Electrical and Mechanical Defects in Solar Cell Materials and Devices

Buonassisi Laboratory for Photovoltaics Research
http://pv.mit.edu
Electrical and Mechanical Defects in Solar Cell

Materials and Devices
Steve Hudelson1, Katy Hartman2, Yun Seog Lee1, and Tonio Buonassisi1
1Department of Mechanical Engineering
2Department of Materials Science and Engineering
Massachusetts Institute of Technology, Cambridge, MA (USA)

http://pv.mit.edu
Foreword: PV Research at MIT
25+ research groups

involved in solar… see http://
pv.mit.edu for list.
Two research groups fully

dedicated to PV research:
Prof. Ely Sachs
Prof. Tonio Buonassisi
http://pv.mit.edu
Foreword: MIT’s PV Neighborhood
T. Buonassisi - 4th JSPS Workshop: Future Direction of PV, Tokyo, 5/March/2008 3

http://pv.mit.edu
PV R&D in Context: Market Drivers for PV Research
Near-Term:
Rapid Growth
Build capacity. Increase efficiency.

Prioritize growth. Reduce yield loss.
Secure feedstock Reduce bottlenecks.
supplies. Increase throughput.
Decrease materials
consumption.

http://pv.mit.edu
Near-Term: Medium-Term:
Rapid Growth Reduce Costs
Build capacity. Increase efficiency. Vertical integration.

Prioritize growth. Reduce yield loss. Statistical process
Secure feedstock Reduce bottlenecks. control.
supplies. Increase throughput. Supply chain
Decrease materials optimization.
consumption. Lean manufacturing.
Novel materials
systems.
Environmental impact
reduction.

http://pv.mit.edu
Near-Term: High Impact Medium-Term:

Rapid Growth University R&D Reduce Costs
Build capacity. Increase efficiency. Vertical integration.

Prioritize growth. Reduce yield loss. Statistical process
Secure feedstock Reduce bottlenecks. control.
supplies. Increase throughput. Supply chain
Decrease materials optimization.
consumption. Lean manufacturing.
Novel materials
systems.
Environmental impact
reduction.

http://pv.mit.edu
PV Research Areas
High Impact Improved device architectures

University R&D
Increase efficiency
Reduce yield loss.
Reduce bottlenecks.
Increase throughput.
Decrease materials
consumption. Improved bulk material quality…

http://pv.mit.edu
Material Electronic Quality (Lifetime) and Cell Efficiency

More is more: Higher bulk
minority carrier lifetimes are
High-efficiency cell architecture crucial for high-efficiency cell
architectures!
(A Fiat engine in a Ferrari does not

make a fast car!)
High bulk lifetime will be an issue

Low-efficiency cell architecture of increasing importance as better
device architectures are
implemented.
Low-efficiency cell modeled using PC1D: 220 m
thick, high Sf, Sb, Rf_ext, Rs, low Rr_int, Rsh.
High-efficiency cell modeled using PC1D: 160
m thick, low Sf, Sb, Rf_ext, Rs, high Rr_int, Rsh.

http://pv.mit.edu
Lifetime-Limiting Defects Multicrystalline Silicon (mc-Si)
A typical mc-Si sample might include…
Metal impurities Dislocations

Iron, Titanium, Nickel, Edge, Screw,
Chromium, Copper… Mixed, Loops...
Non-metals Grain boundaries

Oxygen, Nitrogen CSL, Small-angle,
Carbon… Large-angle…
250m
mc-Si, defect etched to reveal a plethora of structural defects

http://pv.mit.edu
2D: Grain
“Defect Universe” in
Boundaries (CSL,
small-angle,
Photovoltaic Devices
random…),
0D: Point Defects Surfaces, Interfaces
(Vacancies, Interstitials)
Complexes
Intrinsic Structural 3D: Voids
Defects Defects
Complexes 1D: Dislocations
(edge, screw,
Complexes partial…), Stacking
Impurity- Faults
Intrinsic Impurity-SD
Defect Complexes
Complexes
Impurities
3D: Precipitates 2D: Platelets
0D: Point Defects (Metals,

Non-Metals, Dopants,
Passivating Agents,
Complexes)

http://pv.mit.edu
2D: Grain
Boundaries (CSL,
small-angle,
random…),
(Vacancies, Interstitials) “Traditional” defect
Complexes
3D: Voids
studies include:
Intrinsic Structural
Defects Defects
What defects are
Complexes 1D: Dislocations present?
Complexes
(edge, screw,
partial…), Stacking
What are differences
Impurity- Faults between crystal growth
Defect Complexes methods?
Complexes What are the impacts
Impurities
of single defect types?

