Dependence of carrier lifetime on Cu-contacting temperature and ZnTe:Cu thickness in CdS/CdTe thin film solar cells

Cu diffusion from a ZnTe:Cu contact interface can increase the net acceptor concentration in the CdTe layer of a CdS/CdTe photovoltaic solar cell. This reduces the space-charge width (W_d) of the junction and enhances current collection and open-circuit voltage. Here we study the effect of Cu concentration in the CdTe layer on carrier lifetime (τ) using time-resolved photoluminescence measurements of ZnTe:Cu/Ti-contacted CdTe devices. Measurements show that if the ZnTe:Cu layer thickness remains constant and contact temperature is varied, τ increases significantly above its as-deposited value when the contacting temperature is in a range that has been shown to yield high-performance devices (~ 280° to ~ 320 °C). However, when the contacting temperature is maintained near an optimum value and the ZnTe:Cu thickness is varied, τ decreases with ZnTe:Cu thickness.     

Cu-related recombination in CdS/CdTe solar cells

Cu used in the back contact of CdS/CdTe solar cells is known to improve contact behavior and open-circuit voltage. A study of devices made with varying Cu amounts confirmed these observations. However, Cu was also found to be deleterious to current collection. Time-resolved photoluminescence measurements of CdTe devices show that carrier lifetime decreased with increased Cu concentration. Drive-level-capacitance-profiling and low-temperature photoluminescence suggest this decrease in lifetime was associated with increased recombination center density introduced by Cu in the CdTe layer. The resulting impact of increased Cu on device performance was a voltage-dependent collection of photogenerated carriers that reduced fill-factor.     

Phase control of CuxTe film and its effects on CdS/CdTe solar cell

Phase control is critical for achieving high-performance CdTe cells when Cu_xTe is used as a back-contact for CdTe cells. Cu_xTe phases are mainly controlled by the Cu/Te ratio, and they can also be affected by post-heat-treatment temperature. Although Cu₂Te has the highest conductivity, it is unstable and provides more Cu diffusion into the CdS and CdTe films. Cu diffusion into the CdS causes “cross-over”, and Cu diffusion into the CdTe film creates Cu-related defects that lower photogenerated carrier lifetime and result in voltage-dependent collection. A “recontact” experiment clearly indicated that the mechanism giving rise to “roll-over” is the formation of Cu-related oxides, rather than the loss of Cu on the back-contact.     

CdTe thin film solar cells with reduced CdS film thickness

A study was performed to reduce the CdS film thickness in CdTe thin film solar cells to minimize losses in quantum efficiency. Using close space sublimation deposition for CdS and CdTe a maximum efficiency of ~ 9.5% was obtained with the standard CdS film thickness of ~ 160 nm. Reduction of the film CdS thickness to less than 100 nm leads to poor cell performance with ~ 5% efficiency, mainly due to a lower open circuit voltage. An alternative approach has been tested to reduce the CdS film thickness (~ 80 nm) by depositing a CdS double layer. The first CdS layer was deposited at high substrate temperature in the range of 520-540 °C and the second CdS layer was deposited at low substrate temperature of ~ 250 °C. The cell prepared using a CdS double layer show better performance with cell efficiency over 10%. Quantum efficiency measurement confirmed that the improvement in the device performance is due to the reduction in CdS film thickness. The effect of double layer structure on cell performance is also observed with chemical bath deposited CdS using fluorine doped SnO₂ as substrate.     

Initial and degraded performance of thin film CdTe solar cell devices as a function of copper at the back contact

Copper performs an important role in obtaining high-performance thin-film CdTe solar cell devices. Both initial performance and performance after stress depends strongly on the total copper content at the back-contact, the Cd to Te ratio on the backside, the etching process, and the way the copper is activated. With regard to getting high open circuit voltage a small amount of Cu seems sufficient upon the right anneal treatment. However, regarding open circuit voltage degradation for stressed devices there seems to be an optimum amount of Cu. Te-enrichment does not seem to have a big impact on device stability.     

