us doe, office of basic camp energy sciences egysce ces...us doe, office of basic campenergy...
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CAMPUS DOE, Office of Basic Energy Sciences
Adhesion and Thermomechanical ReliabilityCenter for Advanced Molecular Photovoltaics
STAN FORD UN IVERSITY
e gy Sc e ces
Vit li B d Ch i B F d N J ff Y
Adhesion and Thermomechanical Reliability for PV Devices and Modules
Vitali Brand, Chris Bruner, Fernando Novoa, Jeff Yang (PhD students)
Monika Kummel (Post Doc)Reinhold H. Dauskardt ([email protected])
Collaborators:Craig Peters, Roman Gysel and Mike McGehee (Stanford)
Uraib Aboudi and Peter Peumans (Stanford)Uraib Aboudi and Peter Peumans (Stanford)David Miller, Michael Kempe and Sarah Kurtz (NREL)
William Hou and Yang Yang (UCLA)
Industry collaborators include Colin Reese, Shawn Scully and Juanita Kurtin (SpectraWatt), Steve Lin (Vitex), Matthew Robinson (Nanosolar), Christine McGuiness and Darin Laird
(Plextronics).
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Solar OutlookThen To make a difference
1. Efficiency2 R li bilit
1. Cost2 R li bilit
Then… To make a difference…
2. Reliability3. Cost
2. Reliability3. Efficiency
• Engineer durable solar technologies with robust and predictable lifetimes. Start early in development – avoid roadblocks.y
• Leverage from reliability physics in microelectronics – thin-film metrologies, kinetic models, accelerated tests, life prediction.
• Are degradation processes coupled and how?
• Kinetic models for damage evolution - basis for life prediction and accelerated testing (T environment stress solar flux etc )accelerated testing (T, environment, stress, solar flux, etc.)
• Effective defensive strategies – e.g. transparent barriers with anti-reflective properties.
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Degradation and Reliability of PV Devices and ModulesH2O, O2, H2
other active chemicalUV ExposureH2O, O2, H2
other active chemicalUV Exposure
Severe operating environments.
Exposure to thermal cycling, stress, moisture, chemically
other active chemical species
h t h i lcracking and
surface weathering
other active chemical species
h t h i lcracking and
surface weathering
, , yactive environmental species, and UV.
Uncertain degradation kinetics
photochemical reactions
cracking and debonding
defect evolution in
photochemical reactions
cracking and debonding
defect evolution in and reliability models.Substrate nanomaterial
layersSubstrate nanomaterial
layers
AM1 solar spectrum Activation Energies for Bond Rupture:VDW ~ 0.001 - .4 eV/bond H-bonds ~ .1 - .4 eV/bond
Ester Hydrolysis (100% RH)Sun in UV
Ester Hydrolysis (100% RH) E* ~ .81 eV/bond
SiO2 cracking in water E* ~ 1.39 eV/bond
Solar spectrum from B. Van Zeghbroeck, U. Colorado
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Evolution of Defects and Device Reliabilityabsence of chemically active environmental species, damage propagates ify p , g p p g
2/ mJGG cpresence of chemical species and photons, damage propagates even if
environment and stress accelerates 2/ mJGG stress acceleratesdefect evolution
Role of coupled kinetic parameters:
/ mJGG c
H2O
h• mechanical stress
• temperatureH2O
• environmental species
• photons
Substrate(photochemical reactions)
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Typical Film Adhesion Tests that Don’t Work WellIndenter
Interface Crack
IndenterPlastic zone
S b t t
Film• Indentation/Scratch Test
- complex stress and deformation fields- principally qualitative results Substrate
MP
p p y q- (nano) scratch test even less quantitative
Interface CrackFilm
• Peel/m-ELT Test- difficult to apply loads- plastic deformation of film
t t li ti i ELT Substrate
Film
- temperature complications in m-ELT
• Blister Test
PSubstrateFilm- compliant loading system
- environmental effects- etching/machining of cavity difficult
Cavity in Substrate
Major limitations: need detailed film properties, film stress relaxation and film plasticity principally qualitative results for all above methods!
