Highly efficient CIS solar cells and modules made by the co-evaporation process

Thin-film photovoltaic modules which use the chalcopyrite Cu(In,Ga)(Se,S)₂ (CIGS) as the light-absorbing layer have now entered the decisive industrial phase. Companies located mainly in Germany and Japan will produce more than 100 MWp CIGS modules in 2008, demonstrating that the CIGS technology has already achieved a certain maturity. Whereas key features of the technology are already well-optimized, there are several approaches to further improve the productivity of new lines. The ZSW operates a line for 30 × 30 cm² modules in which all process steps - from glass cleaning to module encapsulation - are being developed. A major goal of the development is the very fast and efficient transfer of promising new materials and processes from cells to the industrial module level. Therefore, ZSW is focusing on processes like the in-line co-evaporation method for CIS or chemical bath deposition for buffer layers to optimize the junction. We could demonstrate efficiencies close to 18% for small test cells and 14-15% for modules with modified processes. Different cell and material data from optoelectronic measurements and microscopic analysis will be presented in this contribution.     

CuIn1 − xGaxSe2 photovoltaic devices for tandem solar cell application

CuIn_1 − xGa_xSe₂ (CIGS) solar cells show a good spectral response in a wide range of the solar spectrum and the bandgap of CIGS can be adjusted from 1.0 eV to 1.7 eV by increasing the gallium-to-indium ratio of the absorber. While the bandgaps of Ga-rich CIGS or CGS devices make them suitable for top or intermediate cells, the In rich CIGS or CIS devices are well suited to be used as bottom cells in tandem solar cells. The photocurrent can be adapted to the desired value for current matching in tandem cells by changing the composition of CIGS which influences the absorption characteristics. Therefore, CIGS layers with different [Ga]/[In + Ga] ratios were grown on Mo and ZnO:Al coated glass substrates. The grain size, composition of the layers, and morphology strongly depend on the Ga content. Layers with Ga rich composition exhibit smaller grain size and poor photovoltaic performance. The current densities of CIGS solar cells on ZnO:Al/glass varied from 29 mA cm^− 2 to 13 mA cm^− 2 depending on the Ga content, and 13.5% efficient cells were achieved using a low temperature process (450 °C). However, Ga-rich solar cells exhibit lower transmission than dye sensitized solar cells (DSC). Prospects of tandem solar cells combining a DSC with CIGS are presented.     

Thin film Cu(In,Ga)Se2 solar cells processed from solution pastes with polymethyl methacrylate binder

A non-vacuum, solution-based method is investigated to deposit thin layers of Cu(In,Ga)Se₂, which is the core component of CIGS thin film solar cells. The concept is based on paste coating of Cu, In, and Ga salt solution with an organic binder and a subsequent annealing of the paste in selenium atmosphere. Previous experiments with ethylcellulose as the binder resulted in photo conversion efficiencies up to 6.7%, although further improvements were hindered by a limited thickness of the CIGS layer and a residual carbon layer between the CIGS and metal back contact.In the present work, polymethyl methacrylate (PMMA) is tested as an alternative binder material, which theoretically should leave no char residues upon thermal degradation at temperatures higher than 350 °C. A series of pastes with different solvents are prepared and the resulting CIGS layers are investigated systematically by microscopy, SEM, EDX, XRF, and XRD. Absorber layers are processed into Mo/CIGS/CdS/ZnO solar cells and their I-V characteristics are measured. PMMA can be used as the organic binder alternative to cellulose and more complete evaporation of the organic matrix is achieved as compared to the reference cellulose-containing recipe. However, maximum solar cell efficiencies are limited to 3% because the obtained CIGS layers are porous and contain traces of parasitic oxide phases when heated above 330 °C in ambient atmosphere.     

Raman spectroscopy of CuIn1 − xGaxSe2 for in-situ monitoring of the composition ratio

Metal organic vapor deposition (MOCVD) is a well known method for preparing high quality and large area CuIn_1 − xGa_xSe₂ (CIGS) absorber layers. Some in-situ non-contact monitoring systems are needed when CIGS absorber layers are manufactured in industry. In this study, CuInSe₂ (CIS) and CIGS thin films with different composition ratios, [Cu]/[In + Ga], were prepared by MOCVD using [Me₂In(μ-SeMe)]₂, hexafluoroacetylacetonate Cu(I) (3,3-dimethyl-1-butene), trimethyl gallium and dimethyle diselenide as the In-Se single source, Cu, Ga and Se precursors, respectively. The Raman shift spectra of the films with various composition ratios were analyzed to produce a basic algorithm that can determine the composition ratios of CIS and CIGS thin films indirectly.     