Passivating Agents,
Complexes)

Census of Impurities Buonassisi Laboratory for
in Multicrystalline Photovoltaics Research
Silicon
http://pv.mit.edu
Thereare more than enough metals in a typical solar cell to destroy
device performance!
8 kg of iron
in 40,000 tons
of silicon
(100 ppba)
80 mg of iron
in 40,000 tons
of silicon
(1 pt. per trillion at.)
T. Buonassisi et al., Prog. Photovolt. 14, 513 (2006).
Minoritycarrier lifetime depends on the distribution and chemical nature

of defects and impurities.

http://pv.mit.edu
Synchrotron-Based Techniques
μ-XRF: Map spatial distribution of metal

precipitates, determine elemental
composition of each precipitate.
μ-XAS: Determine chemical state of metals

in the precipitates.
XBIC: Characterize their recombination Analytical Microprobe Beamlines:

activity. -10.3.2, Advanced Light Source
-2-ID-D, Advanced Photon Source
T.Buonassisi et al., Solid State Phenom. 108-109, 577 (2005).
S.A. McHugo et al., J. Cryst. Growth 210, 395 (2000)

Mc-Si Growth Method Affects Metal Distribution http://pv.mit.edu
“Cast” mc-Si Iron (-XRF) Grain Structure
Ribbon mc-Si
Iron (-XRF) Grain Structure
T. Buonassisi et al., Prog. Photovolt. 14, 513 (2006).

Visualizing Impurity Buonassisi
ParticlesLaboratory for Photovoltaics
Using Synchrotron Research
Radiation
http://pv.mit.edu
T.Buonassisi et al., J.Appl.Phys. 97, 63503 (2005) and J.Appl.Phys. 97, 74901 (2005).
Large (up to 25 μm) inclusions
Often found within grains.

Found in low density.
Fe is dominant, often with presence of other

slowly diffusing metals (e.g., Cr, Mo, Ti).
Fe often oxidized and very similar to Fe2O3 .
Small (10’s of nm) nanoprecipitates
Typically accumulated along structural

defects (e.g., dislocations, GBs).
Found in high density.
Very few slowly diffusing metals detected.

T. Buonassisi - 4th JSPS Workshop: Future Direction
Consist ofofFe,
PV, Tokyo,
Cu, or 5/March/2008
Ni in a silicide 15
form.
Metal Distributions Buonassisi Laboratory for Photovoltaics Research
http://pv.mit.edu
Metal impurities can take many forms in mc-Si:

a) Point Defects:
Atomically distributed
[M] 1013 cm-3
b) Nanoprecipitates:
10’s of nm, microns apart
[M] 1015 cm-3
c) Inclusions:
m-sized, 100+ m apart
[M] 1016 cm-3
d) Segregated Metals:
Atomically distributed
along extended defects
T. Buonassisi, A.A. Istratov et al., Nature Mat. 4, 676 (2005) [M] = ?

Contamination Buonassisi Laboratory for Photovoltaics Research
http://pv.mit.edu
Pathways
Foreign External
Particles Sources
Silicon
Silicon Fe Dissolved
of Metals
Melt
Melt Atomically in Melt
particulate
liquid-solid interface ---------- & dissolved
Crystal
Crystal metals in
(warm) Precipitation Segregation
(warm)
Directly from to Structural feedstock,
temperature
impurities
impurities
mobile Melt Dissolved Defects production
mobile
atomically equipment,
in Crystal growth
surfaces,
etc.
----------
Crystal
Crystal Homoge-
(cool)
(cool) neously
Fe Point
Defects distributed
along
Precipitates structural
Inclusions (Fe silicide) defects
T. Buonassisi, A.A. Istratov et al., J. Appl. Phys. 97 (2005) 074901
http://pv.mit.edu
2D: Grain
Boundaries (CSL,
small-angle,
random…),
(Vacancies, Interstitials) Newer “Defect” Studies
Complexes
3D: Voids
include:
Intrinsic Structural
Defects Defects
Defect interactions.
Complexes 1D: Dislocations Defect evolution
(edge, screw,
Complexes partial…), Stacking
during processing.
Impurity- Faults Manipulating defects
Defect Complexes to reduce their impact
Complexes on performance
Impurities
(defect engineering).