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Quantitative Adhesion/Cohesion and Debond KineticsP/2P/2
Pre-notch
Thin films
43
P/2P/2Pre-notch
Thin films
43
Al (100 nm)h
b
LL
a
Thin filmsh
b
LL
a
Thin films
P 0
P 0
FPB adhesionITO (150 nm )
PEDOT:PSS (50-100 nm)
( )Ca (7 nm)
P3HT/PCBM (~150 nm)cohesive
failure
Degradation Kinetics
a
P
Thin films
bh
a
P
Thin films
bh
DCB cohesion
Glass Substrate
10-5
10-4
(m/s
)
UV intensity2
J/m
2 )
Degradation Kinetics(temp/environment /UV effects)
Adhesion/Cohesion
DTS system and support contact [email protected]
10-7
10-6
10
Rat
e, d
a/dt
No UV
1.2 mW/cm2
1
1.5
ergy
, G (J
10 10
10-9
10-8
k G
row
th R 0 mW/cm2
0 60.5
1
hesi
on E
n
threshold crucial
0 1 2 3 4 5 6 710-11
10-10
Cra
ck
Strain Energy Release Rate, G (J/m2)
0.6 mW/cm2
0
Coh
Solar Cells
for reliability
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Inherent Solar Cell Thermomechanical Reliability, Gc
Grad students: Vitali Brand, Jeff Yang and Chris Bruner
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Adhesion/Cohesion Sample Preparation
Glass Substrate
Thin films sandwiched between elastic substrates
P/2P/2Pre-notch
43
P/2P/2Pre-notch
43
Al (100 nm)Ca (7 nm)
Epoxy Bond (2 m) h
b
LL
a
Thin filmsh
b
LL
a
Thin films
FPB adhesion
ITO (150 nm )PEDOT:PSS (50-100 nm)
P3HT/PCBM (200 nm)P
Thin films
bh
0P
Thin films
bh
0
Gunes, et. Al. Chem. Rev. 2007.
Glass Substratea
P
a
P DCB cohesion
Fabricated 4-point bend adhesion and DCB cohesion test structures using standard epoxy bonding techniques.Si il t t l b t t h idSimilar transparent glass substrates on each side.
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8
Adhesion/Cohesion of P3HT/PCBM Structures
6
m2 )
Std. 1:1 P3HT:PCBM
Thicker P3HT:PCBM
Al (100 nm)Ca (7 nm)
P3HT/PCBM (200 nm)cohesive4
rgy,
G (J
/m
compositionP3HT:PCBM1:0 3:1 1:3
G S
ITO (150 nm )PEDOT:PSS (50-100 nm)
P3HT/PCBM (200 nm) failure
2
ctur
e E
ner
Glass Substrate
0
Frac
Solar Cells
• XPS reveals similar debond path for DCB and 4-pt bend samples• C ~ 92%, S ~ 6%, O ~ 2%
Suggests cohesive failure in PCBM:P3HT layerXPS Spectra
• Suggests cohesive failure in PCBM:P3HT layer
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Factors Effecting Cohesion of P3HT/PCBM Layers
• Heterojunction layer thickness 16
18
20
PAE/SiCN (Mixed-Mode)
J/m
2 )
• Heterojunction layer thickness– cohesion in polymer layers is sensitive
to layer thickness– plastic energy dissipation in organic layers 6
8
10
12
14
16( )
PAE/SiO2 (Mixed-Mode)
PAE/SiCN (Mode I)
e En
ergy
, Gc (
J
plastic energy dissipation in organic layers
0 50 100 150 200 2500
2
4
6
Frac
ture
Film Thickness, h (nm)
Kearney, Dauskardt, et.al. Acta Mat. 2008
• Composition of the heterojunction layer– limited bonding to fullerene – expect low cohesion– preliminary measurements indicate higher ratios
( )
p y gof P3HT to PCBM make stronger active layer
• AnnealingAnnealing– morphology of the P3HT:PCBM film
changes with annealing, expect effect of morphology on cohesion
Thermal Anneal (150C)before 30 min 2 h
TEM of P3HT:PCBM filmHeeger, et. Al. Adv. Func. Mat. 2005.
