Solar Cell Technology

Current State of the Art

Where are we headed?

Gerald Gourdin

Introduction to Green Chemistry

Fall 2007

1
 Introduction
 1839: Photovoltaic effect was first recognized by French physicist
Alexandre-Edmond Becquerel.
 1883: First solar cell was built by Charles Fritts, who coated the
semiconductor selenium with an extremely thin layer of gold to form the
junctions (1% efficient).
 1946: Russell Ohl patented the modern solar cell
 1954: Modern age of solar power technology arrives - Bell Laboratories,
experimenting with semiconductors, accidentally found that silicon doped
with certain impurities was very sensitive to light.
 The solar cell or photovoltaic cell fulfills two fundamental functions:
 Photogeneration of charge carriers (electrons and holes) in a light-absorbing
material
 Separation of the charge carriers to a conductive contact to transmit electricity

Nov-21-07 2
 Photon Absorption
Photons absorption creates mobile electron-hole pairs

 Photon is absorbed and energy is given to an electron in the crystal lattice

 Usually this electron is in valence band, tightly bound in covalent bonds.
 Energy given by the photon “excites” it into the conduction band
 Covalent bond now has one fewer electron (hole).
 Bonded electrons of neighboring atoms can move into the ‘hole’, leaving another hole
behind – hole can propagate through lattice.
 Free electrons flow through the material to produce electricity.
 Positive charges (holes) flow in opposite direction.
 Different PV materials have different
band gap energies.
 Photons with energy equal to the band
gap energy are absorbed to create
free electrons.
 Photons with less energy than the
band gap energy pass through the
material

Nov-21-07 3
 Doped Semiconductor
p-n Junction Diode
 Semiconductor doped to change
Contact Surface n-Layer
electronic properties
 n-type semiconductor
 increase number free electrons Extra
electrons
 p-type semiconductor
 increase number free ‘holes’

Junction
1. Absorption of a photon
2. Formation of electron-hole pair (exciton)
3. Exciton diffusion to Junction
Extra
4. Charge separation
holes
5. Charge transport to the anode (holes)
and cathode (electrons)
6. Supply a direct current for the load.
Contact Surface p-Layer

Nov-21-07 4
 Electricity Generation

 p-n junction in thermal equilibrium w/ zero bias voltage applied.

 Electrons and holes concentration are reported respectively with blue and red lines.
 Gray regions are charge neutral.
 Light red zone is positively charged; light blue zone is negatively charged.
 Electric field shown on the bottom, the electrostatic force on electrons and holes and the
direction in which the diffusion tends to move electrons and holes.

Nov-21-07 5
 Cell Structures
 Homojunction Device
 Single material altered so that one side is p-type and the other side
is n-type.
 p-n junction is located so that the maximum amount of light is
absorbed near it.
 Heterojunction Device
 Junction is formed by contacting two different semiconductor.
 Top layer - high bandgap selected for its transparency to light.
 Bottom layer - low bandgap that readily absorbs light.
 p-i-n and n-i-p Devices
 A three-layer sandwich is created,
 Contains a middle intrinsic layer between n-type layer and p-type
layer.
 Light generates free electrons and holes in the intrinsic region.

Nov-21-07 6
 Overview
 First Generation
 Single crystal silicon wafers (c-Si)
 Second Generation
 Amorphous silicon (a-Si)
 Polycrystalline silicon (poly-Si)
 Cadmium telluride (CdTe)
 Copper indium gallium diselenide (CIGS) alloy
 Third Generation
 Nanocrystal solar cells
 Photoelectrochemical (PEC) cells
• Gräetzel cells
 Polymer solar cells
 Dye sensitized solar cell (DSSC)
 Fourth Generation
 Hybrid - inorganic crystals within a polymer matrix
Nov-21-07 7
 First Generation (Silicon)
First generation photovoltaic cells are the dominant technology in the
commercial production of solar cells, accounting for more than 86% of
the solar cell market.

 Cells are typically made using a crystalline silicon wafer.

