Issues on the chalcopyrite/defect-chalcopyrite junction model for high-efficiency Cu(In,Ga)Se2 solar cells

Considering the chalcopyrite/defect-chalcopyrite junction model for Cu(In_1−xGa_x)Se₂-based devices and our previously reported findings for the Cu(In_1−xGa_x)₃Se₅ defect chalcopyrites, we have postulated that uniform high-Ga-content photovoltaic structures (with x > 0.35) do not yield acceptable device performance due to the electrical and structural differences between both types of materials (chalcopyrite and defect-chalcopyrite).In this contribution, the structural properties of the surface region of Ga containing absorber materials have been studied by grazing incidence X-ray diffraction. We find that there are significant differences between surface and bulk. A structural model is proposed for the growth of the chalcopyrite/defect-chalcopyrite junction relative to its Ga content. And we demonstrate that closely lattice matched high-Ga-content structures (x > 0.35) can produce solar cells withv acceptable performances. The high-voltage and low-current electrical outputs from high Ga structures are very desirable in module fabrication because overall resistive losses can be substantially reduced.     

Examination of blocking current-voltage behaviour through defect chalcopyrite layer in ZnO/CdS/Cu(In,Ga)Se2/Mo solar cell

Blocking current-voltage behaviour of ZnO/CdS/Cu(In,Ga)Se₂/Mo solar cells, which is either temperature- or light-conditioned, is examined using a comprehensive numerical device simulator. Effects of defect states in the defect-chalcopyrite layer and at the CdS/defect-chalcopyrite interface are investigated. Acceptor-like defect states either in a defect-chalcopyrite layer or at the CdS/defect-chalcopyrite interface cause different trapping under red light or white light. This results in different potential profiles throughout the structure, which determine the changeable I−V behaviour under forward bias. Simulation results show that these acceptor-like defect states can also control the temperature-conditioned blocking I−V behaviour.     

Cu(In,Ga)Se2 solar cells on stainless-steel substrates covered with ZnO diffusion barriers

ZnO layers were deposited as diffusion barriers by DC magnetron sputtering from a pure Zn target on stainless-steel substrates. It was found that the insertion layer of ZnO between Mo film and stainless-steel substrate had no influence on the orientation and composition of CIGS films, as identified by an X-ray diffractometer and X-ray fluorescence, respectively. However, ZnO diffusion barriers had strongly reduced the diffusion of Fe from stainless-steel substrates into the CIGS films, as investigated by secondary ion mass spectrometry. With such diffusion barriers, the efficiency, open-circuit voltage, and fill factor of CIGS solar cells all increased.     

Effects of heat treatments on the properties of Cu(In,Ga)Se2 nanoparticles

Effects of heat treatment in nitrogen or Se atmosphere on the properties of Cu(In,Ga)Se₂ (CIGS) nanoparticles were investigated to extract optimum sintering conditions for fabrication of solar cell applicable CIGS absorber films. In nitrogen atmosphere, as the temperature increases from 100 to 400 °C the intensity of X-ray diffraction (XRD) peaks corresponding to the (1 1 2), (2 2 0) and (3 1 2) planes of the chalcopyrite CIGS increases, and the peak positions shift to lower angle regions without any particle growth in scanning electron microscopy (SEM) analysis, which is in consistent with the significant In and Ga loss in the EDS data. When the temperature further goes up to 500 °C, parts of CIGS are decomposed and Cu and CuSe₂ phases are observed. From these results, the heat treatment in nitrogen atmosphere is found to have no beneficial effect on the sintering of the particles and only induces loss of In and Ga. On the other hand, heat treatment in Se atmosphere at a substrate temperature of 550 °C with Se vapor evaporated at 250 and 450 °C provided much enhanced growth of the particles, specially up to 500 nm at 450 °C, and increased crystallinity without In or Ga loss, reflecting that Se supply played a critical role in the growth of the CIGS nanoparticles.     

CuIn(Ga)Se2-based devices via a novel absorber formation process

A novel pathway for the formation of copper–indium (gallium) diselenide has been developed. This two-stage process consists of (a) the formation of Cu–In–(Ga)–Se precursors, and (b) subsequent thermal treatment to form CuIn(Ga)Se₂. The morphology, structure and growth mechanism for several different precursor structures prepared under various conditions were studied and correlated to the deposition parameters as well as the structure and morphology of the annealed films. Photovoltaic devices prepared from CuInSe₂ and CuIn_0.75Ga_0.25Se₂ resulted in efficiencies of 10% and 13%, respectively.     

