CIS/CIGS Solar Cells

Mark-Daniel Gerngroß, Julia Reverey

02/04/2008 12:00 - 12:45
A. 241

Mawi Seminar WS 07/08 Prof. Dr. H. Föll

 Motivation

solution: solar cells, especially CIS/ CIGS solar cells

problem: short running
problem: global oil resources
warming andclimate
and raising power
changedemand
http://world.honda.com/environment/2006report/05010000_12.jpg
http://www.smh.com.au/ffximage/2005/10/07/arctic_wideweb__430x308.jpg
http://blog.kir.com/archives/oil%20and%20gas%20well%20at%20sunset3.jpg
http://www.photon-magazine.com/news/news_2004-03%20ap%20sn%20Honda_big.jpg
http://www.elenatour.uz/photo/uzb/images/Uzbekistan.%20Desert%20Kizil%20Kum.%20Takir.jpg
http://cache.eb.com/eb/image?id=91641&rendTypeId=4
Contents

• Introduction
• Material Properties
• Growth Methods for Thin Films
• Development of CIGS Thin Film Solar Cells
• Fabrication Technology
• Conclusion & Prospect
Introduction

• CIS = CuInSe2 (copper indium diselenide)

CIGS = CuInxGa1-xSe2 (copper indium gallium diselenide)
• compound semiconductor ( I-III-VI)
• heterojunction solar cells
• high efficiency (≈19% in small area, ≈13% in large area modules)
• very good stability in outdoor tests

• applications:
– solar power plants
– power supply in aerospace
– decentralized power supply
– power supply for portable purposes

http://www.copper.org/innovations/2007/05/images/civilian_flex_panel.jpg
http://www.rgp.ufl.edu/publications/explore/v12n2/images/thin-film.jpg
http://www.baulinks.de/webplugin/2007/i/0732-wuerthsolar1.jpg
http://www.esa.int/images/ISS_2004_web400.jpg
Contents

• Introduction
• Material Properties
• Phase diagram
• Impurities & Defects
• Growth Methods for Thin Films
• Development of CIGS Thin Film Solar Cells
• Fabrication Technology
• Conclusion & Prospect
Material Properties I

• crystal structure:
– tetragonal chalcopyrite structure
– derived from cubic zinc blende structure
– tetrahedrally coordinated
• direct gap semiconductor
• band gap: 1.04eV – 1.68eV

• exceedingly high adsorptivity

• adsorption length: >1µm

• minority-carrier lifetime: several ns

• electron diffusion length: few µm
• electron mobility: 1000 cm2 V -1 s-1 (single crystal)

ShiyouHamakawa,
Chen and X.
Yoshihiro:
G. Gong:Thin
Physical
Film Solar
ReviewCells,
B 75,Springer,
2052092004.
2007
Material Properties II

• simplified version of the ternary phase diagram

• reduced to pseudo-binary phase diagram along the red dashed line
• bold black line: photovoltaic-quality material
• 4 relevant phases: -, -, -phase and Cu2Se

Hamakawa, Yoshihiro: Thin Film Solar Cells, Springer, 2004.

Material Properties III

• -phase (CuInSe2):
– range @RT: 24-24.5 at%
– optimal range for efficient thin film solar cells: 22-24 at %
 possible at growth temp.: 500-550°C, @RT: phase separation into +

• -phase (CuIn3Se5)
– built by ordered arrays of defect pairs
( VCu, InCuanti sites)

• -phase (high-temperature phase)

– built by disordering Cu & In sub-lattice

• Cu2Se
– built from chalcopyrite structure by
Cu interstitials Cui & CuIn anti sites

Hamakawa, Yoshihiro: Thin Film Solar Cells, Springer, 2004.

Impurities & Defects I

problem: a-phase highly narrowed @RT

– solution: widening -phase region by impurities
• partial replacement of In with Ga
– 20-30% of In replaced
– Ga/(Ga+In) 0.3
band gap adjustment

• incorporation of Na
– 0.1 at % Na by precursors
 better film morphology
passivation of grain-boundaries
 higher p-type conductivity
 reduced defect concentration

Hamakawa, Yoshihiro: Thin Film Solar Cells, Springer, 2004.

Impurities & Defects II

• doping of CIGS with native defects:

– p-type:
• Cu-poor material, annealed under high Se vapor pressure
• dominant acceptor: VCu
• problem: VSe compensating donor

– n-type:
• Cu-rich material, Se deficiency
• dominant donor: VSe

• electrical tolerance to large-off stoichiometries

– nonstoichiometry accommodated in secondary phase
– off-stoichiometry related defects electronically inactive
Impurities & Defects III

• electrically neutral nature of structural defects

– Efdefect complexes < Efsingle defect
 formation of defect complexes out of certain defects
VCu, InCu, CuIn, InCu and 2Cui, InCu
 no energy levels within the band gap

• grain-boundaries electronically nearly inactive

Contents

• Introduction
• Material Properties
• Growth Methods for Thin Films
• Coevaporation process
• Sequential process
• Roll to roll deposition
• Development of CIGS Thin Film Solar Cells
• Fabrication Technology
• Conclusion & Prospect
Growth Methods for Thin Films I

coevaporation process:
– evaporation of Cu, In, Ga and Se from elemental sources
– precise control of evaporation rate by EIES & AAS or mass spectrometer
– required substrate temperature between 300-550°C
– inverted three stage process:
• evaporation of In, Ga, Se
• deposition of (In,Ga)2Se3
on substrate @ 300°C
• evaporation of Cu and Se
deposition at elevated T
• evaporation of In, Ga, Se
 smoother film morphology
highest efficiency
Hamakawa, Yoshihiro: Thin Film Solar Cells, Springer, 2004.
Growth Methods for Thin Films II

sequential process:
– annealing of from
selenization stacked elemental layers
vapor:
• substrate: soda lime glass coated with Mo
• deposition of Cu and In, Ga layers bysputtering
films by sputtering
• deposition
selenizationofunder
Se layer by atmosphere
H2Se evaporation
• rapid thermal
thermal processprocess
for conversion into CIGS
advantage: large-area deposition
avoidance
disadvantage: of toxic
use of toxic H2(H
gases Se 2Se)

Hamakawa, Yoshihiro: Thin Film Solar Cells, Springer, 2004.

