE LLC, Georgetown, MA 01833,
www.icknowledge.com/misc_technology/ Atomic
%20Layer%20Deposition%20Briefing.pdf
B.S.Lim, A. Rahtu and R.G. Gordon, Nature Materials, 2
(2003) 749-754

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