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Effect of Composition of BHJ on Cohesion
33
(J/m
2 ) Failure path 75% P3HTP3HT/PCBM
2
ergy
, Gc
glass
1
ure
Ene
Failure pathfor 100% P3HT
P3HT
0
Frac
t
glass
0 25 50 75 100Composition P3HT/PCBM (%)
Cohesion increases with P3HT due to increased network formation
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Phase TopographyTopography
AFM of Failure Path Near Ca Interface
5 µmp g p y
Ra = 20 nmRq = 24 nm
Annealing effects
AlCa
0 5
ea g e ec sduring Al vapor deposition is a
possibility20 µmcohesive surfaces
0.5 µm
1 µmTopography
PEDOT:PSSITO
P3HT/PCBM
ITO
R = 25 nm
GlSubstrate
Glass Substrate
Ra = 25 nmRq = 30 nm
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Small Molecule Solar Cell Thin Films
C60 CuPc BCPC60 CuPc BCP
1.E-041.E-03
m/s
)
10-3
m/s
) Gc ~ 1.1 J/m223oCGc 1.1 0.4 J m2Ryan Birringer, Uraib Aboudi and Peter Peumans
BCP (~ 20 nm)Ag (~ 100 nm)
1.E-071.E-061.E-05
eloc
ity, v
(m
10-7
10-5
Velo
city
, v (m 50% R.H.
c
CuPc (~ 12 nm)CuPc:C60 (~ 16 nm)
C60 (~ 38 nm)( )
1.E-101.E-091.E-08
Deb
ond
Ve
10-9
11
Deb
ond
V
Threshold ~
0.7 J/m2
Glass SubstrateITO 1.E-11
0 0.5 1 1.5
Debond Driving Force, G (J/m2)
D 10-11
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Molecular Bond Rupture KineticsMolecular Bond Rupture Kinetics(Barrier Films)
Grad student: Fernando Novoa and Monika Kummel
environment and 2/JGG stress acceleratesdefect evolution
2/ mJGG c
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Weathering Test of Polysiloxane Barrier
UV exposure: 28 mW/cm2 at 6 mm UV-257nm
120 min 15 min 5 min120 min…………….15 min……………………5 min
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Environment and Stress Accelerates DamageSi l t d UV EDoes UV exposure accelerate decohesion in solar cells? Simulated UV Exposure
applied load
Does UV exposure accelerate decohesion in solar cells?
What are the kinetics?
O i
UV Exposuretransparent substrate
Substrate
OrganicLayer Environmental Chamber
(gaseous and aqueous)
Debond TipDebond
Substrate
h Debond Tiph Debond Tip Reactions
Activation Energies:VDW ~ 0.001 - .4 eV/bond H-bonds ~ .1 - .4 eV/bond
Ester Hydrolysis (100% RH)
Substrate
y y ( )E* ~ .81 eV/bond
SiO2 cracking in water E* ~ 1.39 eV/bond
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Assessing UV and Environment on Debonding KineticsSimulated UV Exposure
Glass Substrate
ITO
ITO
polysiloxanebarrier
Glass Substrate
ITO
Po
ad, P automated load
relaxation debond
Debonding Kineticsexplore role of:
test dataDTS Delaminator v4.0
Loa
ngth
, a
dP/dtrelaxation debond growth analysis
compliance analysis
• UV flux
• humidity, O2, OH, …
Cra
ck L
en
Time (s)
da/dt • temperature
• mechanical loadingsensitivity to < 10-10 m/s
DTS system and support contact [email protected]
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UV Exposure (3 4 eV)
UV Effects on Molecular Bond Rupture
10 5
10-4(m
/s)
UV Exposure (3.4 eV)
UV intensity1 2 mW/cm2
10-6
10-5
da/d
t(
Ghv ~ 1.3 J/m21.2 mW/cm2
10-8
10-7
h R
ate,
No UV0 mW/cm2
10-9
10
Gro
wth
2
i h htip GGda0 6 W/ 2
10-11
10-10
Cra
ck
Ghv ~ 0.8 J/m2
sinh htipov
dt0.6 mW/cm2
0 1 2 3 4 5 6 7Strain Energy Release Rate, G (J/m2)
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Modeling Bond Rupture Kinetics• Interaction of moisture with strained debond tip bonds h
)complex activated() tipdebond( *2 B
hBOnH
• Interaction of moisture with strained debond tip bonds
H2O
h
kTU
kTUfrate o
**
expexp Substrate
• Atomistic bond rupture models:
2sinh htip
o
GGv
dda
Si-O-Si + H2O
activation barrier
h
• Damage growth rate:
odt 2
Si-OH + HO-Si
h