Growth Methods for Thin Films III

roll to roll deposition:

– substrate: polyimide/ stainless steel foil coated with Mo
– ion beam supported low temperature deposition of Cu, In, Ga & Se

Mo Cu,Ga,In,Se CdS ZnO

advantages: low cost production method

flexible modules and high power per weight ratio
disadvantages: lower efficiency

http://www.solarion.net/images/uebersicht_technologie.jpg
Contents

• Introduction
• Material Properties
• Growth Methods for Thin Films
• Development of CIGS Thin Film Solar Cells
• Cross section of a CIGS thin film
• Buffer layer
• Window layer
• Band-gap structure
• Fabrication Technology
• Conclusion & Prospect
Development of CIGS Solar Cells I

Zn0 front contact 0.5µm

CdS buffer 50nm

CIGS absorber 1.6 µm

Mo back contact 1µm

soda lime glass

substrate 2mm

www.kolloquium-erneuerbare-energien.uni-stuttgart.de/downloads/Kolloq_2006/Dimmler_EEKolloq-290606.pdf
Development of CIGS Solar Cells II

Buffer layer: CdS

• deposited by chemical bath deposition (CBD)
• layer thickness: 50 nm
properties:
• band gap: 2.5 eV
• high specific resistance
• n-type conductivity
• diffusion of Cd 2+ into the CIGS-absorber (20nm)
 formation of CdCu- donors, decrease of recombination at CdS/CIGS
interface
function:
• misfit reduction between CIGS and ZnO layer
• protection of CIGS layer

Hamakawa, Yoshihiro: Thin Film Solar Cells, Springer, 2004.

 Development of CIGS Solar Cells III

Window layer: ZnO

• band gap: 3.3 eV
• bilayer high- / low-resistivity ZnO deposited by RF-sputtering / atomic
layer deposition (ALD)
• resistivity depending on deposition rate (RF-sputtering)/flow rate (ALD)

• high-resistivity layer:
- layer thickness 0.5µm
- intrinsic conductivity
• low-resistivity layer:
- highly doped with Al (1020 cm-3)
- n-type conductivity

function:
• transparent front contact
R.Menner, M.Powalla: Transparente ZnO:Al2O3 Kontaktschichten für CIGS Dünnschichtsolarzellen
Development of CIGS Solar Cells IV

band gap structure:

• i-ZnO inside space-charge region
• discontinuities in conduction band structure
– i-ZnO/CdS: 0.4eV
– CdS/CIGS: - 0.4eV –0.3eV
depends on concentration of Ga

• positive space-charge at CdS/CIGS

• huge band discontinuities of
valance-band edge
 electrons overcome heterojunction
exclusively

• heterojunction: n+ip
Meyer, Thorsten: Relaxationsphänomene im elektrischen Transport von Cu(In,Ga)Se2, 1999.
Contents

• Introduction
• Material Properties
• Growth Methods for Thin Films
• Development of CIGS Thin Film Solar Cells
• Fabrication Technology
• Cell processing
• Module processing
• Conclusion & Prospect
Fabrication Technology I

cell processing:
• monolithical
– deposition integration:
Ni/Al
of
substrate washbuffer
#1collector
layer grid
–
– during cell #2
deposition
patterning processing
of antireflection coating
metal base electrode
–
– fabrication
deposition ofn-type
patterning of
#1 complete modules
window layer
– patterning#3
formation of p-type CIGS absorber

substrate
Hamakawa, Yoshihiro: Thin Film Solar Cells, Springer, 2004.
Fabrication Technology II

module processing:
– packaging technology nearly identical to crystalline-Si solar cells

tempered glass as cover glass ethylene vinyl acetate (EVA) as pottant

soda-lime glass as substrate

Al frame
junction box with leads
CIGS-based circuit

Hamakawa, Yoshihiro: Thin Film Solar Cells, Springer, 2004.

Contents

• Introduction
• Material Properties
• Growth Methods for Thin Films
• Development of CIGS Thin Film Solar Cells
• Fabrication Technology
• Conclusion & Prospect
Conclusion & Prospects

conclusion:
prospects:
• high
increasing
reliability
utilization (solar parks, aerospace etc.)
• high efficiencyof(≈19%
optimization in small
fabrication area, ≈13% in large area modules)
processes
• less
gainconsumption
in efficiency for
of materials
large areaand
solar
energy
cells
• monolithical
possible shortintegration
run of indium and gallium resources
• high level of automation

http://img.stern.de/_content/56/28/562815/solar1_500.jpg
www.kolloquium-erneuerbare-energien.uni-stuttgart.de/downloads/Kolloq_2006/Dimmler_EEKolloq-290606.pdf
 Thank you for your attention!

sources:
Hamakawa, Yoshihiro: Thin Film Solar Cells, Springer, 2004.
Meyer, Thorsten: Relaxationsphänomene im elektrischen Transport von
Cu(In,Ga)Se2, 1999.
Dimmler, Bernhard: CIS-Dünnschicht-Solarzellen Vortrag, 2006.