 Consists of a large-area, single layer p-n junction diode.
 Approaches
 Ingots can be either monocrystalline or multicrystalline
 Most common approach is to process discrete cells on wafers sawed from
silicon ingots.
 More recent approach which saves energy is to process discrete cells on silicon
wafers cut from multicrystalline ribbons
 Band gap ~1.11 eV

Nov-21-07 8
 First Generation: Research Cells

13-14%

Source: National Renewable Laboratory

Nov-21-07 9
 First Generation: Evaluation

 Advantages
 Broad spectral absorption range
 High carrier mobilities
 Disadvantages
 Requires expensive manufacturing technologies
 Growing and sawing of ingots is a highly energy intensive process
 Fairly easy for an electron generated in another molecule to hit a hole left
behind in a previous photoexcitation.
 Much of the energy of higher energy photons, at the blue and violet end of the
spectrum, is wasted as heat

Nov-21-07 10
 Second Generation: Overview
Thin-film Technology

 Based on the use of thin-film deposits of semiconductors.

 Using of thin-films reduces mass of material required for cell design.
 Contributes greatly to reduced costs for thin film solar cells.
 Several technologies/semiconductor materials currently under investigation or
in mass production
 Deposition of thin layers of non-crystalline-silicon materials on inexpensive
substrates using PECVD.
 Devices initially designed to be high-efficiency, multiple junction photovoltaic
cells.

Nov-21-07 11
 Second Generation: PECVD
Plasma Enhanced Chemical Vapor Deposition
 Thin-film deposition
 Technique for depositing a thin film of material onto a substrate.
 Layer thickness can be controlled to within a few tens of nanometers
 Single layers of atoms can be deposited

 Chemical vapor deposition (CVD)

 Chemical process using a gas-phase precursor.
 Often a halide or hydride of the deposited element. Pressure
 PECVD - Plasma Enhanced CVD sensors Exhaust

 Uses an ionized vapor, or plasma, as a precursor Reactor

 Relies on electromagnetic means (electric current,
microwave excitation) to produce plasma. Valve Burner
Anode

gas Substrate

Cathode Pumping
Anode
system

Schematic of a single-chamber VHF-

VHF
GD deposition system

Nov-21-07 12
 Second Generation: Types
 Amorphous silicon cells deposited on stainless-steel ribbon
 Can be deposited over large areas by plasma-enhanced chemical vapor deposition
 Can be doped in a fashion similar to c-Si, to form p- or n-type layers
 Used to produce large-area photovoltaic solar cells
 Band gap ~ 1.7 eV
 Polycrystalline silicon
 Consists solely of crystalline silicon grains (1mm), separated by grain boundaries
 Main advantage over amorphous Si: mobility of the charge carriers can be orders of
magnitude larger
 Material shows greater stability under electric field and light-induced stress.
 Band gap ~ 1.1 eV
 Cadmium telluride (CdTe) cells deposited on glass
 Crystalline compound formed from cadmium and tellurium with a zinc blende (cubic) crystal
structure (space group F43m)
 Usually sandwiched with cadmium sulfide (CdS) to form a p-n junction photovoltaic solar
cell.
 Cheaper than silicon, especially in thin-film solar cell technology - not as efficient
 Band gap ~ 1.58 eV
 Copper indium gallium diselenide (CIGS) alloy cells
 Deposited on either glass or stainless steel substrates
 More complex heterojunction model
 Band gap ~ 1.38 eV
Nov-21-07 13
 Second Generation: Research Cells

13-14%

9%

Source: National Renewable Laboratory

Nov-21-07 14
 Second Generation: Evaluation

 Advantages
 Lower manufacturing costs
 Lower cost per watt can be achieved
 Reduced mass
 Less support is needed when placing panels on rooftops
 Allows fitting panels on light or flexible materials, even textiles.
 Disadvantages
 Typically, the efficiencies of thin-film solar cells are lower compared
with silicon (wafer-based) solar cells
 Amorphous silicon is not stable
 Increased toxicity

