Lecture 8

Thin Film Solar Cells (II)

References: 1. Physics of Solar Cells. Jenny Nelson. Imperial College Press, 2003. 2. Clean Electricity from Photovoltaics, Volume 1. Mary D. Archer, Robert Hill. Imperial College Press, 2001. 3. Handbook of Photovoltaic Science and Engineering. Antonio Luque, Steven Hegedus. Wiley, 2003. 4. Nanostructured Materials for Solar Energy Conversion. Tetsuo Soga, Elsevier Science, 2007. 5. Wikipedia (http://en.wikipedia.org/wiki/Main_Page).


Non-Si Based Thin Film Technology
Non-Si based thin film was developed with the motivation to find a low cost and high efficiency alternative to Si based photovoltaic technology. One of the most efficient thin film PV technologies in the early years: copper sulfide/cadmium sulfide (Cu2S/CdS) solar cells: Now the most successful non-Si based thin film PV technologies are CuInGaSe2 and CdTe based thin film solar cells. Both have been manufactured in large scale and are commercialized.

1.2 eV

2.4 eV

EC p-Cu2S n-CdS

In a survey of Fuji Keizai Co. Ltd, the market for CIGS solar cells will sharply grow from the 4.5 billion yen in fiscal 2006 to 472.5 billion yen in fiscal 2010. That is, CIGS Solar Cell Market to Expand 105 Times in 4 Years. In addition, organic photovoltaics (OPV) have attracted much attention as a promising new thin film PV technology for the future.


Laboratory Thin Films Cell Efficiencies
Efficiency is the Best Metric to Gauge Progress


or CIS) is a direct band gap sc with a band gap of ~1. CuInSe2 was proposed as a photovoltaic material by S.05 eV and an optical absorption amongst the highest known for any semiconductor. Wagner with a power conversion efficiency of 12% for a single-crystal cell. In 1974. In 1953.CIGS Thin Film Solar Cells Materials Properties Copper indium diselenide (CuInSe2. CuInSe2 was synthesized for the first time by H. Hahn. 4 .

CIGS Thin Film Solar Cells Structures Evolution: Diamond Si → Zincblende ZnS → Chalcopyrite CuInS2 Doping: Because of the native defects. the conductivity of CIGS is ptype. Other I-III-VI Semiconductors: 5 . The defect is mainly In vacancies and Cu atoms on In sites. It can be controlled by varying the Cu/In ratio during growth of the material.

CIGS Thin Film Solar Cells In most photovoltaic structures the alloy CuInGaSe2 (CIGS) are used in place of CIS. Addition of Ga improves the photovoltaic characteristics. as well as the electronic properties of the rear contact. 6 . gallium and selenium. indium. and the selenization of Cu/In films. CIGS is deposited by two main methods: vapor co-deposition of copper. by raising the band gap.

using n-CdS emitter on a lightly doped p-CIS base. CIS p-n homojunction solar cells can be made. which tend to grow in a columnar structure so that grain boundaries are more likely to lie normal to the pn junction. Highly doped CdS serves as window layer to reduce the collection losses due to surface recombination and transport electrons from junction to front surface with minimum series resistance.Structure of CIGS Thin Film Solar Cells CIS consists of grains of size ~1 µm. Better devices can be made with heterojunction structure. but have an efficiency of only 3-4%. 7 .

or both at the interface. it introduces several problems: • Differences between the crystal structure or lattice constants of the two materials introduces intra-band gap defect states at the junction. 8 . or the formation of new chemical compounds in the junction region. • Differences between the chemical composition of the two materials may lead to the diffusion of species across the junction. • Differences between the electron affinity and band gap of the two materials may lead to the situation where there is a spike in the CB or VB.Heterojunction in CIGS Thin Film Solar Cells Short diffusion length requires the use of window layer to reduce the loss of high energy photons. CuInSe2 cannot easily be doped n-type. may lead to Fermi level pinning. In addition. which encourage SRH recombination. So a heterojunction has to be used. However.

Recombination losses are introduced by less-than-ideal collection efficiencies of photo-generated carriers. and the higher the likelihood of recombination. which is similar to the grain size. The longer the wavelength. Improved recombination requires a longer electron diffusion length (Ln is ~ 2 μm). Buffer absorption represents one of the major losses in todayʼs CIGS thin-film solar cells.Loss in CIGS Thin Film Solar Cells • Reflection losses are introduced by partial coverage of the front surface by nontransparent contacts or by reflection at material interfaces. • • 9 . Thinning of the CdS or replacing it with a higher band-gap material are possible alternatives. the deeper the generation of carriers.

During air annealing.Fabrication of CIGS Thin Film Solar Cells Oxygenation: Air annealing has been an important process step. 10 . Cahen-Noufi model: the surface defects at grain boundaries are positively charged Se vacancies. the chemical bath deposition of CdS removes the passivating oxygen and re-establishes the beneficial type inversion of the film surface. the band bending and the recombination probability for photo-generated electrons are reduced. these sites are passivated by O atoms. Eventually. Because of the decreased charge at the grain boundary. crucial for the efficiency of the solar cells based on CuInSe2.

