Physical mechanisms of

residual stress in metallic thin

films
- A review of the literature -

February 19th, 2008

Felix Lu

Applied Quantum Technologies / Duke University

1
 Outline
• Stresses & Strains
• Residual stresses
• Thin film formation
• Growth modes
• Mechanisms of intrinsic stress
• Effect of sputtering

2
 Stresses & Strains
Unreleased structure Released structure with stress Thermally actuated structure

http://matthieu.lagouge.free.fr/phd_project/extractor.html

• Stress (σ) = force/area Elastic region Ultimate

– Typically in Dynes/cm2, where 1 dyne = strength

10-5 N or 1 g·cm/s2 σ Plastic deformation

Yield
strength

• Strain (ε) = (∆ length)/length (%)

σ = Eε, where E is Young’s modulus ε
3
Definitions
 Stresses & Strains
in MEMS structures
• Thin film stresses ~/> Yield strength
or ultimate strength

Stoney equation for calculating

R
interfacial stress in a plate
df
1 Es ds2
σf = ds νs Es
6R (1-νs) df

σf = stress, R = radius of curvature, Es = Young’s These surfaces stretched

modulus, ds = substrate thickness, df = film
thickness, νs = Poisson’s ratio of substrate

This particular form of the Stoney equation assumes that

film thickness << substrate thickness

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Approach to analyzing films
 Types of residual stress
Extrinsic stress: due to post-deposition
processing or external influences
– Thermal property differences
– Impurity contamination
Intrinsic stress: stress in the as-deposited
film
– Caused by microstructure of the film
• Function of process parameters

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Residual stress
 Origins of extrinsic stress
• Thermal stress –
– deposition T ≠ measurement T
• Adsorption of polar molecules within
porous structure of film. Polar molecules
interact with each other which introduces
extra forces.

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Extrinsic stress
 Thin film formation
• Thermodynamics
surface free energies arguments…
• But deposition process strongly influenced by kinetics
parameters, defects, … which determine when and how
nucleation takes place…
 not in thermodynamic equilibrium
• Basically…
– Film atoms do not wet the substrate surface

Volmer-Weber growth mode
– Film atoms wet the substrate surface

Frank-Van der Merwe growth mode
– Other cases where it is in between (mixed mode)…

Stranski-Krastanov growth mode

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Materials Science
 Thin film formation
• Physical vapor deposition (PVD)

Sputtered atoms ~5-40 eV 1,2

of polycrystalline thin films
– Evaporation And hybrids and variants
– Sputtering
• Typically follow Volmer-Weber (Wikipedia)
growth patterns for lower
substrate temperatures

~0.1 eV 2
Evaporated atoms
• Epitaxial growth typically follows
Frank-van der Merwe growth Thermal
mode. evaporation

8
 Volmer-Weber growth
TEM of Ag films deposited in UHV on MgF2 coated
glass substrates

Defects, surface reconstruction, impurities

affect orientation of nuclei 3

After Koch (1994)

A simple
Film becomes
polycrystalline
continuous (percolation
grain structure
After C.V.
or network stage3)
Thompson (2004)

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Materials Science
 Percolation
Control of percolation thickness important for applications:
- Near percolation thickness, small changes in
composition, bias, temperature

large changes in electrical conductivity & optical transparency2

• delayed percolation
larger grains

• higher nucleation densities Thinner

grains are smaller percolation

higher areal coverage thickness

Increase deposition rate

Lower substrate temperature
Plasma treatment of substrate surface

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 Volmer-Weber mode
characteristics
• Non-equlibrium supersaturation
• Crystallite does not maintain equilibrium shape
(with crystal facets) due to kinetic reasons
• At percolation, film mostly continuous
• Film thickness not increased until most channels
are filled – (Ostwald ripening or similar)
• If grain size preserved
columnar growth,
otherwise, increase in lateral size of grains due
to recrystallization

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 Frank-van der Merwe and Stranski-
Krastanov mode characteristics

• Frank-van der Merwe mode

– Basically similar to Volmer-Weber mode
– “islands” are 2-D instead of 3-D
– Goes through network stage, fills in remaining
channels and then forms continuous layer
before growing next layer.
• Stranski-Krastanov mode
– Mixed modes due to extrinsic factors
• Misfit stress, interfacial alloy or compound, etc.
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 Mechanisms of intrinsic stress in
Volmer Weber growth mode
Small angle grain boundaries
• grains of differing orientations laterally touch.
• areas of reduced density
grain boundaries.
• interatomic forces try to close gap
stretch grains

tensile stress
• tensile stress ~ grain boundary area ~ 1/(grain size)
• Tensile stress larger for fine grained films.

Domain walls (special type of grain boundary)

• presumed to be due to weak film/substrate adhesion
• islands grow with same orientation since not
constrained by substrate
• atoms that fill the gaps between islands form the most
bonds at the deepest part of the gap
higher density of
atoms in gaps
compressive stress After Koch (1994)

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Intrinsic stress
 Mechanisms of intrinsic stress in
Volmer Weber growth mode
Recrystallization processes
• self diffusion allows reorganization of
disordered areas
• grains become larger (no new material added)
• tension increases a small amount as grain
boundaries are closed3,7
• due to smaller grain boundary area, as the
grain boundaries shrink, the tension between
surviving grain boundaries tends to increase.

