Lecture 3 Types of Solar Cells (experiment )3 generations Generation 1: Single- and poly-Crystalline Silicon Growth, impurity diffusion, contacts

Modules, interconnection Generation 2: Polycrystalline thin films, crystal structure, deposition techniques CdS/CdTe (II-VI) cells CdS/Cu(In,Ga)Se2 cells Amorphous Si:H cells
Generation 3: High-efficiency Multi-junction Concentrator Solar Cells based on III-Vs and III-V ternary analogs Dye-sensitized cells Organic (excitonic) cells Polymeric Cells Nanostructured cells including Multi-carrier per photon cells, quantum dot and quantum confined cells

Figure 3. The three generations of solar cells. First-generation cells are based on expensive silicon wafers and make up 85% of the current commercial market. Second-generation cells are based on thin films of materials such as amorphous silicon, nanocrystalline silicon, cadmium telluride, or copper indium selenide. The materials are less expensive, but research is needed to raise the cells' efficiency to the levels shown if the cost of delivered power is to be reduced. Third-generation cells are the research goal: a dramatic increase in efficiency that maintains the cost advantage of second-generation materials. Their design may make use of carrier multiplication, hot electron extraction, multiple junctions, sunlight concentration, or new materials. The horizontal axis represents the cost of the solar module only; it must be approximately doubled to include the costs of packaging and mounting. Dotted lines indicate the cost per watt of peak power (Wp). (Adapted from ref. 2,) Green.)

Generation I.

Single Crystal Ingot-based PVs

Single crystal wafers made by Czochralski process, as in silicon electronics Comprise 31% of market Efficiency as high as 24.7% Expensivebatch process involving high temperatures, long times, and mechanical slicing Wafers are not the ideal geometry Benefits from improvements developed for electronics industry

http://hydre.auteuil.cnrs-dir.fr/dae/competences/cnrs/images/icmcb03.jpg

ProductionProcess
mono- or multicrystalline Silicon crystal growth process

6.6.06 - 8.6.06

Clemson Summer School Dr. Karl Molter / FH Trier / molter@fhtrier.de

Production process
1. Silicon Wafer-technology (mono- or multi-crystalline)

Most purely silicon

99.999999999%

melting / crystallization Tile-production Plate-production cleaning Quality-control Wafer

Occurence: Siliconoxide (SiO2) = sandcutting: Mechanical Thickness about 300m

typical Wafer-size: Minimum Thickness: 10 x 10 cm2

about 100m
Link to

SiO2 + 2C = Si + 2CO
Clemson Summer School Dr. Karl Molter / FH Trier / molter@fhtrier.de

Producers of Silicon Wafers

6

6.6.06 - 8.6.06

Energa Fotovoltaica Celdas Solares

De Silicio monocristalino
Material: Silicio monocristalino Temperatura de Celda: 25C Intensidad luminosa: 100% rea de la celda: 100 cm2

Voltaje a circuito abierto: Vca = 0.59 volts Corriente a corto circuito: Icc = 3.2 A Voltaje para mxima potencia: Vm = 0.49 volts Corriente para mxima potencia: Im = 2.94 A Potencia mxima: Pm = 1.44 Watts

Polycrystalline Ingot-based PVs

Fastest-growing technology involves casting Si in disposable crucibles Grains mm or cm scale, forming columns in solidification direction Efficiencies as high as 20% in research Production efficiencies 13-15% Faster, better geometry, but still requires mechanical slicing

Polycrystalline Si Ribbon PVs

String method
Two strings drawn through melt stabilize ribbon edge Ribbon width: 8 cm

Carbon foil method (edge-defined film-fed growth, EFG)

Si grows on surface of a carbon foil die Die is currently an octagonal prism, with side length 12.5 cm

Pros and Cons

Method can be continuous Requires no mechanical slicing Efficiencies similar to other polycrystalline PVs Balancing growth rate, ribbon thickness and width

Generation II.

Flat-Plate Thin-Films
Potential for cost advantages over crystalline silicon
Lower material use Fewer processing steps Simpler manufacturing technology

Three Major Systems

Amorphous Silicon Cadmium Telluride Copper Indium Diselenide (CIS)

Production Process
Thin-Film-Process (CIS, CdTe, a:Si, ... ) semiconductor materials are evaporated on large areas Thickness: about 1m Flexible devices possible less energy-consumptive than c-Silicon-process

only few raw material needed

Typical production sizes: 1 x 1 m2

CIS Module
Clemson Summer School Dr. Karl Molter / FH Trier / molter@fhtrier.de

6.6.06 - 8.6.06

14

Photon Energy

Amorphous Silicon
a-Si:H Discovered in 1970s

Made by CVD from SiH4

http://www.solarnavigator.net/images/uni_solar_triple_junction_flexible_cell.jpg

Material

Level of efficiency in % Lab Approx. 24 Approx. 18 Approx. 13

Level of efficiency in % Production 14 to 17 13 to 15 5 to 7

Monocrystalline Silicon Polycrystalline Silicon Amorphous Silicon

Amorphous Silicon Growth by Thermal CVD

Basic Cell Structure

p-i-n structure
Intrinsic a-Si:H between very thin p-n junction Lower cells can be aSi:H, a-SiGe:H, or microcrystalline Si