The benefit of the CdS layer is manifold: • • • • CBD deposition of CdS provides complete coverage of CIGS surface. the natural type inversion at the CdS/CIGS interface. The Cd ions also diffuse to a certain extent into the Cu-poor surface layer of the absorber material supporting the type inversion of the buffer/absorber interface. reacting first with the absorber surface. as a consequence. The Cd ions.Fabrication of CIGS Thin Film Solar Cells Buffer Layer Deposition: Surface passivation and junction formation is most easily achieved by the CBD deposition of a thin CdS film from a chemical solution containing Cd ions and thiourea. which provides protection against damage and chemical reactions resulting from the subsequent ZnO deposition process. The VOC limitations imposed by interface recombination can be overcome by a low surface recombination velocity in addition to the type inversion of the absorber surface. remove elemental Se. possibly by the formation of CdSe. 11 . The chemical bath removes the natural oxide from the film surface and thus re-establishes positively charged surface states and.

CIGS Thin Film Solar Cells One inherent advantage of thin-film technology for photovoltaics is the possibility of using monolithic integration for series connection of individual cells within a module. The interconnect scheme has to ensure that the front ZnO of one cell is connected to the back Mo contact of the next one. Scribing of the semiconductor layer is performed by mechanical scribing or laser scribing. and the final one after window deposition. The first Mo patterning by laser scribing. 12 . The second patterning is performed after absorber and buffer deposition.

Japan. Global Solar (flexible cells). USA. USA and Germany. 13 .CIGS Thin Film Solar Cells Major companies of CIGS cells: ZSW. etc. USA. Showa. Sweden. Siemens. Angstrom Solar Centre. Energy Photovoltaics. Germany.

Laboratory Thin Films Cell Efficiencies Efficiency is the Best Metric to Gauge Progress 14 .

close to the optimum for photo-conversion. 15 . Eg=2.CdTe Thin Film Solar Cells Materials Properties Cadmium Telluride (CdTe) is the semiconductor from the II-VI group of materials. It is one of the only two II-VI compounds (the other is ZnTe.26 eV) which can be doped p type as well as n type. and a very high optical absorption. It has a direct band gap of 1.44 eV.

no additional doping has to be introduced. like GaAs. 16 . In most deposited CdTe films. but has poorer transport properties. hexagonally packed alternating Cd and Te layers tend to lie in the plane of the substrate (the 111 axis being perpendicular to the substrate). CdTe grows natively p-doped in thin-film form.CdTe Thin Film Solar Cells Materials Properties The crystal of CdTe adopts the wurtzite crystal structure. due to a high density of native defects at the grain boundaries giving rise to defect states deep in the band gap. leading to columnar growth of crystallites.

so that the light is absorbed in the CdTe close to the junction. CdTe is lightly p-doped.Structure of CdTe Thin Film Solar Cells The n-CdS/p-CdTe heterojunction solar cell must be illuminated through the CdS window. the n-CdS film is deposited onto a transparent TCO film. and finally a low-resistance contact is made to the CdTe followed by a back electrode. 17 . Light-generated electrons in the CdTe experience a drift field and move toward the junction into the CdS. In the preferred fabrication procedure. So all the electric field drops within the CdTe layer. CdS is heavily n-doped. extending to a depth of ~1 μm. a value comparable with the optical absorption length. Next the CdTe is deposited onto the CdS. typically SnO2.

Screen printing. Atomic layer epitaxy (ALE). good crystallinity and high minority carrier mobility. Cell Activation It has become common practice to activate the cells by using the influence of CdCl2 at elevated temperatures. the CdS should be as highly doped as possible. An alternative option is chemical bath deposition.ions are supplied during the growth process. etc. Galvanic deposition. It may improve the crystallinity of the material. dried and annealed or CI. Numerous deposition technologies have been developed: Sublimation-condensation (Close-spaced sublimation). Physical vapor deposition and chemical spraying are the main options. Chemical vapor deposition. The deposited CdTe films are wetted with solutions of CdCl2 in methanol. 18 . To maximize the photovoltage. CdTe Absorption Layer Deposition The deposition process used for CdTe should utilize the advantageous materials properties such as the native p-doping. and sputtering.Fabrication of CdTe Thin Film Solar Cells CdS Window Layer Deposition The CdS film should be as thin as is feasible with pinhole-free and continuous. Chemical spraying.

ZnTe:Cu. HgTe. some methods may combine the above two approaches by first contacting CdTe with a more easily doped semiconductor (generating a p-p+ junction). In practice. 19 . p-doping in CdTe suffers from a strong acceptors self-compensation. For example. However. low-cost metals of work function greater than 4. As the electron affinity of CdTe is 4.3 eV. Create a highly doped back-surface layer in the semiconductor.Fabrication of CdTe Thin Film Solar Cells Back Contact There are two general principles for making Ohmic contacts to p-CdTe: 1. and then with metals of high work function. Te and Cu2Te. Generally a TCO film is considered good if its conductivity is <10 ohms square-1 and its optical transmission is >80% in the region of solar sensitivity of the device. Use a metal of higher work function. etc. Substrate and TCO Film The substrate onto which thin-film solar cells are deposited will to a large extent determine the cost of the final module. 2. and dopants generally diffuse preferentially along grain boundaries.5 eV are not available.