Nov-21-07 15
 Third Generation: Overview
Different Semiconductor Technology

 Very different from the previous semiconductor devices

 Do not rely on a traditional p-n junction to separate
photogenerated charge carriers.
 Devices include:
 Nanocrystal solar cells
 Photoelectrochemical cells
• Gräetzel Cell
 Dye-sensitized hybrid solar cells
 Polymer solar cells

Nov-21-07 16
 Third Generation: Types
Nanocrystal solar cells

 Solar cells based on a silicon substrate with a coating of nanocrystals

 Silicon substrate has small grains of nanocrystals, or quantum dots
• Lead selenide (PbSe) semiconductor
• Cadmium telluride (CdTe) semiconductor
 Quantum dot is a semiconductor nanostructure
• Confines the motion of conduction band electrons, valence band holes, or
excitons in all three spatial directions.
 Thin film of nanocrystals is obtained by a process known as “spin-
coating”
 Excess amount of solution placed onto a substrate then rotated very
quickly
 Higher current potential for solar cells

Nov-21-07 17
 Third Generation: Types
Photoelectrochemical (PEC) cells
 Separate the two functions provided by silicon in a traditional cell
design
 Consists of a semiconducting photoanode and a metal cathode
immersed in an electrolyte.
 K3 Fe(CN)6/K4 Fe(CN)6
 Iodide/Triiodide
 Fe(CN)64-/Fe(CN)63-
 Sulphide salt/sulphur
 Charge separation not solely provided by the semiconductor, but
works in concert with the electrolyte.
 Gräetzel cells
 Dye-sensitized PEC cells
 Semiconductor solely used for charge separation,
 Photoelectrons provided from separate photosensitive dye
 Overall peak power production represents a conversion efficiency of about 11%

Nov-21-07 18
 Third Generation: Gräetzel Cells
Dyes
 ruthenium metal organic Load
complex
 carboxylic acid functionalized
porphyrin arrays

Dye and TiO2

Electrolyte

 Dye molecules are hit by light

 Electrons in the dye are transmitted to TiO2.
 The electrons are collected by front electrode and supplied to external
load.
 Dye molecules are electrically reduced to their initial states by electrons
transferred from redox couple in the electrolyte.
 The oxidized ions in the electrolyte, diffuse to the back electrode to receive
electrons
Nov-21-07 19
 Third Generation: Types
Polymer solar cells
 ‘Bulk heterojunctions’ between an organic polymer and organic molecule
as electron acceptor.
 Fullerene embedded into conjugated polymer conductor
 Lightweight, disposable, inexpensive to fabricate, flexible, designable on
the molecular level, and have little potential for negative environmental
impact.
 Present best efficiency of polymer solar cells lies near 5 percent
 Cost is roughly one-third of that of traditional silicon solar cell technology
 Band gaps ≥ 2eV

Nov-21-07 20
 Third Generation: Polymer Cell
 After excitation in photoactive polymer, the electron is transferred to the C60
due to its higher electron affinity
 Photoinduced quasiparticle (polaron P+) formed on the polymer chain and
fullerene ion-radical C60-

e-

PEDOT Al
Load
ITO
e-

PET foil

The scheme of plastic solar cells.

 PET - Polyethylene Terepthalate
 ITO - Indium Tin Oxide (In2O3/SnO2) PET
 PEDOT - Poly(3,4-ethylenedioxythiophene)
 Al - Aluminium
PEDOT

Nov-21-07 21
 Third Generation: Types
Dye sensitized solar cell (DSSC)
 Separate the two functions provided by silicon in a traditional cell design
 Semiconductor used solely for charge separation
 Photoelectrons provided from separate photosensitive dye
 Typically a ruthenium metal organic dye

 Cell Design:
 Dye-sensitized titanium dioxide
 Coated and sintered on a transparent semi-conducting oxide (ITO)
 p-type, polymeric conductor, such as PEDOT or PEDOT:TMA, which carries
electrons from the counter electrode to the oxidized dye.

 Similar to Gräetzel cell except the electrolyte is replaced with a conductive

polymer.

