Physical mechanisms of residual stress in metallic thin films

- A review of the literature February 19th, 2008 Felix Lu
Applied Quantum Technologies / Duke University

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


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

• Stress (σ) = force/area
– Typically in Dynes/cm2, where 1 dyne = 10-5 N or 1 g·cm/s2

Elastic region

Ultimate strength Yield strength

• Strain (ε) = (∆ length)/length (%)


Plastic deformation

σ = Eε, where E is Young’s modulus


Stresses & Strains in MEMS structures
• Thin film stresses ~/> Yield strength or ultimate strength
Stoney equation for calculating interfacial stress in a plate 1 σf = 6R Es ds2 (1-νs) df ds df νs Es
These surfaces stretched


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


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

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.


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

Materials Science

Thin film formation
• Physical vapor deposition (PVD) of polycrystalline thin films
– Evaporation – Sputtering
And hybrids and variants
Sputtered atoms ~5-40 eV 1,2

• Typically follow Volmer-Weber growth patterns for lower substrate temperatures • Epitaxial growth typically follows Frank-van der Merwe growth mode.


Evaporated atoms ~0.1 eV 2

Thermal evaporation


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 polycrystalline grain structure
After C.V. Thompson (2004)

Film becomes continuous (percolation or network stage3)

Materials Science

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 thickness higher areal coverage
Increase deposition rate Lower substrate temperature Plasma treatment of substrate surface

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

Frank-van der Merwe and StranskiKrastanov 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.

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)


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.


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 – until they contact each other…

Grains press against each other creating compression 15

See Koch paper for more details and references on lattice expansion

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


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


Mechanisms of intrinsic stress in Volmer Weber growth mode
Evaporated films in UHV Relatively high melting point metals
Low mobility Volmer-Weber Growth

Relatively low melting point metals
High mobility Volmer-Weber Growth



compressive Much smaller scale
After Koch(1994); (Abermann)

After Koch(1994); ( Abermann)


Intrinsic stress

Mechanisms of intrinsic stress in Volmer Weber growth mode
Influence of substrate temperature
Cr deposited in UHV onto MgF2 coated glass

Influence of O2 partial pressure
Cu film force vs. film thickness and time
Deposited in UHV at 300K onto MgF2 coated glass. O2 pressure in mbars.

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

Increasing Tsub resembles high mobility VW growth

For highest O2 pressure:
1. 2. Force maximum shifts to smaller thickness (higher nucleation density and smaller grain size Reduced crystallization rate – many small grains which produce tension. 19

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)


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


Effect of impurities
• Impurities act similarly to the effect of low substrate temperature. • Impurities concentrate at grain boundaries • Critical impurity concentration layer passivation

• Passivation layer promotes secondary nucleation

After Kaiser (2005); Barna (1995)


• • • • • 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.


John A. Thornton, “High Rate Thick Film growth”, Ann Rev. Mater. Sci. 1977, 7:239-60 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, 24 1. 2.

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