Atomic Layer Deposition

ENMA465
14 May 2003
Nicole Harrison
Bryan Sadowski
Anne Samuel
Kunal Thaker
 Presentation Outline
• ALD Theory and Processes
• Applications
– Focus on ALD applications in gate
dielectrics
• Equipment
• Comparisons to other Processes
• Current and Future Development
• Questions
 What is ALD?
• ALD (Atomic layer deposition) previously
known by the name ALE (Atomic layer
Epitaxy) was originated by T.Suntola in
Finland.
• 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.
 ALD
• Surface reactions on ALD are all self-
limiting.
• Self-limiting characteristics of the process
steps is the foundation of ALD.
• Two fundamental self-limiting mechanisms
in ALD: CS-ALD and RS-ALD.
• CS-ALD: Chemisorption Saturation process
followed by exchange reaction.
• RS-ALD: Sequential surface chemical
reaction.
 CS-ALD Process
• Substrate is exposed to the first
molecular precursor. The first molecular
precursor is retained on the surface by
chemisorption.

• Second precursor is introduced on to the

surface, which reacts on the surface of
the first precursor.

• Exchange reaction takes place between

the two precursors and by-products are
formed.

• Exchange reaction continues till the

second precursor reacts with first
precursor: self-limiting step.

• Final reaction is ML2+AN2→MA(film) + 2

LN

• Sequence is repeated to grow films.

 RS-ALD Process
• Promoted by chemistry between
reactive surface and reactive
molecular precursor.

• Deposition process is as a result of

the chemical reaction between
reactive molecular precursors and
substrate.

• Substrate surface is made reactive

by certain surface groups. And first
precursor is introduced to this
surface.

• The reaction now looks like this

AN + ML2 → AML +NL(A)
reaction self-saturates until AN
groups are converted to AML groups.
 RS-ALD Process
• Followed by this reaction, the first precursor is removed by inert
gas purging prior to the introduction of second precursor.

• Second precursor is introduced, which reacts with ML surface to

form
AML + AN2 → MAN + NL(B)
– Self saturates

• The surface now looks like initial surface (AN) and surface is now
ready for reaction (A). The repetition of ABAB…sequence will
deposit films.

• During each half-reaction(A&B), surface functionality changes

from one surface species to another.
 ALD Precursor
Requirements
• Must be volatile and thermally stable
• Preferrably liquids and gases
– Can be solids
• no sintering related problems
• Should Chemi-sorb on surface or react agressively with
surface groups and each other
– Short saturation time, good deposition rate, no gas phase
reactions
• Should not self-decompose
– Destorys self-limiting property
• Affects thickness, uniformity, and containation
• Should not etch, dissolute into film or substrate
– Prevents self-limiting film growth
• Examples of substrates
– Zn, Cd, S, Se, metal halides like AlCl3, TiCl4,TaCl5, Alkyls, β-
Diketonates etc [2].
 Applications
• Transistor Gate • Interconnect seed
Dielectrics layer
• MEMS • DRAM and MRAM
• Opto-electronics dielectrics
• Diffusion Barriers • Embedded
• Flat- Panel displays capacitors
– Organic Light • All thin films
Emitting Diodes
(OLED) (<90 nm)
• Interconnect • Electromagnetic
Barriers recording heads
 Applications
• Transistor gate dielectrics
– Smaller transistor sizes
• Smaller channel lengths
• Thinner gate oxide (limit
of ~2.3 nm)
• Larger leakage current
– Need for high-K dielectrics
for transistor gate dielectrics
• Will allow for the use of
thicker gate dielectrics
• Lower leakage current
• Lower power loss
 Applications
• New processes are concurrently being
developed as new materials are being
tested
• ALD provides one of the best alternatives
for depositing these new materials
– Conformality
– Uniformity
– Compositional
Control
– Thickness control
 Equipment
● Closed System Chambers
- The Reaction chamber walls
are such that they effect the
transport (trajectory, etc.) of
the precursors.
● Open System Chambers
- Dimensions of reaction
chamber do not interfere with
ALD process (very large
relative to wafer position).
● Semi-Closed System chambers
- A channel is used with the top and bottom surfaces consisting
of two separate wafers and the precursor gas is passed
through the center.
● Semi-Open System chambers
- Similar to a semi-closed system except one side is a wafer
and the other side is gas- limited.
 Equipment
• CVD conversion to ALD
– The installation of a module: facilitates fast gas switching
• ALD specific equipment
– Wafer output
– Reaction volume
– Factory Automation Basic
ALD

– Consistency
Mecha
nism

– Conformality
– Uniformity

ALD
Mode
 Equipment
• Research into more efficient equipment design continues
– PEALD/ ALD reactor developed by Genitech
Corporation

● Hf[N(CH3)2]4 as the reactant

species with an O2 plasma
and H2O
● Temperature in the range of
200-350C
● Ar is the carrier and purge
gas
● Allows for increase in the
choice of reactants
● Better film quality
● Increased deposition rates
Comparison of ALD to
CVD and PVD
• Process description
– ALD
• atomic layer-by-layer deposition process where precursor
is introduced into system, allowed to react with substrate
surface until saturation, remaining by-products or
unreacted gases are purged, process is repeated to form a
monolayer/film
– CVD
• chemical reaction between gaseous precursors in gas
phase; solid product of reaction is deposited on surface of
substrate.
– PVD
• deposition process in gas phase where source material is
physically transferred in the vacuum to the substrate
without any chemical reactions being involved
Comparison Continued
• self-limiting: gas-surface reactions occur till
surface is saturated
• Precursors are introduced into system separately
• reactions occur at the surface
• precise thickness control
• 100% step coverage even at high aspect ratios
• Films are very uniform, smooth, and stoichiometric
 Comparison Continued