Nov-21-07 22
 Third Generation: DSSC
Dye-sensitized, hole-conducting polymer cell

e- Load e-

ITO

Dye and TiO2 PEDOT:TMA

hv

The scheme of DSSC.

 PET - Polyethylene Terephtalate
 ITO - Indium Tin Oxide
 PEDOT:TMA - Poly(3,4-ethylenedioxythiophene)-tetramethacrylate

Nov-21-07 23
 Third Generation: Research Cells

13-14%

9%
8%

Source: National Renewable Laboratory

Nov-21-07 24
 Third Generation: Evaluation
 Advantages
 Low-energy, high-throughput processing technologies
 Polymer cells - solution processable, chemically synthesized
 Polymer cells - low materials cost
 Gräetzel cells - attractive replacement for existing technologies in “low
density” applications like rooftop solar collectors
 Gräetzel cells - Work even in low-light conditions
 DSSC - potentially rechargeable => upgradeable?

 Disadvantages
 Efficiencies are lower compared with silicon (wafer-based) solar cells
 Polymer solar cells:
• Degradation effects: efficiency is decreased over time due to environmental
effects.
• High band gap
 PEC cells suffer from degradation of the electrodes from the electrolyte
Nov-21-07 25
 Fourth Generation

Hybrid - nanocrystal/polymer cell

Composite photovoltaic technology

combining elements of the solid
state and organic PV cells

Nov-21-07 26
 Fourth Generation: Overview
 Use of polymers with nanoparticles mixed together to make a single multispectrum
layer.
 Significant advances in hybrid solar cells have followed the development of
elongated nanocrystal rods and branched nanocrystals
 More effective charge transport.
 Incorporation of larger nanostructures into polymers required optimization of blend
morphology using solvent mixtures.

 Cell Design:
 Solid state nanocrystals (Si, In, CuInS2, CdSe)
 Imbedded in light absorbing polymer (P3HT)
 p-type, polymeric conductor, such as PEDOT:PS, carries ‘holes’ to the counter electrode.
 Coated on a transparent semi-conducting oxide (ITO)

P3HT PEDOT:PS
Nov-21-07 27
 Fourth Generation: Nanocrystals

CdSe nanocrystals shown by transmission electron micrographs

(TEMs) at the same scale, have dimensions:
(A) 7 nm by 7 nm, (B) 7 nm by 30 nm and (C) 7 nm by 60 nm.

Nov-21-07 28
 Fourth Generation: Hybrid
 Hybrid - nanocrystalline oxide polymer composite cell
1. Photon absorbed by polymer (P3HT)
2. Photon excites electron in nanocrystal
3. Excited electron is conducted to electrode
4. Polymer (PEDOT:PS) conducts ‘hole’ to
counter electrode
5. Current used to drive load
6. Electron recombines with hole

Scheme of hybrid solar cells.

 CdSe - cadmium (II) selenide
 P3HT - Poly-3-hexylthiophene
 ITO - Indium Tin Oxide (In2O3/SnO2)
 PEDOT:PS - Poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate)
 Al - Aluminium

Nov-21-07 29
 Fourth Generation: Future

 Thin multi spectrum layers can be stacked to make multispectrum solar

cells.
 Layer that converts different types of light is first
 Another layer for the light that passes
 Lastly is an infra-red spectrum layer for the cell
 Converting some of the heat for an overall solar cell composite
 More efficient and cheaper
 Based on polymer solar cell and multi junction technology
 Future advances will rely on new nanocrystals, such as cadmium telluride
tetrapods.
 potential to enhance light absorption and further improve charge transport.
 Gains can be made by incorporating application-specific organic
components, including electroactive surfactants which control the physical
and electronic interactions between nanocrystals and polymer.

