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Who We Are Who We Are An international not- -for for- -profit, scientific society profit, scientific society An international not 8 ,000 of more than 8 ,000 engaged in solid state and engaged in solid state and of more than
Who We Are Who We Are
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William D. Brown William D. Brown Photovoltaic Research Center Photovoltaic Research Center Department of Electrical Engineering Department of Electrical Engineering University of Arkansas, Fayetteville University of Arkansas, Fayetteville Arkansas 72701 USA
Collaborators
Arkansas 72701 USA LARGE GRAIN POLYCRYSTALLINE AND EPITAXIAL SILICON FILMS FORMED AT LOW TEMPERATURES FOR SOLAR CELLS
Collaborators Marwan Barghouti, Hameed A. Naseem, Li Cai, Min Zou, Maruf Marwan Barghouti, Hameed A. Naseem, Li Cai, Min Zou, Maruf Hussain, Khalil Sharif, Hussain, Khalil Sharif, Husam H. Abu
Husam H. Abu-
- Safe,
Safe, Ram Kishore, Adnan Al
Ram Kishore, Adnan Al-
- Shariah, and Hengyu Wang
Shariah, and Hengyu Wang
23 23
24 24
Order of Presentation Order of Presentation
Thin Film PV Power Generation Thin Film PV Power Generation Powering the US with Solar Cells Powering the US with Solar Cells PV Production Growth PV Production Growth Metal Induced Crystallization Metal Induced Crystallization Experimental Experimental AIC Large Grain Growth AIC Large Grain Growth Epitaxial Growth Epitaxial Growth Results and Discussion Results and Discussion Summary and Conclusion Summary and Conclusion Acknowledgements Acknowledgements
Powering the US
nsumption for a ng 2.5 percent of this radiation
- Sunlight striking the earth for 40 minutes is
equivalent to global energy co year.
- 250,000 square miles of land in the Southwest
US are suitable for constructing solar power
- plants. This area is slightly larger than the
combined areas of Arizona and New Mexico.
- This area of land receives 4,500 quadrillion
British thermal units (Btu) of solar radiation per
- year. Converti
into electricity would match the nation’s total energy consumption in 2006.
25 25
Powering the US
Total cost to implement = $400 billion over Plan would require 14% efficiency and an Several methods of providing electricity : Is $1.00/watt installed still a
- the next 40 years.
- installation cost of $1.20 per watt of capacity.
- during non-electricity producing times have
been proposed. QUESTION realistic number considering that the cost of oil has increased by a factor of 5 since the $1.00/watt target was established.
Scientific American, page 63, January 2008
26 26
World PV Production
- PV production has been
doubling every 2 years since 2002 making it the fastest growing energy source.
- Existing grid-connected
solar PV capacity is 7.8 GW
27 27
PV Production by Selected Countries
China:
- tripled PV production in 2006
- doubled PV production in 2007
- market share in 2003 was 1%
- market share today is 18%
- 400 PV companies
28 28
29 29
Thin Film PV Production
Thin film production grew from 4 to 7% of the PV market from 2003 to 2007
PV Market Share
30 30
Market share of solar cell types sold during 2006.
(Source: Materials Today, Volume 10, Issue 11, page 21, November 2007)
PV Needs and Concerns
- World uses about 13 TW of pow
2050
- Conventional multicrystalline silicon solar cell modules of
today have an efficiency of about 12% and provide electricity at a cost of $0.27/kWh compared to today’s grid electricity cost of $0.06/kWh
- In addition to the solar cell cost, the installation costs are
also high . er – will rise to 30 TW by
- Any new solar cell must have an efficiency of at least 10
percent to be economically viable.
- Scalability is also an issue, as are reliability and lifetime
(Source: Photonics Spectra, page 70, November 2007)
31 31
EFFICIENCY (%) AREA (cm2 24.7 4.0 20.3 1.0 rystalline Si) 10.1 1.2 µc-Si/αSi:H 11.7 14.2
(Best to Date)
PV Cell Efficiencies
TYPE OF CELL ) Crystalline Si Multicrystalline Si Amorphous (and nanoc micro-morph cell
32 32
PV Cost and Projected Cost
33 33
Efficiency and cost projections for first- (I), second- (II), and third- generation (III) PV technologies (wafer-based, thin films, and advanced thin films, respectively)
- CURRENT = $2-3 PER WATT
(1ST GENERATION CELLS)
- BY 2009 = $1 PER WATT
(2ND GENERATION CELLS)
- BY 2010 = $0.70 PER WATT
(3RD GENERATION CELLS) - POSSIBLY TO 0.20 PER WATT EVENTUALLY
[Source: Materials Today, Volume 10, No. 11, page 42, November 2007].
