Sn whisker formation as a stress-induced nucleation and growth process

Eric Chason and Fei Pei

Brown University, School of Engineering
- Whiskers have been known
about since the 1950s
- Problem has become critical since RoHS
legislation mandating Pb-free processing

(Examples from NASA website)

SEM images of whisker growing out of Sn surface

- Studied by many (apologize for leaving out attribution)

Form spontaneously
Stress is believed to be driving force
Relatively rare: only one out of 104-105
grains deforms into whisker
- Fundamental questions:
- What determines why they form at
specific sites (nucleation)?
- What controls how fast they grow?

Brown University, supported by NSF

Earlier work: showed how stress and

whisker density relate to IMC growth
Pure Sn on Cu
IMC

- Real-time measurements
- IMC volume (sample weight)
- stress (wafer curvature)
- whisker density (optical microscopy)
Results:

Sn
Cu

stress

- IMC grows continuously

- preferentially in Sn g.b.s
-rate slows with time
- Creates stress that saturates
- Onset of plastic deformation

whiskers

- Whiskers start to grow after stress

saturates (seen in SEM movies too)
Stress is driving force for whisker
growth

Chason et al, APL 2008

Si
Electrodeposited
1.2 m Sn/0.6 m Cu

Doesnt explain why whiskers grow where they do

What is different about grains that form whiskers?
Potential culprits (some of these may play a
role but are not necessary for whiskering):
Surface defects
not seen in SEM images
before whisker starts to grow
Weak oxide -

14 hrs

19 hrs
Jadhav, JOM 2010

- put hole in oxide with FIB

- hillock pops out of adjacent
region without hole
Special grain orientation
- EBSD shows that whiskering
grains (numbered) dont have
special orientation

Pei et al, APL 2012

Why do whiskers grow where they do?

Sn surface with hillocks

After stripping Sn to
expose IMC

IMC formation
-

Necessary to generate stress

But no excess accumulation

around roots of hillocks
Pei et al, JOM 2012

Surface grains
- Grain with oblique boundaries
under them (commonly seen
morphology)

- Stress-driven flux of
atoms into whisker grain

-Puts normal force

on grain boundary

- Pushes Sn out as
whisker/hillock

Smetana IEEE 2007,

also Boettinger, 2005

Where do these surface

grains come from?
Study nucleation kinetics

Problem: Cant control stress created by IMC

Use thermallyinduced stress Can be controlled by heating
Provides insight into underlying mechanisms controlling whiskers
CTE mismatch induces compressive stress in Sn since it is fixed to Si substrate.

=(Si - Sn)T
Strain proportional to temperature change
Uniform biaxial stress state

Measure stress and whisker density

simultaneously
Heating stage induces strain
MOSS system to monitor wafer curvature
Calculate stress (Stoney equation)
Optical microscope plus oblique illumination
Extruded whiskers/hillocks scatter light
Bright spots under the optical microscope.

Example: measuring stress and whisker density simultaneously

while inducing thermal stress (65 oC cycle)

 Whiskers/hillocks start to pop out after the temperature reaches ~ 60 C

 Stress relaxation becoming apparent

as temperature held constant

Stress/whisker evolution
Several regimes of evolution
1) Elastic
Stress proportional to T
No relaxation/no whiskers
2) Nucleation
Whiskers/hillocks nucleate.
Rapid stress relaxation starts.
3) Saturation
Saturation of whiskering and stress

When whiskers/hillocks start to grow, stress starts to relax although

temperature is still increasing.

Stress/whisker evolution
Several regimes of evolution
1) Elastic
Stress proportional to T
No relaxation/no whiskers
2) Nucleation
Whiskers/hillocks nucleate.
Rapid stress relaxation starts.
3) Saturation
Saturation of whiskering and stress

When whiskers/hillocks start to grow, stress starts to relax although

temperature is still increasing.

Stress/whisker evolution
Several regimes of evolution
1) Elastic
stress proportional to T
No relaxation/no whiskers
2) Nucleation
Whiskers/hillocks nucleate.
Rapid stress relaxation starts.
3) Saturation
Saturation of whiskering and stress

When whiskers/hillocks start to grow, stress starts to relax although

temperature is still increasing.