Manufacturing and application of CIS solar modules

The pilot production of Cu(In,Ga)Se₂ (CIS) modules at Würth Solar has progressed steadily, and the pilot line could be transferred successfully into a continuous operation reaching maximum capacity in 2005 of 1.5 MW_p. Best modules on the standard size of 60 cm × 120 cm reached 85 W_p, which corresponds to 13% aperture area efficiency. The average module efficiency has been steadily improved reaching values between 11% and 12% in the year 2005. The overall process yield of the pilot line could be increased and stabilised at high values well above 80%.In April 2005 the Würth Group has decided to invest in a new production line with a starting capacity of 15 MW_p/a. This capacity will be available at the end of 2006. The new building at the new location in Schwäbisch Hall/Germany will be ready in mid 2006.The long-time reliability of Würth Solar CIS modules could be proven by passing successfully the certified test according to EN61646 and by stable operation in the field for several years. Additionally, outdoor results with CIS modules in various applications show high energy ratings which are at least as good as the best c-Si systems. Furthermore, various CIS module types have been developed for building integration and other applications.     

Optical and electrical properties of electron-irradiated Cu(In,Ga)Se2 solar cells

The optical and electrical properties of electron-irradiated Cu(In,Ga)Se₂ (CIGS) solar cells and the thin films that composed the CIGS solar cell structure were investigated. The transmittance of indium tin oxide (ITO), ZnO:Al, ZnO:Ga, undoped ZnO, and CdS thin films did not change for a fluence of up to 1.5 × 10¹⁸ cm^− 2. However, the resistivity of ZnO:Al and ZnO:Ga, which are generally used as window layers for CIGS solar cells, increased with increasing irradiation fluence. For CIGS thin films, the photoluminescence peak intensity due to Cu-related point defects, which do not significantly affect solar cell performance, increased with increasing electron irradiation. In CIGS solar cells, decreasing J_SC and increasing R_s reflected the influence of irradiated ZnO:Al, and decreasing V_OC and increasing R_sh mainly tended to reflect the pn-interface properties. These results may indicate that the surface ZnO:Al thin film and several heterojunctions tend to degrade easily by electron irradiation as compared with the bulk of semiconductor-composed solar cells.     

Fabrication and characterisation of Cu(In,Ga)Se2 solar cells on polyimide

Solar cells with the structure ZnO:Al/i-ZnO/CdS/Cu(In,Ga)Se₂/Mo/polyimide were examined using a range of techniques. The elemental composition of the Cu(InGa)Se₂ (CIGS) layers, their crystalline structure and optical properties were studied. Photoluminescence (PL) spectra of the CIGS absorber layers were studied as functions of temperature (4.2-240 K) and excitation power density. The band gap energy E_g of the CIGS layers was determined by employing photoluminescence excitation (PLE) spectroscopy. The influence of sodium incorporation on the PL properties of CIGS was analysed. Correlations of the optical properties of the CIGS absorber layers and the photovoltaic parameters of the solar cells were revealed.     

Substitution of the CdS buffer layer in CIGS thin‐film solar cells

This contribution provides an overview of current activities in the area of alternative buffer layers for Cu(In,Ga)(S,Se)₂ (CIGS) thin‐film solar cells. Good cell and module results were achieved by replacing the standard Cds buffer with Zn(O,S), In₂S₃, (Zn,Sn)O_y or (Zn,Mg)O grown by various methods like chemical bath deposition (CBD), thermal evaporation, sputtering, atomic layer deposition, and spray ion layer gas reaction. The “dry” deposition methods like sputtering and thermal evaporation could be favorable in an industrial environment on glass substrates or application in a roll‐to‐roll coater. Significant progress was made within the last two years for various Cd‐free CIGS devices. We list current records for cells with alternative buffers, e. g. Zn(O,S)‐buffered champion cells with efficiencies between 18—20 % and In₂S₃‐buffered cells with 16—17 %. Both materials have the potential to substitute CdS with efficiencies approaching the 20 % mark already surpassed by CIGS cells with CBD CdS buffers.     