In situ monitoring of the growth of Cu(In,Ga)Se2 thin films

Thin films of Cu(In,Ga)Se₂ were grown by co-evaporation process in a conventional vacuum coating system at the base pressure of 10⁻⁵ mbar. The controllable of the two-stage growth process was developed. During the growth process, substrate temperature, graphite heater temperature, heating output power and temperature of the CIGS surface were monitored simultaneously. In this setup, we use the change in the thermal behavior of the substrate due to the variations in emissivity of CIGS film during the transition of Cu-rich to Cu-poor in the second stage corresponding to the change of power fed into the substrate heater as the control signal. By observing the variation of control signals, the desired final composition of the film can be obtained. Using our device fabrication, Al/ZnO(Al)/CdS/CIGS/Mo/SLG solar cells with efficiency over 14% (without AR) were achieved.     

Cu(In,Ga)Se2 solar cells with superstrate structure using lift-off process

Cu(In,Ga)Se₂ (CIGS) solar cells with a superstrate structure were fabricated using a lift-off process. To widen the variety of substrate choices for CIGS solar cells, a lift-off process was developed without an intentional sacrificial layer between the CIGS and Mo back-contact layers. The CIGS solar cells fabricated on Mo/soda-lime glass (SLG) were transferred to an alternative SLG substrate. The conversion efficiency of the CIGS solar cells with the superstrate structure was 5.1%, which was almost half that of the CIGS solar cells with a substrate structure prior to the lift-off process. The low conversion efficiency was caused by the high series resistance and low shunt resistance, which would be due to the junction resistance between the CIGS/back contact and cracks introduced during the lift-off process, respectively.     

Current routes in polycrystalline CuInSe2 and Cu(In,Ga)Se2 films

Local electrical transport measurements with scanning probe microscopy on polycrystalline (PX) p-CuInSe₂ and p-Cu(In,Ga)Se₂ films show that the photovoltaic and dark currents for bias voltages smaller than 1 V flow mainly through grain boundaries (GBs), indicating inversion at the GBs. Photocurrent for higher bias flows mainly via the grains. Based on these results and our finding of 100 meV GB band bending we deduce the potential landscape around the GBs. We suggest that high grain material quality, leading to large carrier mobilities, and electron–hole separation at the GBs, by chemical and electrical potential gradients, result in the high performance of these PX solar cells.     

Study of CdS/Cu(In, Ga)Se2 heterojunction interface using admittance and impedance spectroscopy

The interface properties of an unusual CdS/Cu(In, Ga)Se₂ solar cell have been studied by admittance and impedance spectroscopy. The current transport in this device has previously appeared to be dominated by tunnelling enhanced recombination at junction interface. The existence of this unexpected route was attributed to the presence of Cu-rich and indium depleted thin layer which might possibly be formed on the absorber surface. We have performed temperature dependent admittance and impedance measurements in order to clarify this phenomenon. An acceptor level with ionization energy of about 50 meV seems to be strongly correlated to the appearance of the CuGaSe₂ layer. The impedance spectra obtained at 100 K and 300 K exhibited single semi-circles. This indicates the dominance of the heterojunction interface without the effect of any other capacitive components. The equivalent circuit model consisting of a parallel resistor and capacitor in series with a resistor has been found to give a good fit to the experimental data.     

Photoconductivity of Cu(In, Ga) Se2 films

Polycrystalline CuIn_{1 − x}Ga_xSe₂ (0 ≤ x < 0.3) films (CIGS) were deposited by coevaporating the elements from appropriate sources onto glass substrates (substrate temperature 720 to 820 K). Photoconductivity of the polycrystalline CIGS films with partially depleted grains were studied in the temperature range 130–285 K at various illumination levels (0–100 mW/cm²). The data at low temperature (T < 170 K) were analyzed by the grain boundary trapping model with monovalent trapping states. The grain boundary barrier height in the dark and under illumination were obtained for different x-values of CuIn_1−xGa_xSe₂ films. Addition of Ga in the polycrystalline films resulted in a significant decrease in the barrier height. Variation of the barrier height with incident intensity indicated a complex recombination mechanism to be effective in the CIGS films.     