attemptfrequencyrg
y
kTu
Nwfv o
o1exp2
Bond Rupture ParametersN - bonds per unit area fo - attempt frequencyuo - work of rupture u1 - energy barrier
G
q yEn
e kTNw
o p 1 gy - N uo - 2NkTw - crack width Bond Rupture Reaction
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UV SourcesFluorescent Lamp
AM1 solar spectrum
Mercury LampMercury Lamp (Pen-Ray from uvp)
3.4eV 4.9eV4.1eV
Solar spectrum from B. Van Zeghbroeck, U. Colorado
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UV exposure 4 9 eV
UV Effects on Molecular Bond Rupture
1E-5
s) 10-5
UV exposure 4.9 eVadhesive failure at 20°C 40%RH
adhesive
1E-6
da/d
t (m
/s
10-6
Gl S b t t
Simulated UV Exposure
1E-7
h R
ate,
d
6.6
2 mW/cm2
4.6 mW/cm210-7
Glass Substrate
polysiloxanebarrier
1E 9
1E-8
d G
row
th mW/cm2
No UV10-8
10 9
Glass Substrate
0 1 2 3 4 5 61E-10
1E-9
Deb
ond 10-9
10-10
Simulated UV Exposure
0 1 2 3 4 5 6Strain Energy Release Rate, G (J/m2)
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Delamination of EVA-TPE Lamination• Poly-ethylene vinyl acetate (EVA) copolymer extensively used by solar modulePoly ethylene vinyl acetate (EVA) copolymer extensively used by solar module
manufacturers, particularly for laminating c-Si photovoltaic modules.• Good optical properties and high adhesive contact with glass cover and Si cells.• Inexpensive and relatively easy fabrication.p y y
Parreta Antonio, et al., Solar Energy Materials & Solar Cells, 2005
• Delamination can occur between EVA and the front surface of the solar cells.• More frequent and in hot and humid climates• More frequent and in hot and humid climates.• Exposure to atmospheric water and/or ultraviolet radiation leads to EVA
decomposition to produce acetic acid, lowering the pH and increasing corrosion.• EVA Tg ~ -15°C so lower temperatures may result in “ductile-to-brittle” transition inEVA Tg 15 C so lower temperatures may result in ductile to brittle transition in
adhesive/cohesive properties.
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Tedlar (Polivinylfluoride) II
Delamination of EVA-TPE Laminationadhesion
EVA main l t
Tedlar (Polivinylfluoride)PET
EVA seedTPE
EVA
II
40
45
50
55
Rat
e, G
(J/m
2 )
I
adhesion
Glass Substrate
encapsulantEVA
I15
20
25
30
35
ergy
Rel
ease
R
II
EVA TPE- Bridging TPE- No Bridging0
5
10
15
Stra
in E
ne
II
m/s
)
G 46 J/ 2 G =377 J/m2
time dependant debondingg g g g
Location of Failure
10-6
10-5
Rat
e, d
a/dt
(m Gc=46 J/m2 Gc=377 J/m2
Interface “I” located between EVA and GlassInterface “II” inside the TPE multilayer
9
10-8
10-7
nd G
row
th R IV III
0 100 200 300 400
10-9
Deb
on
Strain Energy Release Rate, G (J/m2)
10°C 10%RH
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Summary for PV Durability and ReliabilityWe want to engineer durable PV devices and modulesWe want to engineer durable PV devices and modules
with robust and predictable lifetimes.L f li bilit h i i i l t i• Leverage from reliability physics in microelectronics –mechanisms, kinetic models, accelerated tests and life prediction
• Develop metrologies to quantitatively characterize thermo-• Develop metrologies to quantitatively characterize thermo-mechanical properties (e.g. adhesion, cohesion), photochemical and environmental degradation processes
• Are degradation processes coupled and how?
• Kinetic models of damage evolution - basis for life prediction and accelerated testing (effect of operating temperature, environment, mechanical stress, solar flux, etc.)
• Effective transparent barriers with anti reflective properties and• Effective transparent barriers with anti-reflective properties and low cost.