Nov-21-07 30
 Fourth Generation: Research Cells

15%
Hybrid
Nanocrytal/polymer

9%
8%
6.0%

Source: National Renewable Laboratory

Nov-21-07 31
 Fourth Generation: Evaluation

 Advantages
 Solution processable
 Lower materials cost (polymer)
 Self-assembly
 Printable nanocrystals on a polymer film
 Improved conversion efficiency (potentially)
 Disadvantages
 Efficiencies are lower compared to silicon (wafer-based) solar cells
 Potential degradation problems similar to polymer cells
 Optimize matching conductive polymers and nanocrystal

Nov-21-07 32
 Technological Improvements
 Multijunction Devices
 Stack of individual single-junction cells in descending order of
bandgap.
 Top cell captures high-energy photons and passes rest on to
lower-bandgap cells.
 Mechanical stack:
• Two individual solar cells are made independently
• Then are mechanically stacked, one on top of the other.
 Monolithic stack:
• One complete solar cell is made first
• Layers for subsequent cells are grown or deposited.
 Example: GaAs multijunction
• Triple-junction cell of semiconductors: GaAs, Ge, and GaInP2

 Concentrator Photovoltaic (CPV)

 Use large area of lenses or mirrors to focus sunlight
on a small area of photovoltaic cells
 Increase efficiency ~35%

Nov-21-07 33
 Research Cells

15%
Hybrid
Nanocrytal/polymer

9%
8%
6.0%

Nov-21-07 34
 Summary
Technology Com Eff (%) Champ Eff (%) Module ($/W) Installed ($/W) LCOE (cents/kWh)
Wafer Si 15 25 2 8 17
a-Si 6.5 13 1.2 4.5 21.7
c-Si 5 10 1.3 4.8 18.3
CdTe 9 16.5 1.21 4.5 19.9
CIGS 9.5 19.5 1.8 6.3 22.2
Organic PV - 5.2 0.70 - -
DSSC 8 11 1.9 - -
Hybrid - 6 - - -
Coal 5 to 8

 Polymer Cells Efficiency (η) is calculated:

 Not commercially available yet
 Much lower cost
 Shorter payback period (<1 yr)
– AM 1.5
 DSSC
– Pm = 1000 W/m2
 1st commercial plant Oct 07 - G24 Innovations
– Ac = 1 m2
 Build your own lab kits - 5 cells/$66 ([Link])
– E = energy output (W)
 Hybrid
 Not commercially available yet
 Similar costs to polymer cell
 Potentially much greater efficiency
Nov-21-07 35
 References
1. Efficient Titanium Oxide/Conjugated Polymer Photovoltaics for Solar Energy Conversion. Advanced Materials, 2000. 12(22): p. 4.
2. Alivisatos, A.P., Hybrid Nanorod-Polymer Solar Cell, in Subcontractor Report, NREL, Editor. 2002, National Renewable Energy
Laboratory: Golden, CO. p. 13.
3. Arici, E., N.S. Sariciftci, and D. Meissner, Advanced Functional Materials, 2003. 13(2): p. 7.
4. Baumann, A., et al., Photovoltaic Technology Review. 2004, University of California at Berkeley: Berkeley, CA. p. 40.
5. C. J. Brabec, N.S.S.J.C.H., Plastic Solar Cells. Advanced Functional Materials, 2001. 11(1): p. 15-26.
6. Campbell, W., Harvesting the Sun with Synthetic Porphyrin Dyes Massey University: Auckland, New Zealand.
7. Capper, P. and Inspec, Properties of narrow gap cadmium-based compounds. EMIS datareviews series, no. 10. 1994, London:
INSPEC, the Institution of Electrical Engineers.
8. Cravino, A. and N.S. Sariciftci, Double-cable polymers for fullerene based organic optoelectronic applications. Journal of Materials
Chemistry, 2002. 12: p. 12.
9. Energy, U.S.D.o. Photovoltaics. Solar Energy Technologies Program 2006 04/13/2006 [cited 2007 November 8]; Available from:
[Link]
10. Feitknecht, L.A., Microcrystalline Silicon Solar Cells In The N-I-P Configuration: Optimisations On Light Scattering Back-Reflectors, in
Institut de Microtechnique. 2003, Universit ́e de Neuchˆatel.
11. Gasman, L. Thin-film and Organic PV on the Rise. 2006 2006 [cited 2007 11/9/07]; Available from:
[Link]
12. Gebeyehua, D., et al., Synthetic Metals 2001. 125(3): p. 8.
13. Ginley, D., National Solar Technology Roadmap: Organic PV in National Solar Technology Roadmap. 2007, National Renewable
Energy Laboratory: Golden, CO. p. 5.
14. Gratzel, M., J. of Sol-Gel Sci. and Tech., 2001. 22: p. 7.
15. Halme, J., Dye-sensitized nanostructured and organic photovoltaic cells: technical review and preliminary tests, in Department of
Engineering Physics and Mathematics. 2002, Helsinki University of Technology. p. 115.
16. Hoppe, H. and N.S. Sariciftci, Organic solar cells: An overview. Journal of Materials Research, 2004. 19(7): p. 22.
17. Hoppe, H. and N. Serdar Sariciftci, Organic solar cells: An overview J. Mater. Res, 2004. 19(7): p. 1924-1945.
18. Keyes, B., National Solar Technology Roadmap: Film-Silicon PV in National Solar Technology Roadmap. 2007, National Renewable
Energy Laboratory: Golden, CO. p. 7.