Highly efficient Cu(In,Ga)Se2 mini-modules

In this contribution, we present results and the philosophy of our mini-module efforts. These efforts have achieved world record levels as well as a reproducible process. Various mini-module designs are tested using two different baseline Cu(In,Ga)Se₂ deposition recipes. Gridded mini-modules achieve highest efficiencies and are much less demanding on the ZnO:Al top contact than their conventional counterpart. For all of the designs tested, our experimental results are in the order of the expectations from our modeling. Gridded modules can achieve efficiency levels very close to those of the cells.     

A new approach to high-efficiency solar cells by band gap grading in Cu(In,Ga)Se2 chalcopyrite semiconductors

High efficiencies in Cu(In,Ga)(S,Se)₂ solar cells result from alloying CuInSe₂ base material with the corresponding Ga- or S-containing compound. Compositional grading is one important issue in these devices. To obtain high efficiencies a reconstructed Cu-depleted absorber surface is essential. We consider this Cu/In grading non-intentional, process related and present a model which explains its importance. Another approach to improve performance is controlled intentional band gap grading via Ga/In and S/Se grading during the deposition. We show that appropriate grading can improve current and voltage of the device simultaneously. The key objective is to design a larger band gap for recombination and a lower band gap for absorption to energetically separate the mechanisms of carrier recombination and current generation.     

X-ray fluorescence investigation of the Ga distribution in Cu(In,Ga)Se2 thin films

The efficiencies of Cu(In,Ga)Se₂/CdS/ZnO solar cell devices in which the absorbers are produced by classical two-step processes are significantly lower that those in which co-evaporated absorbers are used. A significant problem related to two-step growth processes is the reported segregation of Ga towards the Mo back contact, resulting in separate CuInSe₂ and CuGaSe₂ phases. Furthermore, it is often reported that material losses (especially In and Ga) occur during high-temperature selenization of metallic precursors. In this study, X-ray fluorescence (XRF) analysis was used to study the diffusion behaviour of the chalcopyrite elements in single-stage and two-stage processed Cu(In,Ga)Se₂ thin films. This relatively simple characterization technique proved to be very reliable in determining the degree of selenium incorporation, possible material losses and the in-depth compositional uniformity of samples at different stages of processing. This information is especially important in the case of two-stage growth processes, involving high-temperature selenization steps of metallic precursors. Device quality Cu(In,Ga)Se₂ thin films were prepared by a relatively simple and reproducible two-step growth process in which all the metals were evaporated from one single crucible in a selenium-containing environment. The precursors were finally treated in an H₂Se/Ar atmosphere to produce fully reacted films. XRF measurement indicated no loss of In or Ga during this final selenization step, but a significant degree of element diffusion which depended on the reaction temperature. It was also possible to produce Cu(In,Ga)Se₂ thin films with an appreciable amount of Ga in the near-surface region without separated CuInSe₂ and CuGaSe₂ phases.     

Study of CdS/Cu(In,Ga)Se2 interface by using n values extracted analytically from experimental data

This paper presents that an analytical method based on Lambert W-function can be applied to estimate the value of the diode ideality factor n, of a ZnO/CdS/Cu(In,Ga)Se₂ (CIGS) solar cell by using its dark current-voltage characteristics. The method is tested at different temperatures in the dark and found that the resulting n(T) values are in good agreement with those estimated experimentally from the slopes of the straight-line regions of Log I-V plots. The suggested values of n(T) under illumination are also determined using the exact explicit analytic solutions for the current-voltage relation expressed in terms of Lambert W-functions and experimentally estimated parasitic series and shunt resistances (R_s, R_sh), diode saturation current (I_o), open circuit voltage (V_oc) and short circuit current (I_sc) values at various temperatures. Temperature dependence of the diode ideality factor revealed that after illumination still tunnelling enhanced interface recombination mechanism dominates the current transport with relatively low tunnelling energy as compared to the dark case.     

Improved compositional flexibility of Cu(In,Ga)Se2-based thin film solar cells by sodium control technique

The effects of sodium on off-stoichiometric Cu(In,Ga)Se₂ (CIGS)-based thin films and solar cells were investigated. The CIGS-based films were deposited with intentionally incorporated Na₂Se on Mo-coated SiO_x/soda-lime glass substrates by a multi-step process. By sodium control technique high-efficiency ZnO : Al/CdS/CIGS solar cells with efficiencies of 10–13.5% range were obtained over an extremely wide Cu/(In + Ga) ratio range of 0.51–0.96, which has great merit for the large-area manufacturing process. The improved efficiency in the off-stoichiometric regions is mainly attributed to the increased acceptor concentration and the formation of the Cu(In,Ga)₃Se₅ phase films with p-type conductvity. A new type of solar cell with p-type Cu(In,Ga)₃Se₅ phase absorber materials is also suggested.     