Passivating Agents,
Complexes)

http://pv.mit.edu
Engineering Defects and Impurities

Goal: To develop technologies to engineer impurities and defects, to
improve bulk material quality.
Complicating Factors: Impurity interactions, precipitation kinetics,
formation of second phases.
T. Buonassisi et al., Nature Mat. 4, 676 (2005)

http://pv.mit.edu
Defect Engineering in Mc-Si: Some Boundary Conditions
Time and temperature must

be sufficient, to enable
desired defect redistribution.
Relation between (diffusion

distance L) and (time t,
temperature T, activation
energy EA), for point defects:
E A

kT
L Do t e

http://pv.mit.edu
Defect Engineering in Crystal Growth
Full temperature range!

http://pv.mit.edu
Harnessing Impurity Interactions During Crystal Growth
Ingot 1: Abundance of fast

diffusers (Cu and Ni). Fe
highly localized.
Ingot 2: Low concentration of

fast diffuser. Fe less
localized. Cell efficiency
~0.3% lower.

MultiMetal-Silicide Precipitates
Cu3Si http://pv.mit.edu
Mixed-Metal Silicide
T.Buonassisi et al., Acta Materialia 55, 6119 (2007);

M. Heuer et al., Phys. Rev. B 73, 235204 (2006)

http://pv.mit.edu
Co-Precipitation of Metallic Species

Understanding interactions between metallic impurity
species.
(Ni,Fe)(Si,Cu)2 (Co,Cu)Si2 (Ni,Co,Fe)Si2
T.Buonassisi, to be submitted (2007).

Segregation Gettering Buonassisi Laboratory for Photovoltaics Research
at High Temperatures?
http://pv.mit.edu
Dissolved impurities.
High T
Possibility 1: Segregation to Possibility 2: Segregation to a

a Liquid MM-Si Droplet. Solid MMSix Precipitate.
- Impurity solubility in
Cu Cu precipitate: atomic %.
Ni and/ Ni - Impurity solubility in bulk:
Fe or Fe ppb to ppm.
= Effective impurity segr.
coef.: Large?
Low T
Impurity Supersaturation upon cooling, Phase
Segregation in Solid MSix Precipitates.
Phase 1
Phase 2 T.Buonassisi et al., Acta Materialia

55, 6119 (2007);

Buonassisi
Defect Engineering in Ribbon Laboratory for Photovoltaics Research
Growth
http://pv.mit.edu
Inribbon-Si growth, metals are never more than 100 m away from a
free surface!
CO Gas
Introduce gas during growth

Gas creates defect-rich layer near surface, injects point defects.

Buonassisi
Defect Engineering in Ribbon Laboratory for Photovoltaics Research
Growth
http://pv.mit.edu
Surface gettering of impurities during ribbon-Si growth very effective.
Si material grown from a melt containing Cu+Ni+Fe in

parts per thousands concentrations.
Surface Impurity Bulk Impurity

Distribution Bulk Lifetime
Distribution
Without
Surface ~0.3 s
Gettering
With
Surface >10 s
Gettering
D. Khanal et al., Appl. Phys. Lett. 90, 102110, (2007)

http://pv.mit.edu
Metal interactions with Structural Defects
-XRF EBSD Defect Structure
1. Quantify Metals 2. Determine GB 3. Identify Defect

at GBs; Characters; Structure.