Industrial Status of CdTe Solar Cells The following are the individual steps for module production from glass to module: (1) cleaning of substrate glass. (3) scribing step. (7) scribing step 2. (10) edge insulation and contact attachment. (11) lamination. (6) activation. these processes must be integrated into a production line. (9) scribing step 3. (4) CdS deposition. 20 . (13) power test and inspection. (12) safety check. A typical module connected in series is made by applying three sets of separation cuts to the growing film stack during production by means of laser ablation or mechanical machining. For mass production. (2) TCO-deposition. (5) CdTe deposition. (8) back contact deposition.

Commercial Module Target (15%) 21 .98/watt for the fourth quarter of 2008. And the total capacity is expected to be more than 1 GW by the end of 2009. is the largest manufacturer of thin film solar modules. $0.Industrial Status of CdTe Solar Cells First Solar Inc. breaking the $1 per watt price barrier. having expanded manufacturing capacity to 735 MW in 2008. First Solar has achieved the lowest manufacturing cost per watt in the industry.

1906 – Pochettino discovered photoconductivity in solid anthracene 1950 – Chlorophyll and related organic dyes were studied. Kearns and Calvin worked with magnesium phthalocyanine 1980 – First polymer based solar cells 1986 – Breakthrough: first cell with donor and acceptor by Tang 1991 – First dye/dye based cell by Hiramoto 1993 – First polymer/C60 based cell by Sariciftci 1995 – First polymer/polymer based cell by Yu and Hall 2000 – Oligomer-C60 dyads/triads as active materials by Peters and Van Hall 2001 – Cell with double-cable polymers by Ramos 22 .Organic Photovoltaic Devices: A Brief History Organic photovoltaics (OPV) are comprised of electron donor and electron acceptor materials rather than semiconductor p-n junctions.

Materials for Organic Photovoltaic Devices Polymer Photovoltaics Conjugated polymers possess delocalized π electrons. Donor Acceptor 23 .

24 . And there is no lack of the resources of elements like some of the inorganic semiconductors.Materials for Organic Photovoltaic Devices Photovoltaics Made of Small Molecules phthalocyanine These organic semiconducting materials have tunable band gap and other electronic properties.

Bulk Heterojunction in Organic Photovoltaics Bulk heterojunctions constitute intimate blends of organic donor and acceptor materials that allow for efficient charge separation throughout the photoactive layer and provide independent pathways to transport the charge carriers to the contacts. 25 .

where they were created. LUMO PPV Charge transfer LUMO PPV hν Exciton diffusion LUMO PCBM + HOMO PPV HOMO PCBM + HOMO PPV CT-state LUMO PCBM 2.Device Physics of Organic Solar Cells 1. photon absorption within the PPV layer first leads to the creation of a bound e-h pair–the exciton. The exciton diffusion length is limited to ~5-20 nm. which forms the metastable bound eh pairs (CT-state). photon induced charge transfer process takes place very rapidly (fs). Charge transfer at D-A interface Because of the difference in ionization potential and electron affinity between donor and acceptor. Exciton creation and diffusion Upon illumination. HOMO PCBM 26 . Excitons may diffuse during their lifetime within the material.

Device Physics of Organic Solar Cells 3. weakly interacting molecules.+ HOMO PPV - LUMO PCBM + + Dissociation to free carriers HOMO PCBM - - - - + + + + Charge transport and collection HOMO PPV HOMO PCBM 4. exciton binding energy is normally stronger in organics. Transport of free charge carrier to the electrodes: Once the charge carriers have been separated. Dissociation of e-h pairs at D-A interface: Because of the larger dielectric constant. The e-h pairs are dissociated at the interface across by the energy level offset. and localized wave functions. 27 . the donor material serves to transport the holes whereas the electrons travel within the acceptor material. which highly dependent on the internal phase structure of the D– A blend. LUMO PPV Charge transport and collection LUMO PCBM LUMO PPV .

and recombine instead at trap sites or remain in the device as undesirable space charges that oppose the drift of new carriers. The latter problem can occur if electron and hole mobilities are highly imbalanced. the carriers will not reach the contacts. 28 . In addition. if mobility is not sufficiently high.Recombination in Organic Solar Cells LUMO PPV Exciton recombination - + + + + + + Decay to ground state - - LUMO PCBM - - - HOMO PPV Recombination to CT-state HOMO PCBM Firstly. percolating paths are required to ensure that the charge carriers will not experience the fate of recombination due to trapping in dead ends on an isolated material’s domain. such that one species is much more mobile than the other.

Fabrication of Organic Solar Cells Roll-to-roll printing of organic solar cells by Konarka 29 .

Industrial Status of Organic Solar Cells Siemens AG Konarka Organic ThinFilm Solar Cell Modules Before the stability issue could be solved and higher efficiency could be achieved in solar modules. 30 . there is still long way to go for OPV to be used in niche market.

Summary 31 .

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