PV Module Cost per Watt
34 34
35 35
Photovoltaic Power Generation Photovoltaic Power Generation
Photovoltaic Market Growth ~ 25%/y Photovoltaic Market Growth ~ 25%/y Production reached ~ 1.6 GW/y Production reached ~ 1.6 GW/y International PV Roadmap International PV Roadmap – – 100 GW/y by 2030 (10%) 100 GW/y by 2030 (10%) – – 50% from renewables by 2050 50% from renewables by 2050 – – 2/3 Solar (PV/thermal) by 2100 2/3 Solar (PV/thermal) by 2100 Methods for Success Methods for Success – – Module Cost Reduction Module Cost Reduction – – Availability of Silicon Availability of Silicon – – Higher Efficiency Higher Efficiency – – Increased Module Lifetime Increased Module Lifetime
36 36
Planned Solar Cell Planned Solar Cell Production Capacity by 2010 Production Capacity by 2010
Expected market Expected market 1000 MW 1000 MW Capacities Announced Capacities Announced 2200 MW 2200 MW Thin Film Share Thin Film Share 328 MW 328 MW Crystalline Share Crystalline Share 1872 MW 1872 MW
Thin Film Silicon Solar Cells Thin Film Silicon Solar Cells A Viable Option A Viable Option
C C-
- Si Solar Cells
Si Solar Cells
- cell processing; 40% module)
cell processing; 40% module) g for Increased Absorption g for Increased Absorption Substrate Cost is ~40% in Substrate Cost is ~40% in (20% (20% Thin Si Films on Low Cost Substrates Offer Thin Si Films on Low Cost Substrates Offer Great Potential Great Potential Hydrogenated Amorphous Silicon Thin Film Hydrogenated Amorphous Silicon Thin Film Technology is Mature Technology is Mature Development of Microcrystalline, Development of Microcrystalline, Polycrystalline and Epitaxial Silicon Polycrystalline and Epitaxial Silicon Light Trappin Light Trappin Surface Passivation for Low Recombination Surface Passivation for Low Recombination Velocity Velocity
37 37
Experimental Experimental
Hydrogenated Amorphous Silicon Hydrogenated Amorphous Silicon Deposited by Plasma Enhanced Chemical Deposited by Plasma Enhanced Chemical Vapor Deposition (PECVD) as well as rf Vapor Deposition (PECVD) as well as rf Magnetron Sputtering Magnetron Sputtering Aluminum Film Deposited by rf Magnetron Aluminum Film Deposited by rf Magnetron Sputtering Sputtering Annealing for Crystallization by Annealing for Crystallization by Conventional Furnace, Optical, and Laser Conventional Furnace, Optical, and Laser Beam Systems Beam Systems Characterization by XRD, SEM, TEM, HR Characterization by XRD, SEM, TEM, HR-
- TEM, AES, etc.
TEM, AES, etc.
38 38
U of A (Sputtering/PECVD) Cluster Tool U of A (Sputtering/PECVD) Cluster Tool
39 39
40 40
ITZ Robotic Arm MPZ5 Silicon Sputter Annealing Chamber MPZ1 MPZ2 MPZ4 MPZ3 Substrate Loading station a-Si:H/a-SiN:H PECVD Aluminum Sputter Doped a-Si:H PECVD
41 41
Large Grain Silicon Thin Films by Metal-Induced Crystallization
Large Grain Needed for Reducing EHP Large Grain Needed for Reducing EHP Recombination at the Grain Boundaries Recombination at the Grain Boundaries
Vs Glass Substrate Crystallized Si Glass Substrate
42 42
Fabrication Process
Glass
Aluminum
a-Si:H
Poly- Si
- xide
Annealing at < 450 C/ 20 min
Results (cont..) Results (cont..)
SEM Images
43 43
44 44
Grain Size Control Grain Size Control
Amorphous Si microstructure can Amorphous Si microstructure can influence grain size of crystallized influence grain size of crystallized
- silicon. Hydrogen and doping can
- silicon. Hydrogen and doping can
also influence grain size and also influence grain size and crystallization rates. crystallization rates. Introducing an interface layer (of Introducing an interface layer (of silcon oxide, aluminum oxide, or silcon oxide, aluminum oxide, or even other types of layers) can even other types of layers) can influence grain size influence grain size
Results Results
SEM image of a ‘zero minute
- xide layer) crystallized at 400
etched away from the sample. SEM Image ’ sample (no °C. Al has been
45 45
Results (cont.)
Oxide SEM Images
Results (cont.)
No oxide
46 46
Results (cont..) Results (cont..)