Metal – GB interactionsBuonassisi
in mc-SiLaboratory for Photovoltaics Research
http://pv.mit.edu
Metal precipitation at GBs
Generally, metal decoration increases with decreasing atomic

coincidence within the grain boundary plane (higher ).
A few low- GBs demonstrated anomolously high metal
contents. These were analyzed in greater detail…
T. Buonassisi et al., APL 89, 042102 (2006)
Buonassisi
Dislocation interactions with GBs,Laboratory
metals for Photovoltaics Research
http://pv.mit.edu
3 with Abundant Metal Precipitates
3 with Few Metal Precipitates
T. Buonassisi et al., APL 89, 042102 (2006)
T. Buonassisi - 4th JSPS Workshop: Future Direction of PV, Tokyo, 5/March/2008

25 m30
Buonassisi Laboratory
Metal Dislocation Interactions for Photovoltaics
& Dislocation EngineeringResearch
http://pv.mit.edu
Regions of high dislocation density have low performance; resist
upgrading during solar cell processing.
(Unpublished figures removed.)
Similar work: Various (1980’s), M. Kittler (2004), A. Bentzen (2006), O. Schultz (2006).
http://pv.mit.edu
“Dislocation Density Engineering” in Mc-Si: Latest Results!
“Dislocation Density Engineering” lowers dislocation density!
(Unpublished figures removed.)

http://pv.mit.edu
Defect Engineering during Traditional Cell Fabrication
Reduced Temp range!

http://pv.mit.edu
Sample Impurity Flow Diagram during Cell Processing

http://pv.mit.edu
Reducing Iron Point Defects in Silicon

The concentration of Fe
point defects in as-grown
multicrystalline silicon
(mc-Si) is high, and
roughly the same for a
wide range of materials
and growth conditions.
WHY?
T. Buonassisi et al., 21st EU-PVSEC, p.

1505 (2006).

http://pv.mit.edu
Optimal Conditions for Iron Precipitation

To optimize relaxation gettering, an optimal temperature must be
found, at which the temperature is low enough to provide a large
driving force for preciptiation (supersaturation), but
simultaneously the temperature is high enough to allow iron to
diffuse.
Diffusivity Solubility
This optimum is too Low: too High:
Interstitial Iron Conc.
Fe cannot diffuse No driving force
reflected in the iron to precipitates. for precipitation.
“time-temperature-
transformation
diagram (right).
Precipitation
Optimized.
Annealing Temperature
http://pv.mit.edu
Iron Time-Temperature-Transformation (TTT) Diagram

Previous research on float-zone silicon identified an optimum iron
annealing temperature at 500°C.
TTT diagram: Iron in FZ-Si

W.B. Henley and D.A. Ramappa, J.
Appl. Phys 82, 589 (1997)

http://pv.mit.edu
TTT Diagram for Iron in Mc-Si

Mc-Si contains a variety of regions with different structural defect
concentrations. Despite the noise, TTT diagrams can
nevertheless be constructed for mc-Si wafers.
As-grown Evergreen String Ribbon

wafers, annealed for 30 minutes. Iron
point defect concentrations averaged
over the entire wafer. Despite scatter
in the data, Fei-Bs reduction is
observed after annealing at low
(<500°C) temperatures.
M.D. Pickett and T. Buonassisi, Applied

Physics Letters 92, 122103 (2008).

http://pv.mit.edu
Application of TTT Diagrams to Solar Cell Processing

A short low-temperature anneal (500°C, 30 min.) can be
employed after phosphorus diffusion, but before glass etch.
Benefits: Enhanced Fei segregation to n+ layer, defect-rich region
near surface, no shunting of metallization.
Result: Efficiencies increased by

~2% relative in Fe-rich feedstock.
No efficiency improvement noted
in ultra-high-purity feedstock.
M.D. Pickett and T. Buonassisi, Applied

Physics Letters 92, 122103 (2008).

http://pv.mit.edu
Manipulation of Fe During Cell Processing

As-Grown P-Diffused LT-Gettered
Precipitated Fe
Fe Point Defects < <

http://pv.mit.edu
PV Research Areas
High Impact
University R&D
Increase efficiency.
Reduce yield loss.
Reduce bottlenecks.
Increase throughput.
Decrease materials
consumption.