The role of transparent conducting oxides in metal organic chemical vapour deposition of CdTe/CdS Photovoltaic solar cells

A systematic study is made between the relationship of Cd_0.9Zn_0.1S/CdTe photovoltaic (PV) device properties for three different commercial transparent conducting oxide (TCO) materials and some experimental CdO to determine the role of the TCO in device performance. The resistance contribution from the TCO was measured after depositing the gold contact architectures directly onto the TCOs. These were compared with the Cd_0.9Zn_0.1S/CdTe device properties using the same contact arrangements. Series resistance for the commercial TCOs correlated with their sheet resistance and gave good agreement with the PV device series resistance for the indium tin oxide (ITO) and fluorine doped tin oxide (FTO) 15 Ω/Sq. superstrates. The devices on the thicker FTO 7 Ω/sq superstrates were dominated by a low shunt resistance, which was attributed to the rough surface morphology causing micro-shorts. The device layers on the CdO substrate delaminated but devices were successfully made for ultra-thin CdTe (0.8 μm thick) and compared favourably with the comparable device on ITO. From the measurements on these TCOs it was possible to deduce the back contact resistance and gave an average value of 2 Ω.cm². The correlation of fill factor with series resistance has been compared with the predictions of a 1-D device model and shows excellent agreement. For high efficiency devices the combined series resistance from the TCO and back contact need to be less than 1 Ω.cm².     

Effects of high-temperature annealing on ultra-thin CdTe solar cells

High-temperature annealing (HTA), a process step prior to vapor cadmium chloride (VCC) treatment, has been found to be useful for improving the crystallinity of CdTe films and the efficiency of ultra-thin CdTe solar cells. Scanning electron microscopy, optical absorption, photoluminescence measurements and analyses on photoluminescence results using spectral deconvolution reveal that the additional HTA step produces substantial grain growth and reduces grain boundary defects. It also reduces excessive sulfur diffusion across the junction that can occur during the VCC treatment. The HTA step helps to produce pinhole-free CdTe films and reduce electrical shorts in ultra-thin CdTe solar cells. An efficiency of about 11.6% has been demonstrated for ultra-thin CdS/CdTe solar cells processed with HTA step.     

Effect of back-contact barrier on thin-film CdTe solar cells

The presence of a back-contact barrier affects the current–voltage characteristics of thin-film CdS/CdTe/metal solar cells primarily by impeding hole transport, a current-limiting effect commonly referred to as “rollover.” In this work, the CdS/CdTe solar cell with a CdTe/metal back-contact barrier is modeled by two opposite polarity diodes in series. Analytic simulations are fitted to the measured current–voltage curve, the voltage distribution between the two diodes is shown under different conditions, and the back-contact barrier height is extracted. Room-temperature barrier heights exceeding 0.5 eV will generally result in significant fill-factor reduction.     

A detailed study of the series resistance effect on CdS/CdTe solar cells with Cu/Mo back contact

CdS/CdTe thin film solar cells with an area of 1 cm² were obtained and studied in detail. A ZnO buffer layer was deposited by reactive RF-sputtering on commercial ITO substrates. The CdS layer was grown on ZnO also by using RF-sputtering and CdTe thin film was deposited by conventional CSS technique. The chlorination of the solar cells is performed into Freon atmosphere at 400 °C. The CdTe thin film surface was chemically etched by using Br-Methanol solution. The back contact was deposited using RF-sputtering from a pure Cu and Mo targets. The procedure developed in this work led us to make systematically solar cells with good efficiency. However, the series resistance has a high value for an area of 1 cm² (22 Ω cm²). In order to make more detailed study, the solar cell with an area of 1 cm² was divided in a 3 × 3 matrix. A good homogeneity in cell properties is observed and the efficiency increases to more than 11%, fundamentally through decreasing series resistance.     