AFM Images No oxide Oxide
47 47
XRD Results
26 28 30 32 34 36 38 200 400 600 800 Aluminum Silicon (111) CPS(arb.) 2θ (
0)
a acuum , Curve II is a 10 minute ambient , and Curve two days (two- . Oxide layer allization XRD spectra of three
- samples. Curve I is for
sample kept in v (zero-minute ambient exposure time)
(111)
sample kept outside for minutes (10-
48 48
40 42 III II I
exposure time) III is for one kept in the ambient for day ambient exposure time) The curves are shifted vertically to compare the peak heights. increases cryst temperature.
Nano Nano-
- Aluminum
Aluminum-
- Induced
Induced Crystallization Crystallization
Substrate was oxide coated silicon wafer Substrate was oxide coated silicon wafer PECVD a PECVD a-
- Si thickness was 100 nm
Si thickness was 100 nm Aluminum thickness was 40 nm Aluminum thickness was 40 nm Annealing temperature: 300 Annealing temperature: 300-
- 450
450˚ ˚C C Annealing temperature ramp Annealing temperature ramp-
- up time
up time was varied to influence nucleation was varied to influence nucleation density density Excess aluminum was removed by Excess aluminum was removed by etching etching
49 49
Nano-Aluminum-
aled for 10 20 30 40 50 60 300 Largest Grain Size (µm) Anne 30 minutes 350 400 450 Annealing Temperature (oC)
Induced Crystallization
Crystallite size versus annealing temperature
50 50
Nano-Aluminum-Induced Crystallization
5 10 15 Annealing Ramp Up Time (Hour) nano-AIC traditional AIC A B 30 60 90 120 Grain Size (um) 20
51 51
Relationship between grain size and ramp up time of annealing
- temperature. It shows that grain size significantly increased with
ramp up time for nano-AIC of a-Si:H, but changes little for traditional AIC of a-Si:H.
Nano-Aluminum-Induced Crystallization
50 µm
Microscopy image of sample annealed at 300oC for 30 minutes
52 52
Nano-Aluminum-Induced Crystallization
53 53
20 µm
ages of the grains on the samples with 20 hour p time. The largest grain size is about 93 mm Microscopy im annealing ram .
a-S 200 nm Al 30 nm Al Si (220) Si (311) 300 600 900 Intensity (arbitrary unit) Si (111) i:H 25 35 45 55 65 75 2θ (degree)
XRD spectra of (a) a-Si:H, (b) nano-AIC of a-Si:H, and (c) traditional AIC of a-Si:H. The large peaks around 2θ=28.5 degree are Si (111), indicating crystallization occurred for both (b) and (c).
Nano-Aluminum-Induced Crystallization
54 54
aphy of
- other
b
55 55
3-D SPM images showing the surface topogr (a) a-Si:H; and polycrystalline silicon films produced by (b) nano-AIC, and (c) traditional AIC. It shows that nano-AIC creates much sm
a
surfaces than traditional AIC.
c
Nano-Aluminum-Induced Crystallization
Area in micrograph is 1.275 mm wide by 0.95 mm high. Crystallite size varies from 0.1 to 1.0 mm.
56 56
57 57
University of Arkansas Patented University of Arkansas Patented Solar Cell Process Using MIC Solar Cell Process Using MIC
HF Clean Thin SX or MC Si HF Clean Thin SX or MC Si Deposit a Deposit a-
- Si:H on Front by
Si:H on Front by PECVD/Sputtering PECVD/Sputtering Deposit n Deposit n+
+(5% P) doped
(5% P) doped a a-
- Si:H on Back
Si:H on Back Deposit Al on Front and Deposit Al on Front and Back Back Anneal to Crystallize and Anneal to Crystallize and Texture (200 Texture (200-
- 300
300° °C) C)
Thin N-Type X-Si Thin N-Type X-Si Thin N-Type X-Si Thin N-Type X-Si Thin N-Type X-Si Thin N-Type X-Si
Etch Grid and Deposit AR Etch Grid and Deposit AR
58 58
Comparison of Standard Vs U of A Comparison of Standard Vs U of A Technologies Technologies
at 1000°C High Temp Labor Intensive Sputt/PECVD a-Si:H Backside n+ a-Si:H Sputter Al Phosph Diff Process Start with P-Type X-Si Standard Technology Start with N-Type X-Si Anneal 200-300°C a-SiN:H AR Coating New Patented Tech Batch Back and Side Lapping Screen Printing Contacts Sintering at >600°C Bowing AR Coating High
- Sur. Rec.