http://pv.mit.edu
Increasing Manufacturing Yields

Big cost drivers include yield, efficiency, and area costs.
Fixed Area Costs ($/m2 )
Cost of PV ($/Wp ) =
Yield (%) Efficiency (%) Illumination (Wp /m2 )
Thinner wafers Reduced Breakage
http://www.meyerburger.ch/en/products/wire-saws/ds-262

Stress Measurement:Buonassisi
NIR Photoelasticity Imaging Research
Laboratory for Photovoltaics
http://pv.mit.edu
First applications to solar cells from the

groups of Danyluk [1] and Vallera [2].
Commercial tool made by Stress

Photonics, Inc. [3]
[1] T. Zheng and S. Danyluk, Matl. Evaluation 50,

1227 (2001); (b) Shijiang He, Ph.D. Dissertation,
Georgia Institute of Technology (December 2005).
[2] M.C. Brito et al., Rev. Sci. Instr. 76, 013901
(2005); M.C. Brito et al., Solar Energy Mater. &
Solar Cells 87, 311 (2005).
[3] US Patent 6,219,139

Experimental Data Matches Finite
Buonassisi Element
Laboratory ModelingResearch
for Photovoltaics
http://pv.mit.edu
For stressed wafers, stress relief during annealing matches

finite element modeling, for certain types of stress relief.
Care must be taken to avoid artifacts!

Evaluation of “Good”Buonassisi
and “Bad” Laserfor
Laboratory Cuts
Photovoltaics Research
http://pv.mit.edu
Microscope objective combined with the CCD.

The quality of a cut is immediately discernable!

Evaluation of “Good”Buonassisi
and “Bad” Laserfor
Laboratory Cuts
Photovoltaics Research
http://pv.mit.edu
Low Stress Cut
2
ShearMax [a.u.]
1.5
0.5
0
0 50 100 150 200 250 300
Distance [a.u.]
High Stress Cut 2
ShearMax [a.u.]
1.5
0.5
0
0 50 100 150 200 250 300
Distance [a.u.]
The quality of a cut is quantifiable!

Theory Buonassisi Laboratory for Photovoltaics Research
http://pv.mit.edu
Schoenfelder [1] proposed that “a layer of molten and
solidified material induces stress in the sample surface
reducing the strength of samples.”
SEM of “Bad” Cut, from [1] SEM of “Good” Cut, from [1]
[1] S. Schoenfelder et al., 21st EU-PVSEC (Dresden, 2006).

Recast Removal = Stronger Wafers
http://pv.mit.edu
4-Bar Flexture Test Photoelasticity: Edge Stress
Stronger wafers result by removing the stress in the recast,

either by removing the recast zone entirely (etching,
polishing), or by annealing out the stress.

Conclusions Buonassisi Laboratory for Photovoltaics Research
http://pv.mit.edu
Cost reductions in Si-based PV can originate from an increased
understanding of defect interactions, and their effects on:
Microstructural / Electrical Properties:
Advanced characterization techniques elucidate novel phenomena
(multiple metal interactions), inspiring the development of defect
engineering technologies (e.g., Fe point defect engineering, surface
gettering using specialty gasses, dislocation density engineering).
Mechanical Properties:
IR photoelasticity imaging permits one to observe stress
distributions in silicon wafers.
Measure as-grown stresses.
Monitor process-induced stresses.
Understand, predict, and avoid yield loss mechanisms.

Acknowledgments http://pv.mit.edu
Synchrotron colleagues: Matthew Marcus (ALS); Barry Lai, Zhonghou Cai, and
Steve Heald (APS).
Former UC Berkeley Colleagues: Matthias Heuer (Berlin Solar), Andrei Istratov

(Siltronic), Matthew Pickett (HP Labs), Devesh Khanal, and Eicke R. Weber
(Fraunhofer ISE).
Jon Lesniak, M. Spencer, Brad Boyce at Stress Photonics for stress

measurement development.
Current and Former Members of the R&D team at Evergreen Solar, including,
Voy Anuszkiewicz, Sarah Decourcy, Larry Felton, Tom Ford, Eric Gabaree,
Andrew M. Gabor, David Harvey, Colan Jones, Dick Krauchune, Luey Nyugen,
Minh Le, Adam M. Lorenz, Alan Rolke, Gary J. Tarnowski, and Richard Wallace.
Colleagues from NTNU defect engineering workshop.
Insightful discussions with colleagues at Tohoku University (N. Usami, K.