Nov-21-07 36
 References (cont)
19. Laboratory, N.R.E. [cited; Available from: [Link].
20. Licht, S., A Description of Energy Conversion in Photoelectrochemical Solar Cells. Nature, 1987. 300(12): p. 148-151.
21. Licht, S. and D. Peramunage, Efficient Photoelectrochemical Solar Cells from Electrolyte Modification. Nature, 1990. 345(24): p. 330-
33.
22. Lorenzo, E., Solar electricity engineering of photovoltaic systems. 1994, Sevilla, Spain: PROGENSA.
23. Luque, A. and S. Hegedus, Handbook of photovoltaic science and engineering. 2003, Hoboken, NJ: Wiley.
24. Matson, R., National Solar Technology Roadmap: Sensitized Solar Cells, in National Solar Technology Roadmap. 2007, National
Renewable Energy Laboratory: Golden, CO. p. 6.
25. Mozer, A.J. and N.S. Sariciftci, Conjugated polymer photovoltaic devices and materials. Comptes Rendus Chimie 2006. 9(5-6): p. 568-
577.
26. Noufi, R. and K. Zweibel, High Efficiency CdTe and CIGS Thin Film Solar Cells: Highlights of the Technologies Challenges, in 006
IEEE 4th World Conference on Photovoltaic Energy Conversion (WCPEC-4). 2006: Waikoloa, Hawaii.
27. Sopori, B., National Solar Technology Roadmap: Wafer-Silicon PV in National Solar Technology Roadmap. 2007, National Renewable
Energy Laboratory: Golden, CO. p. 6.
28. Tennakone, K., et al., An efficient dye-sensitized photoelectrochemical solar cell made from oxides of tin and zinc. Chemical
Communications, 1998: p. 2.
29. Tongpoola, R., et al., Dye-SensitizedSolarCell (DSSC), National Metal and Materials Technology Center (MTEC): Klongluang,
Pathumthani, 12120, Thailand. p. 1.
30. Ullal, H., National Solar Technology Roadmap: CdTe PV in National Solar Technology Roadmap. 2007, National Renewable Energy
Laboratory: Golden, CO. p. 6.
31. von Roedern, B., National Solar Technology Roadmap: CIGS PV in National Solar Technology Roadmap. 2007, National Renewable
Energy Laboratory: Golden, CO. p. 6.
32. Watt, A.R., et al., Lead sulfide nanocrystal: conducting polymer solar cells. J. Phys. D: Appl. Phys, 2005. 38: p. 2006-2012.
33. Wikipedia. Solar Cell. 2007 6 November 2007 [cited 2007 November 8]; Available from: [Link]
34. Wormser, P. and R. Gaudiana, Polymer Photovoltaics –Challenges and Opportunities, in NCPV and Solar Program Review Meeting
2003. 2003, NREL/CD.

Nov-21-07 37
 The End

Thank you!

Nov-21-07 38