Use this approach to study 1) nucleation, 2) growth rate and 3) plastic strain

1) Nucleation rate at different temperatures (strains)

Plot of temperature, stress, whisker density and nucleation rate
Chason et al., JOM 2015

65 C
45 C

75 C

55 C

Stress saturates at same value (appr. -15 Mpa)

Different nucleation kinetics for different temperature/thermal strain
Most rapid nucleation when stress is high
- Still form at lower stress longer time, fewer number

Relate the nucleation rate directly to the stress

Nucleation rate (dN/dt) vs. time

dN/dt

30

Plot nucleation rate (dN/dt) vs.

for all measured temperatures

20
10
0

stress (MPa)

Magnitude of stress vs. time

30
20
10
0
-10

- Nucleation rate increases with driving force (stress)

- Increases with higher T

Determine energy barrier for nucleation

using classical nucleation theory
dN / dt c exp(

G * - G* is nucleation barrier
)
- c is rate of growth of critical cluster
kT

Replot dN/dt vs stress to obtain G*

G* = kT ln

dN / dt
c (T )

Choose values of c(T) to get all

data to overlap
c(T) has Arrhenius behavior:
E = 0.77eV

Results suggest stress enhances whisker

formation by reducing barrier to nucleation

2) Whisker growth rate: Dependence on stress

Measure stress during series of
thermal cycles

Measure corresponding
feature size with SEM

Determine whisker volume vs time for each temperature

Average volume vs time

Whisker volume vs time

- Growth rate decreases

with time (stress)
- Growth rate higher for
higher T (and stress)

Determine whisker volume vs time for each temperature

Average volume vs time

- Correlate whisker growth

with measured stress

Whisker volume vs time

- Whiskers stop growing

when stress reaches
critical value (cr)

cr

Determine whisker volume vs time for each temperature

Average volume vs time

- Correlate whisker growth

with measured stress

Whisker volume vs time

- Whiskers stop growing

when stress reaches
critical value (cr)
- Must consider fact that
stress is changing during
growth
cr

- Compute time-averaged
stress above cr
shaded areas <>t

Whisker volume vs time-averaged stress is linear!

Whisker volume vs time-averaged <> t

Suggests simple model for stress

dependence of average volume (V):

dV = D(T)
dt
- = - cr
( stress above critical value)
<>t (Mpa-min)
Ln (D(T))
vs 1/kT

D(T): temperature dependent

factor
Activation energy = 0.37 eV
Similar to gb diffusion for Sn

1/kT (1/eV)

Results suggest there is critical

value for stress in order to get
whisker growth

3) Plastic strain during heating cycles

Calculate plastic strain
from stress measurements
Total strain given by:

Stress during heating ramp/hold

actual

tot = T= e+ p
Curvature measures elastic stress
(proportional to elastic strain):

Due to plastic strain

= M e

Difference gives plastic strain:

Plastic strain during heating ramp/hold

p = T - /M
- Plastic strain can come from
whiskers and other relaxation
mechanisms (e.g. creep)

p = pwhisker + pcreep
- How much is due to whiskers?

Relationship between plastic strain and whisker formation

45 C cycle

55 C cycle

65 C cycle

75 C cycle

Solid line: total plastic strain determined from wafer curvature (ptotal)
Dashed line: amount of plastic strain calculated from whisker volume (pwhisker)

Plastic strain comes from whiskers and other mechanisms (e.g., creep)

ptotal = pwhisker + pcreep

Estimate plastic strain due to whiskers from volume (dashed lines)

Results indicate whisker/hillock growth is not only relaxation mechanism

Creep is also important (maybe dominant)

Put it all together: model stress generation and relaxation

(Pei et al, unpublished)

Plane stress and Equi-biaxial stress state

Lateral confinement imposed by the substrate:

imposed strain rate

elastic strain rate
strain rate due to diffusion (whisker growth)

power law creep rate (Shin, JMR 2009)

a: radius of whisker (1 m)
b: the region influenced by the whisker

Calculated average stress, volume and plastic strain

45 oC cycle

55 oC cycle

65 oC cycle

Calculations agree with experiments

Whiskers are not main strain relaxation mechanism

Summary
MOSS + optical microscopy + SEM quantify dependence of
nucleation and growth on stress
- Used thermal stress as controlled driving force
Nucleation kinetics:
- rate increases with temperature and stress
- nucleation barrier decreases with stress

nucleation can be as important as growth in whisker suppression

Growth kinetics:
- growth rate proportional to average stress
- minimum critical stress for growth to occur

keep below threshold to suppress whiskers

Strain relaxation:
- whiskers not main strain relaxation mechanism

enhancing creep (lowering stress) can be way to stop whiskers

Thanks to my collaborators:
EMC:
Brown:
Fei Pei (Amphenol)
Gordon Barr
Nitin Jadhav (IBM)
Eric Buchovecky (St. Gobain)
Jae Wook Shin (LAM Res.)
Lucine Reinbold (Raytheon)
Prof. Allan Bower
Prof. Clyde Briant
Prof. Sharvan Kumar

Thanks to NSF-DMR for support

Chason et al., Brown University, supported by NSF

Acknowledgment
This work is support by NSF

Q&A