Silicon Thin Film Solar Cell Silicon Thin Film Solar Cell
With Corrugated Substrate for Efficient With Corrugated Substrate for Efficient Light Trapping Light Trapping p p-
- i
i-
- n Type Solar Cell
n Type Solar Cell Light Ray Traverses hundreds of microns Light Ray Traverses hundreds of microns laterally though Multiple Internal laterally though Multiple Internal Reflection Reflection
Thin Film Solar Cell on Low Cost Glass or Plastic Substrate
59 59
60 60
Growth of Epitaxial silicon
Aluminum a-Si:H Aluminum Epitaxial Si active layer
Anneal at 500°C
Metallurgical Grade (100) Crystalline Si
SEM Image
b No c Protrusions
Si film. The image scale is
a rystallization
SEM image of the 300 nm thick at: a) 20 µm b) 2 µm. Annealed at 525ºC for 60 minutes
61 61
High Resolution X-Sectional TEM
Substrate Epitaxial film
interface a
The interface between the epitaxial film and the (100) silicon substrate
62 62
High Resolution X-Sectional TEM
b
The center of the epitaxial film
63 63
High Resolution X-Sectional TEM
64 64
c
Epitaxial film
the epitaxial silicon film and the aluminum film showing the epitaxial crystal planes of the film The interface between
Al film
thickness. through its entire
Auger Depth Profiles
65 65
Profile Time=0 Profile - Time=10min 120 (b)
20 40 60 80 Atomic % 100 120 200 400 600 800 1000 1200 1400 Depth (nm) C O Al Si
(a) Depth (nm)
20 40 60 80 Atomic % 200 400 600 800 1000 1200 1400 Depth (nm)
O Al
Atomic % Depth (nm)
Profile - Time=15min 20 40 60 80 100 120 200 400 600 800 1000 1200 1400 Depth (nm) Atomic %
O Al Si
(c)
Profile - Time=30min
20 40 60 80 100 120 200 400 600 800 1000 1200 1400 Depth (nm) Atomic %
O Al Si
(d) Atomic %
100
Si
Aluminum Induced Aluminum Induced Crystallization of a Crystallization of a-
- Si:H
Si:H
66 66
a a-
- Si:H crystallized to continuous poly
Si:H crystallized to continuous poly-
- Si
Si films at 150 films at 150-
- 300
300° °C; Grain Size ~ 0.5 C; Grain Size ~ 0.5 µ µm m Grain Size Achieved ~ 20 Grain Size Achieved ~ 20-
- 30
30 µ µm at 300 m at 300-
- 450
450° °C using a 1 C using a 1-
- 3 nm oxide barrier layer
3 nm oxide barrier layer Epitaxial Si film is produced on (100) SX Epitaxial Si film is produced on (100) SX-
- Si at 400
Si at 400-
- 550
550° °C C
Anneal 300-450°C Anneal 150-300°C Anneal 450-550°C
67 67
Summary and Conclusions Summary and Conclusions
Energy Needs of the World are Increasing Energy Needs of the World are Increasing Exponentially Exponentially Sustainable Energy Strongly Suggest Solar Sustainable Energy Strongly Suggest Solar Energy to Dominate by 2100 Energy to Dominate by 2100 Silicon is the Material of Choice in Solar PV Silicon is the Material of Choice in Solar PV Thin silicon Solar Cells, Low Temperature Thin silicon Solar Cells, Low Temperature In In-
- Line Fabrication, Low Cost Substrates
Line Fabrication, Low Cost Substrates Low Temperature Crystallization of a Low Temperature Crystallization of a-
- Si:H
Si:H has Great Potential has Great Potential Large Grain Poly Large Grain Poly-
- Si and Epitaxial Si at Low
Si and Epitaxial Si at Low Temperatures have been Demonstrated Temperatures have been Demonstrated
68 68
Acknowledgement Acknowledgement
We acknowledge the financial support of the We acknowledge the financial support of the following agencies: following agencies:
– – NASA (HQ)/Arkansas EPSCoR NASA (HQ)/Arkansas EPSCoR – – NASA Goddard/Arkansas Space and Planetary NASA Goddard/Arkansas Space and Planetary Center Center – – DOE/Arkansas EPSCoR DOE/Arkansas EPSCoR – – National Renewable Energy Lab (NREL) National Renewable Energy Lab (NREL) – – Oak Ridge National Lab (ORNL) Oak Ridge National Lab (ORNL) – – Southern Universities Research Association Southern Universities Research Association (SURA) (SURA) – – National Center for Electron Microscopy (NCEM) National Center for Electron Microscopy (NCEM) – – NSF (USA)/DST (INDIA) NSF (USA)/DST (INDIA) – – Fulbright Institute Fulbright Institute