Ordered polycrystalline thin films for high performance CdTe/CdS solar cells

An ordered polycrystalline approach is proposed to overcome fundamental problems associated with random polycrystalline thin films, namely grain boundaries and inhomogeneity. The approach consists of two main steps: (1) the deposition of a patterned growth mask and (2) the selective-area deposition of the ordered polycrystals. The ordered polycrystalline approach was investigated using the CdTe/CdS material system. Experimental results demonstrate that SiO₂ and Si₃N₄ are effective growth masks and that temperature is a dominant parameter for selective-area deposition. PL and XRD characterization indicates that the ordered polycrystalline technique has the potential for improving the crystal quality and order of polycrystalline CdTe thin films. The approach appears to be fairly general and could be applied to other material systems.     

Thin-film solar cells

The rapid progress that is being made with inorganic thin-film photovoltaic (PV) technologies, both in the laboratory and in industry, is reviewed. While amorphous silicon based PV modules have been around for more than 20 years, recent industrial developments include the first polycrystalline silicon thin-film solar cells on glass and the first tandem solar cells based on stacks of amorphous and microcrystalline silicon films (“micromorph cells”). Significant thin-film PV production levels are also being set up for cadmium telluride and copper indium diselenide.     

CdTe photoelectrochemical solar cells—chemical modification of surfaces

Chemical modification of bothn andp type CdTe has been found to improve the performance and stability of PEC solar cells. The surfaces, modified by Ru³⁺, have been examined by a variety of techniques. Modification results in enhanced barrier height at the surface due to the formation of a passivating oxide layer.     

Investigation of the excitonic luminescence band of CdTe solar cells by photoluminescence and photoluminescence excitation spectroscopy

The excitonic luminescence band of polycrystalline cadmium telluride layers has been investigated by Photoluminescence (PL) and Photoluminescence excitation spectroscopy (PLE). CdTe was deposited by means of close space sublimation and the samples were activated by different chlorine containing compounds, i.e. cadmium chloride, hydrochloric acid, and sodium chloride as well as by simple air activation or received no post deposition treatment. In the PL spectra, four different peaks within the excitonic luminescence band were resolved. These include the free-exciton peak and two transitions of excitons bound to defects. Furthermore, free excitons and band to band transitions were detected by means of PLE. The PL and PLE spectra are discussed with respect to the post deposition treatments.     

The effect of impurities on the doping and VOC of CdTe/CdS thin film solar cells

The effect of introducing impurities in CdTe, namely antimony (Sb) and oxygen (O), on the net carrier concentration in CdS/CdTe solar cells and on their open-circuit voltage (V_OC) has been investigated. Oxygen was introduced in the CdTe films during the deposition of this layer by the close-spaced sublimation process. The total pressure was held constant at 1330 Pa (N₂ and O₂). The amount of oxygen was varied by varying its partial pressure. Antimony was introduced into CdTe using a post-deposition diffusion process. Following the deposition of CdTe a thin film (a few nm) of Sb was deposited onto the CdTe surface and subsequently heat-treated to cause in-diffusion of Sb. The temperature and time during the diffusion process were varied in the range of 300-525 °C and 20-160 min respectively. In both instances it was possible to vary (increase) the doping concentration in CdTe. The increase in doping was accompanied by an increase in V_OC. However, in all instances the doping in CdTe reached a maximum value, beyond which further increases were not possible leading to saturation in V_OC. The highest V_OC measured was similar to state-of-the-art values in the range of 800-830 mV, and the highest doping concentration measured was in the 10¹⁶ cm^− 3 range.     

Electroconversion of CdS to CuxS for thin film solar cells

Electroconversion of vacuum-evaporated CdS films to cuprous sulphide (Cu_xS) for the fabrication of thin film CdS/Cu_xS solar cells was investigated. The Cu_xS films so formed were characterized by electrochemical and electron diffraction methods. The dependence of the stoichiometry x of the Cu_xS on conversion parameters such as the concentration, pH and temperature of the electrolyte (CuSO₄) and the cathode (CdS) current density was established. A 0.4 M concentration bath with the pH value maintained at 2.5 was found to be most suitable. For this bath, optimum combinations of the bath temperature and cathode current density yielding the most stoichiometric Cu_xS (x?1.99) were found to be in the ranges 55–65°C and 2.5-5.0 mA cm^-2 respectively. The films converted under the optimum conditions exhibit predominantly a chalcocite structure. The observed kinetics of the conversion process was understood in terms of a proposed two-step reaction at the cathode, involving a chemical ion exchange and an electrochemical reduction reaction.     