Antimony assisted low-temperature processing of CuIn1 − xGaxSe2 − ySy solar cells

Application of the Sb-doping method to low-temperature (≤ 400 °C) processing of CuIn_1 − xGa_xSe_2 − yS_y (CIGS) solar cells is explored, using a hydrazine-based approach to deposit the absorber films. Power conversion efficiencies of 10.5% and 8.4% have been achieved for CIGS devices (0.45 cm² device area) processed at 400 °C and 360 °C, respectively, with an Sb-incorporation level at 1.2 mol % (relative to the moles of CIGS). Significant Sb-induced grain size enhancement was confirmed for these low processing temperatures using cross-sectional scanning electron microscopy, and an average 2-3% absolute efficiency improvement was achieved in Sb-doped samples compared to their Sb-free sister samples. With Sb inclusion, the CIGS film grain growth temperature is lowered to well below 450 °C, a range compatible with flexible polymer substrate materials such as polyimide. This method opens up access to opportunities in low-temperature processing of CIGS solar cells, an area that is being actively pursued using both traditional vacuum-based as well as other solution-based deposition techniques.     

Effect of copper-deficiency on multi-stage co-evaporated Cu(In,Ga)S2 absorber layers and solar cells

Solar cell absorber films of Cu(In,Ga)S₂ have been fabricated by multi-stage co-evaporation resulting in compositional ratios [Cu]/([In] + [Ga]) = 0.93-0.99 and [Ga]/([In] + [Ga]) = 0.15. Intentional doping is provided by sodium supplied from NaF precursor layers of different thicknesses. Phases, structure and morphology of the resulting films are investigated by X-ray diffraction (XRD) and scanning electron microscopy. The XRD patterns show CuIn₅S₈ thiospinel formation predominantly at the surface in order to accommodate decreasing Cu content. Correlated with the CuIn₅S₈ formation, a Ga-enrichment of the chalcopyrite phase is seen at the surface. Since no CuS layer is present on the as-deposited films, functioning solar cells with CdS buffer and ZnO window layers were fabricated without KCN etch. The open-circuit voltage of solar cells correlates with the copper content and with the amount of sodium supplied. The highest efficiency cell (open-circuit voltage 738 mV, short-circuit current 19.3 mA/cm², fill factor 65%, efficiency 9.3%) is based on the absorber with the least Cu deficiency, [Cu]/([In] + [Ga]) = 0.99. The activation energy of the diode saturation current density of such a cell is extracted from temperature- and illumination-dependent current-voltage measurements. A value of 1.04 eV, less than the band gap, suggests the heterojunction interface as the dominant recombination zone, just as in cells based on Cu-rich grown Cu(In,Ga)S₂.     

One-step synthesis of Cu(In,Ga)Se2 absorber layers by magnetron sputtering from a single quaternary target

A one-step route was developed to fabricate Cu(In,Ga)Se₂ (CIGS) absorber layers by direct magnetron sputtering from a single quaternary target with the composition of CuIn_0.75Ga_0.25Se₂. The effects of the substrate temperature, the working pressure and the sputtering power on the morphology and phase structure of the CIGS layers were studied using scanning electron microscopy, X-ray diffraction and Raman spectroscopy. The microstructure properties of the layers, including the crystallinity, grain size, compactness and the surface evenness, were found to be strongly dependent on the deposition parameters. CIGS absorbers with compact microstructure and large grains of micrometer size were obtained at 400 °C and 160 W, showing a very strong (220)/(204) orientation preference when sputtered at a higher working pressure. Raman spectra indicated no precipitation of the Cu-Se binary phases, but revealed a slight difference in the Ga/(Ga + In) ratio of different layers. The overall composition of the as-sputtered CIGS film was confirmed to be in agreement with the target composition through energy dispersive X-ray spectroscopy study. In comparison with the conventional co-evaporation or post-selenization synthesis for CIGS, the one-step sputtering route is more simplified and economical, which shows great potential to reduce the production cost of CIGS-based solar cells.     

Flexible Cu(In,Ga)Se2 on Al foils and the effects of Al during chemical bath deposition

Cu(In,Ga)Se₂ (CIGS) solar cells on aluminum foils offer the advantage to be flexible, lightweight and, because of the low cost substrate, can be used for several applications, especially in buildings, where aluminum is already commonly used. There are reports of a-Si solar cells on Al foil, but to our knowledge development of CIGS solar cells on Al foils has not been reported. We have developed CIGS solar cells on coated Al-foil samples. When using Al as substrate, CIGS layers of suitable structural and opto-electronic properties should be grown at low (< 450 °C) deposition temperatures, because of the difference in the thermo-physical properties of layers and substrates. We have grown CIGS layers by evaporation of elemental Cu, In, Ga, and Se at different substrate temperatures and investigated the properties of these CIGS layers by different methods (SEM, SIMS, and EDX). The photovoltaic properties of small area solar cells were characterized with I-V and quantum efficiency measurements. An efficiency of 6.6% has been achieved. We have also observed that some Al from the foil dissolves during chemical bath deposition (CBD) of CdS. The presence of Al in the bath seems, in some cases, to be beneficial for the electrical properties of the CIGS solar cells. Thinner and more homogenous CdS layers are obtained. Elastic Recoil Detection Analysis (ERDA) and SIMS measurements have shown incorporation of Al in the CdS.     