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Intrinsic stress
 Mechanisms of intrinsic stress in
Volmer Weber growth mode
Lattice expansion mechanism
Growing droplet
Lattice expands as drop grows

Substrate lattice spacing

Only seen if adhesion and/or compression is strong

Capillarity stress

Weak adhesion allows gliding to relieve strain – Grains press against each other creating compression
until they contact each other…

See Koch paper for more details and references on lattice expansion 15
 Mechanisms of intrinsic stress in
Volmer Weber growth mode
• Impurities
– Mostly oxygen and water
– High dep rate and good vacuum to maintain “pure”
film, especially for more reactive elements.
• misfit stress
– Lattice mismatch in epitaxy, limits film thickness if a
pseudomorphic interface is desired
• solid state reactions and/or interdiffusion
– Reaction products can change volume at interface

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Intrinsic stress
 Structure-property relationship

Very thin films (~2 Å) –

lattice expansion (compressive)

Thicker films (~2-8 Å) -

small angle grain boundaries (tension)

Percolation point (~8 Å) –

tension maximum

Post-coalescence (> ~8 Å) –
compression from capillarity stress

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 Mechanisms of intrinsic stress in
Volmer Weber growth mode
Evaporated films in UHV

Relatively high melting Relatively low melting

point metals point metals
High mobility Volmer-Weber Growth
Low mobility Volmer-Weber Growth

tensile

tensile compressive

Much
smaller scale

After Koch(1994); ( Abermann) After Koch(1994); (Abermann)

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Intrinsic stress
 Mechanisms of intrinsic stress in
Volmer Weber growth mode
Influence of substrate temperature
Influence of O2 partial pressure
Cu film force vs. film thickness and time

Cr deposited in
Deposited in UHV at
UHV onto
300K onto MgF2
MgF2 coated
coated glass. O2
glass
pressure in mbars.

After Koch(1994); Abermann

After Koch(1994)

For highest O2 pressure:

Increasing Tsub resembles
1. Force maximum shifts to smaller thickness (higher
high mobility VW growth
nucleation density and smaller grain size
2. Reduced crystallization rate – many small grains
which produce tension.

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 Control of intrinsic stress by
impact energy
At low impact energies, film is not fully densified
(porous)
tensile due to grain stretching

At higher energies, the film becomes

compacted and compressive

At even higher energies, the impacted atoms

are plastically deformed (broken bonds).

Curve applies for:

1. Low deposition temperature Td
below Td/Tm ~0.1 where diffusion
based strain relief is absent.
2. No impurity stresses (e.g.
hydrogen, oxygen or water)
3. Continuous films.
After Pauleau (2001); Windischmann (1991)

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Intrinsic stress
 Structure Zone Model (SZM)
Zone 1 – little or no adatom diffusion; morphology
influenced by substrate roughness, has open boundaries
and is rather porous, with increasing porosity with
increasing pressure.
Zone T – Transitional region; fibrous structure,
limiting case of zone 1 structures with infinitely
smooth substrates
Zone 2 – surface diffusion controlled
growth, columnar crystals are roughly the
same size1,2
Zone 3 – bulk diffusion1,2

Higher pressure ~ low impact energy

Low impact energy ~ thermal evap
Higher impact energy ~ sputtering
After Thornton (1977)

Holes in zone 1 between ~3-10, and 20-30 not explained. Presumably due to lack of data in that
region?

1 micron = 1 milliTorr 21
 Effect of impurities

• Impurities act similarly to the effect of low

substrate temperature.
• Impurities concentrate at grain boundaries
• Critical impurity concentration
passivation
layer
• Passivation layer promotes secondary
nucleation

After Kaiser (2005); Barna (1995)

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 Summary
• PVD produces Volmer-Weber growth at low substrate temperatures.
• Interaction of grains, grain boundaries produce stress.
• Stress modulated by grain nucleation density
• Grain nucleation density is a function of process parameters.
• Surface mobility is a function of the melting point of metal, substrate
temperature, partial pressure
• Higher substrate temperatures promote larger grain growth
• Operational parameters are interchangeable 1,6
– E.g. using lower melting point metals ~ increase substrate temp.
– E.g. Impurities during deposition ~ decrease in substrate temp.

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 References
1. John A. Thornton, “High Rate Thick Film growth”, Ann Rev. Mater. Sci. 1977, 7:239-60
2. Norbert Kaiser, Review of the fundamentals of thin film growth, Applied Optics, 1 June 2002 Vol
41, No 16, p 3053
3. R. Koch, J.Phys. Condens. Matter 6 (1994) 9519-9550
4. Carl V. Thompson, The origin and control of residual stress in polycrystalline films for applications
in microsystems, Slides (2004)
5. Y. Pauleau, Generation and evolution of residual stresses in physical vapour-deposited thin films,
Vacuum 61 (2001) 175-181
6. H. Windischmann, intrinsic stress in sputtered thin films, J. Vac. Sci. Technol. A 9 (4), Jul/Aug
1991, p. 2431
7. Milton Ohring, The Materials Science of thin films, Academic Press 1992
8. Abermann et al.(see reference 3)
9. Barna at al., (see reference 3)
Other useful references:
• P.S. Alexopolous, and T.C. Sullivan, Mechanical properties of thin films, Annu. Rev. Mater. Sci.
1990, 20:391-420
• Jerrold A Floro, Eric Chason, Robert C. Cammarata, and David J. Srolovitz, Physical Origins of
intrisic stresses in volmer weber thin films, MRS bulletin, Jan 2002 p 19
• Brian W. Sheldon, Ashok Rajamani, Abhinav Bhandari, Eric Chason, S.K. Hong, R. Beresford,
Competition between tensile and compressive stress mechanisms during Volmer Weber growth of
aluminum nitride films, Journal of Applied Physics 98, 043509 (2005)
• Erik Klkholm, Delamination and fracture of thin films, IBM J. Res Develop. Vol 31 No 5, Sept 1987
• Frederik Claeyssens, Ph.D. Thesis, Fundamental studies of pulsed laser ablation, 2001, Dept of
chemistry, University of Bristol, UK, http://www.chm.bris.ac.uk/pt/diamond/fredthesis/
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