Kutsukake, K. Nakajima), and throughout Japan.

http://pv.mit.edu
Further Information
For slides of our presentation, please visit next week:
http://pv.mit.edu

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Buonassisi Laboratory for Photovoltaics Research

Electrical and Mechanical Defects in Solar Cell

Massachusetts Institute of Technology, Cambridge, MA (USA)

Foreword: PV Research at MIT

25+ research groups

Two research groups fully

Foreword: MIT’s PV Neighborhood

T. Buonassisi - 4th JSPS Workshop: Future Direction of PV, Tokyo, 5/March/2008 3

PV R&D in Context: Market Drivers for PV Research

Build capacity. Increase efficiency.

T. Buonassisi - 4th JSPS Workshop: Future Direction of PV, Tokyo, 5/March/2008 4

PV R&D in Context: Market Drivers for PV Research

Build capacity. Increase efficiency. Vertical integration.

T. Buonassisi - 4th JSPS Workshop: Future Direction of PV, Tokyo, 5/March/2008 5

PV R&D in Context: Market Drivers for PV Research

Near-Term: High Impact Medium-Term:

Build capacity. Increase efficiency. Vertical integration.

T. Buonassisi - 4th JSPS Workshop: Future Direction of PV, Tokyo, 5/March/2008 6

High Impact Improved device architectures

T. Buonassisi - 4th JSPS Workshop: Future Direction of PV, Tokyo, 5/March/2008 7

Material Electronic Quality (Lifetime) and Cell Efficiency

(A Fiat engine in a Ferrari does not

High bulk lifetime will be an issue

T. Buonassisi - 4th JSPS Workshop: Future Direction of PV, Tokyo, 5/March/2008 8

Lifetime-Limiting Defects Multicrystalline Silicon (mc-Si)

A typical mc-Si sample might include…

Metal impurities Dislocations

Non-metals Grain boundaries

mc-Si, defect etched to reveal a plethora of structural defects

0D: Point Defects (Metals,

T. Buonassisi - 4th JSPS Workshop: Future Direction of PV, Tokyo, 5/March/2008 10

3D: Precipitates 2D: Platelets

0D: Point Defects (Metals,

T. Buonassisi - 4th JSPS Workshop: Future Direction of PV, Tokyo, 5/March/2008 11

Minoritycarrier lifetime depends on the distribution and chemical nature

T. Buonassisi - 4th JSPS Workshop: Future Direction of PV, Tokyo, 5/March/2008 12

μ-XRF: Map spatial distribution of metal

μ-XAS: Determine chemical state of metals

XBIC: Characterize their recombination Analytical Microprobe Beamlines:

T. Buonassisi - 4th JSPS Workshop: Future Direction of PV, Tokyo, 5/March/2008 13

“Cast” mc-Si Iron (-XRF) Grain Structure

T. Buonassisi et al., Prog. Photovolt. 14, 513 (2006).

Large (up to 25 μm) inclusions

Often found within grains.

Fe is dominant, often with presence of other

Fe often oxidized and very similar to Fe2O3 .

Small (10’s of nm) nanoprecipitates

Typically accumulated along structural

Found in high density.

Very few slowly diffusing metals detected.

Metal impurities can take many forms in mc-Si:

T. Buonassisi - 4th JSPS Workshop: Future Direction of PV, Tokyo, 5/March/2008 16

3D: Precipitates 2D: Platelets

0D: Point Defects (Metals,

T. Buonassisi - 4th JSPS Workshop: Future Direction of PV, Tokyo, 5/March/2008 18

Engineering Defects and Impurities

T. Buonassisi et al., Nature Mat. 4, 676 (2005)

Defect Engineering in Mc-Si: Some Boundary Conditions

Time and temperature must

Relation between (diffusion

T. Buonassisi - 4th JSPS Workshop: Future Direction of PV, Tokyo, 5/March/2008 20

Defect Engineering in Crystal Growth