Modeling solar cells: A method for improving their efficiency

After a brief discussion on the theoretical basis for simulating solar cells and the available programs for doing this we proceed to discuss two examples that show the importance of doing numerical simulation of solar cells. We shall concentrate in silicon Heterojunction Intrinsic Thin film aSi/cSi (HIT) and CdS/CuInGaSe₂ (CIGS) solar cells. In the first case, we will show that numerical simulation indicates that there is an optimum transparent conducting oxide (TCO) to be used in contact with the p-type aSi:H emitter layer although many experimental researchers might think that the results can be similar without regard of the TCO film used. In this case, it is shown that high work function TCO materials such as ZnO:Al are much better than smaller work function films such as ITO. HIT solar cells made with small work function TCO layers (<4.8 eV) will never be able to reach the high efficiencies already reported experimentally. It will also be discussed that simulations of CIGS solar cells by different groups predict efficiencies around 18–19% or even less, i.e. below the record efficiency reported experimentally (20.3%). In addition, the experimental band-gap which is optimum in this case is around 1.2 eV while several theoretical results predict a higher optimum band-gap (1.4–1.5 eV). This means that there are other effects not included in most of the simulation models developed until today. One of them is the possible presence of an interfacial (inversion) layer between CdS and CIGS. It is shown that this inversion layer might explain the smaller observed optimum band-gap, but some efficiency is lost. It is discussed that another possible explanation for the higher experimental efficiency is the possible variation of Ga concentration in the CIGS film causing a gradual variation of the band-gap. This band-gap grading might help improve the open-circuit voltage and, if it is appropriately done, it can also cause the enhancement of the photo-current density.     

Optimization of Ti/TiN/Mo back contact properties for Cu(In,Ga)Se2 solar cells on polyimide foils

Molybdenum is conventionally used as electrical back contact for Cu(In,Ga)Se₂ (CIGS) solar cells. In this work, a multifunctional stack of Ti/TiN/Mo is introduced as back contact for flexible CIGS solar cells. The multilayer back contact was deposited on 25 μm thick polyimide foil by means of DC reactive sputtering.To optimize electrical conductivity and film stress of the alternative back contact sputter parameters such as total gas pressure, sputtering power, substrate temperature and RF substrate bias have been varied. XRD measurements and quantitative analysis of foil curvature revealed that the film stress is significantly influenced by the argon gas pressure and sputtering power. The electrical conductivity was improved by applying higher sputtering power or RF substrate bias. Analysis of the film microstructure with SEM shows that applied substrate bias influences the density of the sputtered film. The solar cells processed on Ti/TiN/Mo as well as on a conventional Mo bilayer back contact have been compared using standard current density to voltage (J-V) measurements and external quantum efficiency measurements. Conversion efficiencies of 13.4% for the alternative and 14.9% for the conventional design have been obtained.     

Advantages of using amorphous indium zinc oxide films for window layer in Cu(In,Ga)Se2 solar cells

The advantages of using indium zinc oxide (IZO) films instead of conventional Ga-doped zinc oxide (ZnO:Ga) films for Cu(In,Ga)Se₂ (CIGS) solar cells are described. The electrical properties of IZO are independent of film thickness. IZO films have higher mobility (30-40 cm²/Vs) and lower resistivity (4-5 × 10^− 4 Ω cm) compared to ZnO:Ga films deposited without intentional heating, because the number of grain boundaries in amorphous IZO films is small. The properties of a CIGS solar cell using IZO at the window layer were better than those obtained using a conventional ZnO:Ga at the window layer; moreover, the properties tended to be independent of thickness. These results indicate that use of IZO as a transparent conducting oxide layer is expected to increase the efficiency of CIGS solar cells.     

Synthesis of Cu(In,Ga)Se2 absorber using one-step electrodeposition of Cu-In-Ga precursor

One-step Cu-In-Ga electrodeposition on Mo substrate is carried out by potentiostatic method in acidic aqueous media. The applied potential, the pH and the nature of the electrolyte are determined to obtain adequate precursor composition. The electrodeposit is found highly dendritic, due to Cu diffusion-controlled deposition. Selenization at temperatures ranging from 450 to 600 °C leads to Cu(In,Ga)Se₂ (CIGS) absorber. The influence of selenization temperature and duration on Ga distribution as well as on CIGS crystallinity is discussed. Although the precursor is dendritic, relatively compact absorbers can be obtained. The best solar cell, achieved on 0.1 cm², shows 9.3% efficiency (V_oc 456 mV; j_sc 33 mA cm⁻²; FF 62%).     