Produces electric field throughout the cell

http://www.sandia.gov/pv/images/PVFSC36.jpg

CdTe

CdTe/CdS Solar Cell

CdTe : Bandgap 1.5 eV; Absorption coefficient 10 times that of Si CdS : Bandgap 2.5 eV; Acts as window layer Limitation : Poor contact quality with p-CdTe (~ 0.1 Wcm2)

Cadmium Telluride
One of the most promising approaches Made by a variety of processes
CSS HPVD
http://www.nrel.gov/cdte/images/cdte_cell.gif

http://www.sandia.gov/pv/images/PVFSC29.jpg

CdTe and CIGS Review: 2006 World PV Conference

Noufi and Zweibel, NREL/CP -520-39894, 2006

John A. Woollam, PV talk UNL 2007

31

Cadmium Telluride Solar Cells

D.E.Carlson, BP Solar

CdS/CdTe heterojunction: typically chemical bath CdS deposition, and CdTe sublimation.
Cd Toxicity is an issue.

Best lab efficiency = 16.5%

First Solar plans 570 MWp production capacity by end of 2009.

John A. Woollam, PV talk UNL 2007

Nano-Structured CdS/CdTe Solar Cells

Graphite CdTe Nanocrystalline CdS ITO Glass
Nano CdS/ CdTe device Structure.

Band gap of CdS can be tuned in the range 2.4 - 4.0 eV. Nano-structured CdS can be a better window material and may result in high performance, especially in short circuit currents.

Pros and Cons

Pros
A material of choice for thin-flim PV modules
Nearly perfect band-gap for solar energy conversion Made by a variety of low-cost methods Future efficiencies of 19%
"CdTe PV has the proper mix of excellent efficiency and manufacturing cost to make it a potential leader in economical solar electricity." Ken Zweibel, National Renewable Energy Laboratory

Pros
Health Risks Environmental Risks Safety Risks Disposal Fees

Modulos Solares de CdTe

Costo 60% de Si 20 aos garantia Modulos de peliculas delgadas Potencia 50 60 W Eficiencia 9%

Modulos Solares de CdTe

Costo 60% de Si 20 aos garantia Modulos de peliculas delgadas Potencia 50 60 W Eficiencia 9%
100 kW 1 MW

Copper Indium Diselenide

Also seen as CIGS Several methods of production
http://www.sandia.gov/pv/images/PVFSC25.jpg

http://www.sandia.gov/pv/images/PVFSC27.jpg

http://www.sandia.gov/pv/images/PVFSC26.jpg

Tandem Cells

Current output matched for individual cells Ideal efficiency for infinite stack is 86.8% GaInP/GaAs/Ge tandem cells (efficiency 40%)

Tandemcell
Pattern of a multispectral cell on the basis of the Chalkopyrite Cu(In,Ga)(S,Se)2

6.6.06 - 8.6.06

Clemson Summer School Dr. Karl Molter / FH Trier / molter@fhtrier.de

49

Generation III.

High Efficiency Concentrator Solar Cells

Multijunction Concentrators
Similar in technique Exotic Materials More expensive processing (MBE)

http://www.nrel.gov/highperformancepv/entech.html

Spectrolabs Triple-Junction Solar Cell

D.E.Carlson, BP Solar

Spectrolab: 40.7% conversion efficiency at ~ 250 suns.

John A. Woollam, PV talk UNL 2007

[edit] Gallium arsenide substrate Twin junction cells with Indium gallium phosphide and gallium arsenide can be made on gallium arsenide wafers. Alloys of In.5Ga.5P through In.53Ga.47P may be used as the high band gap alloy. This alloy range provides for the ability to have band gaps in the range of 1.92eV to 1.87eV. The lower GaAs junction has a band gap of 1.42eV. The considerable quantity of photons in the solar spectrum with energies below the band gap of GaAs results in a considerable limitation on the achievable efficiency of GaAs substrate cells.

Dye-Sensitized solar cells

Dye-sensitized Solar Cells

ORegan and Grtzel 1991 Organic dye molecules + nanocrystalline titanium dioxide (TiO2) 11% have been demonstrated Benefits: low cost and simplicity of manufacturing Problems: Stability of the devices

Operation Sunlight enters the cell through the transparent SnO2:F top contact, striking the dye on the surface of the TiO2. Photons striking the dye with enough energy to be absorbed will create an excited state of the dye, from which an electron can be "injected" directly into the conduction band of the TiO2, and from there it moves by diffusion (as a result of an electron concentration gradient) to the clear anode on top. Meanwhile, the dye molecule has lost an electron and the molecule will decompose if another electron is not provided. The dye strips one from iodide in electrolyte below the TiO2, oxidizing it into triiodide. This reaction occurs quite quickly compared to the time that it takes for the injected electron to recombine with the oxidized dye molecule, preventing this recombination reaction that would effectively short-circuit the solar cell. The triiodide then recovers its missing electron by mechanically diffusing to the bottom of the cell, where the counter electrode reintroduces the electrons after flowing through the external circuit.