Doping profiles in CdTe/CdS thin film solar cells

CdS/CdTe thin film solar cells showing comparable properties as commercial cells have been prepared by close space sublimation (CSS) in our own laboratory. We characterised the cells by capacitance-voltage profiling (C-V), thermal admittance spectroscopy (TAS), and thermally stimulated capacitance measurements (TSCAP). The doping profiles of the CdTe layer obtained by C-V measurements confirm the well known rise in dopant concentration with increasing depth if the usual evaluation procedure is employed. However, the TAS and TSCAP measurements reveal deep acceptors in the CdTe layer with a large concentration exceeding that of the shallow dopants. Under these conditions, C-V measurements are shown to yield an apparently rising dopant concentration even for homogeneous doping. A combined simulation of doping profiles measured at different temperatures using a fixed and uniform shallow and deep doping fits well to measured doping concentration. These results indicate how to get reliable information on the shallow dopant concentration.     

Physical properties of Bi doped CdTe thin films grown by CSVT and their influence on the CdS/CdTe solar cells PV-properties

The physical properties of Bi doped CdTe films, grown on glass substrates by the Closed Space Transport Vapour (CSVT) method, from different Bi doped CdTe powders are presented. The CdTe:Bi films were characterized using Photoluminescence, Hall effect, X-Ray diffraction, SEM and Photoconductivity measurements. Moreover, CdS/CdTe:Bi solar cells were made and their characteristics like short circuit current density (J_sc), open circuit voltage (V_OC), fill factor (FF) and efficiency (η) were determined. These devices were fabricated from Bi doped CdTe layers deposited on CdS with the same growth conditions than those used for the single CdTe:Bi layers. A correlation between the CdS/CdTe:Bi solar cell characteristics and the physical properties of the Bi doped CdTe thin films are presented and discussed.     

In situ deposition of cadmium chloride films using MOCVD for CdTe solar cells

This paper reports on the first deposition of cadmium chloride (CdCl₂) films by metal organic chemical vapour deposition (MOCVD). As the p-n junction can be deposited by MOCVD, the in situ CdCl₂ treatment of the device allows for containment of the whole process. MOCVD allows a high level of control over material properties and excellent repeatability. Deposition of CdCl₂, on glass and silicon, at different II:VII precursor ratios and substrate temperatures are reported. The precursors used are dimethylcadmium and tertiarybutylchloride or n-hexylchloride, respectively for the cadmium and chlorine species. Results are presented on the surface morphology and layer structure. CdCl₂ was in its hydrate form once exposed to ambient air. Preliminary results on the effects of in situ CdCl₂ treatment on MOCVD CdS/CdTe:As devices are reported and compared with untreated devices, using current-voltage characterisation. The CdCl₂ treatment successfully resulted in MOCVD devices having open-circuit voltage higher than 600 mV and fill factor above 50%.     

Towards ultra-thin CdTe solar cells using MOCVD

A study was made on very thin CdTe absorber < 1 µm layers to investigate limitations in CdTe collection efficiency. Metal organic chemical vapour deposition (MOCVD) was used to deposit cadmium sulfide (CdS), cadmium zinc sulfide (Cd_0.9Zn_0.1S) and cadmium telluride (CdTe). Improvements in photon collection in the blue, where the absorption length is shorter, have been achieved using a wider band gap Cd_0.9Zn_0.1S ternary alloy to replace CdS as the window layer. Solar cell capacitance simulator (SCAPS) modelling software [M. Burgelman, P. Nollet, S. Degrave, Thin Solid Films, 361-362 (2000) 527-532] has been used to calculate device parameters as a function of the absorber layer thickness (controlled by in situ using laser reflectometry). One feature of the MOCVD grown devices is the apparent absence of pin-holes, demonstrated by growth of an ultra-thin absorber (200 nm) with conversion efficiency of nearly 4%.