• less contamination
• low pressures
– typically less than 10-6 torr
• Film thickness can be as low as 1nm
• produces amorphous films
• lower deposition temperatures
– as low as 180oC for HfO2
Comparison Continued
• slow deposition rates
because have to form
monolayer in two steps
– HfO2: dep. rate of
0.1nm/s @ 300oC
• Growth rate
– increases, reaches
a max, and
decreases slightly
as temperature is
increased
– increases with
number of cycles

Thin Solid Films, 427(1-2), p.147-151.

 Current Developments
• Materials being used
– ZrO2 , Al2O3, HfO2

• All exhibit good qualities

– thickness control
– good conformity
– excellent step coverage
 Current Developments
• High-k materials
– traps electrons between barrier gate and SiO2
– prevents burrowing of electrons through SiO2
• High barrier height
– energy required for electrons to pass from gate to
SiO2

material formula kox

silicon oxide SiO2 3.9
silicon nitride Si3N4 7
Oxynitrides SixNyOz 4-7
aluminum oxide Al2O3 9
tantalum pentoxide Ta2O5 25
hafnium oxide HfO2 30 - 40
zirconium oxide ZrO2 25
barium strontium titanate (BST) BaSrTiO3 300
 Future Developments
• HfO2-Al2O3
laminate
– Being Developed
by Samsung
– combines good
qualities of both
– Reduced current
leakage
• due to high-k of
HfO2 and high
barrier height of
Al2O3
 Future Developments
• SiN/SiO2 stack gate-dielectric
– SiO2 experiences soft-breakdown
• due to differences in thermal expansion, high
electric field, and strained Si-O bonds
– low thermal budget (≤550oC)
– lower leakage current
– higher reliability
– soft-breakdown free
• fewer wasted samples
• Reduces Boron penetration in SiO2
Future Developments
 Future Developments
• Zr(t-OC4H9)4, commonly called
ZTB being used to replace ZrCl4
as a precursor when making
ZrO2
– Cl supposed to be purged once Zr
has been reacted
– sometimes reacts with substrate
– can cause damage to whole
system
 References
• Leskela Markku,
Markku, Ritala Mikko.
Mikko. " Atomic Layer Deposition (ALD): From Precursors to
Thin Film Structures". Thin Solid films, 2002 Vol 409. PP 138- 138-139.
• Ritala Mikko.
Mikko. "Fundamentals of ALD Chemistry" presented at AVS Topical Conference Conference
on Atomic layer deposition, May 14- 14- 15. 2001 Monterey, California.
• Sneh Ofer,
Ofer, Phelps Robert et.al. “ Thin film atomiclayer deposition equipment for
semiconductor processing” . Thin solid films, 2001 Vol 402. PP 248- 248-261.
• Scott Thompson, Portland Technology Development, Intel Corp. Paul Paul Packan,
Technology Computer Aided Design, Intel Corp. Mark Sohr, Sohr, Portland Technology
Development, Intel Corp. Intel Technology Journal. MOS Scaling: Transistor Challenges
for the 21st Century. 10 April
2003.<http://www.intel.com/technology/itj/q31998/articles/art_3.htm
2003.<http://www.intel.com/technology/itj/q31998/articles/art_3.htm>. >.
• Ho-
Ho - Kyu Kang. Samsung Electronics Co., LTD. ALD high k materials for gate
gate and
capacitor gate dielectrics. ALD Conference 2002.
• ASM. The process of innovation. Pulsar. Single Wafer Atomic Layer Layer CVD. 10 April
20003. <http://
<http://www.asm.com/prod_pulsar.asp
www.asm.com/prod_pulsar.asp>. >.
• Moo-
Moo-Han Corporation. ALD System. ELFRA 7000 Series. 10 April 2003.<http://www.moo
2003.<http://www.moo--
han.com/eng/html/product_ald_2.html>.
han.com/eng/html/product_ald_2.html>.
• Dae-
Dae-Youn Kim, Kyung-
Kyung-Il Hong, Jeongseok Ha, Cheol-Cheol-Min Chang, Seung-
Seung-Woo Choi,
Choi,
Hyung-
Hyung-Sang, Park, Yong-
Yong-Min Yoo,
Yoo, Wonyong Koh and Choon-Choon-Soo Lee.Plasma Enhanced
Atomic Layer Deposition of HfO2.Genitech, Inc. ALD Conference 2002. 2002.
• Ho-
Ho - Kyu Kang, Samsung Electronics Co., LTD, San#24 Nongseo-
Nongseo Ri, Giheung-
- Ri, Giheung-Eup,
Eup, Yongin-
Yongin-
City, Gyeonggi-
Gyeonggi-Do, Korea 449-449-711
• Anri Nakajima and Shin Yokoyama, Research Center for Nanodevices and Systems,
Hiroshima University 1-1-4-2 Kagamiyama,
Kagamiyama, Higashi-
Higashi-, Hiroshima, Hiroshima 739-739-8527,
Japan
Question and Answer