Influence of growth temperature of transparent conducting oxide layer on Cu(In,Ga)Se2 thin-film solar cells

We have studied the influence of growth temperature (T_G) in the deposition of an indium tin oxide (ITO) transparent conducting oxide layer on Cu(In,Ga)Se₂ (CIGS) thin-film solar cells. The ITO films were deposited on i-ZnO/glass and i-ZnO/CdS/CIGS/Mo/glass substrates using radio-frequency magnetron sputtering at various T_G up to 350 °C. Both the resistivity of ITO and the interface quality of CdS/CIGS strongly depend on T_G. For a T_G ≤ 200 °C, a reduction in the series resistance enhanced the solar cell performance, while the p-n interface of the device was found to become deteriorated severely at T_G > 200 °C. CIGS solar cells with ITO deposited at T_G = 200 °C showed the best performance in terms of efficiency.     

Hydrogen effects on deep level defects in proton implanted Cu(In,Ga)Se2 based thin films

Hydrogen effects on deep level defects and a defect generation in proton implanted Cu(In,Ga)Se₂ (CIGS) based thin films for solar cell were investigated. CIGS films with a thickness of 3 μm were grown on a soda-lime glass substrate by a co-evaporation method, and then were implanted with protons. To study deep level defects in the proton implanted CIGS films, deep level transient spectroscopy measurements on the CIGS-based solar cells were carried out, these measurements found 6 traps (including 3 hole traps and 3 electron traps). In the proton implanted CIGS films, the deep level defects, which are attributed to the recombination centers of the CIGS solar cell, were significantly reduced in intensity, while a deep level defect was generated around 0.28 eV above the valence band maximum. Therefore, we suggest that most deep level defects in CIGS films can be controlled by hydrogen effects.     

CIGS thin-film solar cells on steel substrates

Steel foil is an attractive candidate for use as a flexible substrate material for Cu(In_x,Ga_1 − x)Se₂ solar cells (CIGS). It is stable at the high temperatures involved during CIGS processing and is also commercially available. Stainless chromium (Cr) steel is more expensive than Cr-free steel sheets, but the latter are not stable against corrosion. We processed CIGS solar cells on both types of substrates. The main problem arising here is the diffusion of detrimental elements from the substrate into the CIGS absorber layer. The diffusion of iron (Fe) and other substrate elements into the CIGS layer was investigated by Secondary Ion Mass Spectrometry (SIMS). The influence of the impurities on the solar cell parameters was determined by current voltage (JV) and external quantum efficiency (EQE) measurements. A direct correlation between the Fe content in the CIGS layer and the solar cell efficiency was found. The diffusion of Fe could be strongly reduced by a diffusion barrier layer. Thus we could process CIGS solar cells with a conversion efficiency of 12.8% even on Cr-free steel substrate.     

One-step RF magnetron sputtering method for preparing Cu(In,Ga)Se<Subscript>2</Subscript> solar cells

Cu(In, Ga)Se₂ (CIGS) solar cell is one of the most promising thin film solar cells. However the marketization of the CIGS solar cells is hindered by the uncertainty of the element ratios. Traditional sputtering with post selenization is one of the most widespread methods to produce the CIGS solar cells. Nevertheless, the post selenization process is the most difficult part of this technique, which could lead to element mismatch and heterogeneous. To simplify the preparing process, Cu(In, Ga)Se₂ (CIGS) solar cells were prepared without post-selenization process by RF sputtering CIGS target with abundant Se element. We focus on the effect of working pressure, substrate temperature and sputtering power on the properties of CIGS solar cells. When CIGS thin film was deposited at 580 °C, 0.8 Pa working pressure and 160 W sputtering power, the solar cell showed the highest power conversion efficiency (PCE) of 5.77%, which is only 0.64% lower than that of the solar cell prepared by traditional sputtering with post selenization method, and the two kinds of solar cells have same structure without MgF₂ antireflection layer, but the one-step sputtering method could greatly simplify the manufacture process of the CIGS solar cells. Our work makes clear that element Se would run off almost half during the sputtering process. And the element atomic ratios and the photovoltaic properties could be controlled by changing the sputtering parameters.