Organic Solar Cells

Organic and Nanotech Solar Cells

Benefits: 10 times thinner than thin-film solar cells Optical tuning Low cost for constituent elements High volume production Problems: Current efficiencies < 3-5% Long term stability

Fig. 1. The scheme of plastic solar cells. PET Polyethylene terephthalate, ITO - Indium Tin Oxide, PEDOT:PSS - [[Poly(3,4ethylenedioxythiophene) poly(styrenesulfonate), Active Layer (usually a polymer:fullerene blend), Al - Aluminium.

Nanostructured Solar cells

Nanostructured Solar Cells

Nanomaterials as light harvesters leading to direct conversion or chemical production alone or imbedded in a matrix.

Questions: art_nozik@nrel.gov

Fig.2 (a) Nanostructure of anodically formed Al2O3 template. (b) its cross-section, (c) catalyst deposited at the bottom of the pores, (e) vertically aligned nanotubes, and (f) TEM image of a nanotube.

Cu2S/CdS bulk and nano heterojunction solar cells

Bulk heterojunction
Cr contacts Thin layer of Cu ~ 10 nm Cu2S CdS ITO Glass

Nano heterojunction

Cu/Cr top contact Copper Sulfide Inter-pore spacing Nano-porous Alumina Template Cadmium Sulfide ITO

ITO n-CdS Alumina

z z
Mo/Glass

p-CIS

PTCBI

Porous Al2O3

CuPc ITO

Al or Ag
PTCBI

CuPc

ITO

PV Module Conversion Efficiencies

D.E.Carlson, BP Solar

Modules Dye-sensitized solar cells Amorphous silicon (multijunction) Cadmium Telluride (CdTe) thin film Copper-Indium-Gallium-Selenium (CIGS) Multicrystalline or polycrystalline silicon Monocrystalline silicon High performance monocrystalline silicon 3 5% 6 - 8% 8 - 10% 9 - 11% 12 - 15%20.3% 14 - 16%23% 16 - 19%24.7% -

Lab 11% 13.2% 16.5% 19.5%

Triple-junction (GaInP/GaAs/Ge) cell (~ 250 suns)

40.7%

John A. Woollam, PV talk UNL 2007

Generation III Solar Cells not yet realized experimentally

Multiband Cells

Intermediate band formed by impurity levels. Process 3 also assisted by phonons Limiting efficiency is 86.8%

Quantum Dots

Multiple Quantum Well

Principle of operation similar to multiband cells

Multiple E-H pairs

Many E-H pairs created by incident photon through impact ionization of hot carriers Theoretical efficiency is 85.9%

Figure 3. Photoexcitation at 3Eg creates a 2Pe-2Ph exciton state. This state is coupled to multiparticle states with matrix element V and forms a coherent superposition of single and multiparticle exciton states within 250 fs. The coherent superposition dephases due to interactions with phonons; asymmetric states (such as a 2Pe1Sh) couple strongly to LO phonons and dephase at a rate of -1.

To study MEG processes in QDs, we detect multiexcitons created via exciton multiplication (EM) by monitoring the signature of multiexciton decay in the transient absorption (TA) dynamics, while maintaining a pump photon fluence lower than that needed to create multiexcitions directly. The Auger recombination rate is proportional to the number of excitons per QD with the decay of a biexciton being faster than that of the single exciton. By monitoring the fast-decay component of the TA dynamics at low pump intensities we can measure the population of excitons created by MEG.

The work reported here provides a confirmation of the previous report of efficient MEG in PbSe. We observed a previously unattained 300% QY exciting at 4Eg in PbSe QDs, indicating that we generate an average of three excitons per photon absorbed. In addition, we present the first known report of multiple exciton generation in PbS QDs, at an efficiency comparable to that in PbSe QDs. We have shown that a single photon with energy larger than 2Eg can generate multiple excitons in PbSe nanocrystals, and we introduce a new model for MEG based on the coherent superposition of multiple excitonic states. Multiple exciton generation in colloidal QDs represents a new and important mechanism that may greatly increase the conversion efficiency of solar cell devices.

For the 3.9 nm QD (Eg = 0.91 eV), the QY reaches a surprising value of 3.0 at Ehn/Eg = 4. This means that on average every QD in the sample produces three excitons/photon.

Fig. 2. Calculated efficiencies for different QYII models.