Reversible changes of the fill factor in the ZnO/CdS/Cu(In,Ga)Se2 solar cells

The reversible persistent changes of the fill factor (FF) induced by the illumination and voltage bias along with changes in the electronic properties of the ZnO/CdS/Cu(In,Ga)Se₂ photovoltaic devices have been studied. Admittance spectroscopy and capacitance–voltage characterization reveal a correlation between the FF and the space charge distribution within the absorber. Our experiments provide evidence that a major source of FF loss in efficient devices is caused by excess negative charge close to the interface. We explain the persistent changes in the net acceptor concentration in the interface region by the relaxation effects due to compensating donors—the same mechanism, which leads to metastable changes of the doping level in the bulk of the absorber.     

Quantum efficiency and admittance spectroscopy on Cu(In,Ga)Se2 solar cells

We investigate the electronic transport properties of Cu(In,Ga)Se₂ solar cells by means of quantum efficiency and temperature dependent admittance spectroscopy. A simple evaluation scheme of quantum efficiency data is introduced which accounts for recombinatoric losses in the Us buffer layer and in the Cu(In,Ga)Se₂ absorber. By admittance spectroscopy, we find that the controlled incorporation of Na into the absorber material leads to a shallow acceptor state at about 75 meV above the valence band.     

Near-band-edge photoluminescnce in Cu(In,Ga)Se2 solar cells

Photoluminescence (PL) and PL decay characteristics of the near-band-edge (NBE) PL at room temperature have been studied on the Cu(In,Ga)Se₂ (CIGS) solar cells. The carrier recombination process has been discussed with emphasis on the photovoltaic properties of the solar cell. It has been found that: (i) PL intensity of the CIGS solar cells is much stronger than that in the corresponding CIGS thin films, (ii) the PL decay time of the cell is longer than that of the CIGS film, and (iii) the PL decay time of the CIGS solar cell exhibits strong dependence on the PL excitation intensity. In the CIGS solar cell, intense PL is obtained under the open circuit condition (oc), in contrast to the very low PL yield under the short circuit (sc) condition. The PL decay time under the sc condition is much shorter than that under the oc condition. Excitation intensity dependence of PL intensity and the PL decay time have been studied, and they are discussed with relation to the photo-voltage due to the PL excitation light. PL and injection EL under the external DC bias have been studied. The mapping image of NBE-PL intensity has been compared with that of the laser beam induced current (LBIC), and the PL intensity image reflects the photovoltaic properties of the CIGS solar cells. We demonstrated that NBE-PL of the CIGS solar cell reflects the photovoltaic effect, and it can be utilized as a powerful characterization method.     

Characterization of Cu(In,Ga)Se2 thin films prepared by thermal crystallization on Mo/glass substrate

Thin films of Cu(In,Ga)Se₂ were prepared by thermal crystallization on the sputtered Mo/substrate and characterized. MoSe₂ layer was formed at the interface between Cu(In,Ga)Se₂ and Mo layers after the thermal crystallization. The graded Ga concentration in crystallized Cu(In,Ga)Se₂ thin films was confirmed. Cu(In,Ga)Se₂ thin films prepared on the Mo/soda-lime glass had large and columnar grains rather than those on the Mo/quartz substrate.     

Preparation of Zn doped Cu(In,Ga)Se2 thin films by physical vapor deposition for solar cells

Cu(In,Ga)Se₂ (CIGS) surface was modified with Zn doping using vacuum evaporation. Substrate temperatures and exposure times during the Zn evaporation were changed to control a distribution of Zn in the CIGS films. Diffusion of Zn in the CIGS films was observed at the substrate temperature of over 200°C. The diffusion depth of Zn increases with increasing the exposure time at the substrate temperature of 300°C. Solar cells were fabricated using the Zn doped CIGS films. A distribution of the efficiencies decreases with increasing the exposure time of Zn vapor. The doping of Zn at the film surface improved reproducibility of a high fill factor and efficiency. A solar cell fabricated using the CIGS film modified with Zn doping showed an efficiency of 14.8%.