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.     

Valence band splitting in wurtzite InP nanowires observed by photoluminescence and photoluminescence excitation spectroscopy

We have investigated individual bulk-like wires of wurtzite InP using photoluminescence, photoluminescence excitation spectroscopy and transmission electron microscopy. Using two different methods we find that the top of the valence band is split, as expected theoretically. This splitting of the valence band is peculiar to wurtzite InP and does not occur in zinc blende InP. We find the energy difference between the two bands to be 40 meV.     

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.     

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.     

Yellow luminescence band in undoped GaN revealed by two-wavelength excited photoluminescence

The below-gap emission components including yellow luminescence (YL) band of an MOCVD grown undoped GaN have been studied by the two-wavelength-excited photoluminescence (TWEPL). The nature of each emission line has been investigated by using an intermittent below-gap excitation (BGE) light of 1.17 eV on an above-gap excitation (AGE) light of 3.49 eV. The intensity of DAP and the YL decreased while it increased for I_OX after irradiation of the BGE. The intensity change in PL after addition of the BGE implies the presence of defect levels in the energy position corresponding to the photon energy of the BGE. Possible recombination models are listed and examined. Only the recombination model in which the YL corresponds to the transition from a shallow donor to a deep state at about 1 eV above the valence band maximum satisfies our experimental result. The possible origin of this defect state is discussed.     

The formation of different phases of CuxTe and their effects on CdTe/CdS solar cells

Material studies and device applications of Cu_xTe in an NREL-developed CdTe solar cell structured as glass/Cd₂SnO₄/ZnSnO_x/CdS/CdTe are presented. The Cu_xTe primary back contact was formed by evaporating a Cu layer with various thicknesses at room temperature on HNO₃/H₃PO₄ (NP) solution etched CdTe layer. A post-annealing was then followed. The structural evolution and electrical properties of Cu_xTe were investigated. Cu/Te ratio and post-annealing temperature are two processing parameters in this study. The Cu_xTe phases are mainly controlled by the Cu/Te ratio. After a post-annealing at a low temperature, such as 100 °C, no Cu_xTe phase transformation from its as-deposited phase was observed. A post-annealing treatment at a higher temperature, such as 250 °C, can reveal the stoichiometric Cu_xTe phases based on the Cu/Te ratio used in the devices. But a post-annealing at a further higher temperature, such as 400 °C, resulted in a complicated Cu_xTe phase appearance. CuTe, Cu_1.4Te, and Cu₂Te are three major phases detected by X-ray diffraction (XRD) for different Cu thickness application annealed at 250 °C. Application of Cu thicker than 60 nm degrades open-circuit voltage (V_oc) and shunting resistance (R_sh), but increases series resistance (R_s). The correlation between device performance and the Cu_xTe back contact illustrates that the process used for forming the Cu₂Te back contact failed to produce good fill factor (FF) and also introduced higher barrier height. The best device was observed for a back contact with a mixed Cu_1.4Te and CuTe phases.     

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.     

Role of thermal treatment on the luminescence properties of CdTe thin films for photovoltaic applications

The efficiency of CdTe based solar cells is strongly enhanced by a thermal treatment in HCF₂Cl ambient. CdTe thin films deposited on CdS/ZnO/ITO/glass by Closed Space Sublimation before and after the annealing are characterised. The CdTe morphology is studied by atomic force microscopy and scanning electron microscopy. In the treated films the non-homogeneous distribution of the grain size disappears, in addition an increasing of the dimensions of the grains is observed. Cathodoluminescence analyses show a remarkable difference in the spectra between the treated and untreated structures. A strong increase in the intensity of the 1.4 eV band is observed by increasing the HCF₂Cl content. A model of the electronic levels inside the CdTe band gap, due to incorporation of Cl (or F) is proposed.     

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.     

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.     

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%.     

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.     

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.     

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%.     

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.     

Growth regimes of CdTe deposited by close-spaced sublimation for application in thin film solar cells

We have systematically investigated the growth of CdTe thin films by Close Spaced Sublimation (CSS). Thin films of CdTe were deposited onto CdS substrates held at temperatures in the range 250 to 550 °C. The effect of substrate temperature and evaporation rate on structure and surface morphology of CdTe films were investigated. Up to 450 °C substrate temperature the growth rate was almost constant and decreased exponentially for higher temperatures. The structures of the CdTe films were determined by XRD and a strong (111) orientation was observed within the temperature range 250 °C-470 °C. Above 470 °C the texture changed to mostly (311) and (220) orientations. Surface morphology and grain size of CdTe growth was determined with AFM and SEM. The morphology of the layers showed three major modes: Columnar grains with a diameter of 0.2 μm and a length of 6 μm for temperatures from 250 °C to 350 °C, pyramidal grains with a diameter of 0.5-1.5 μm up to 470°C and irregular shaped grains with a diameter of 5-10 μm for temperatures up to 550 °C. The roughness increased linearly from 15 nm to 220 nm within the substrate temperature range.     

Influence of deviation from stoichiometry on the photoluminescence in CdTe doped with indium

Low temperature photoluminescence of vacuum and cadmium annealed CdTe:In is reported here. A new peak at ∼ 1·14 eV related to transitions from the conduction band to an acceptor involving a tellurium vacancy has been observed.     

CdTe thin film solar cells: Interrelation of nucleation, structure, and performance

The performance of CdTe solar cells as prototype of thin film solar cells strongly depends on film morphology. The needs for high solar cell performance using thin film materials will be addressed covering nucleation and growth control of thin film materials. In order to understand the basic growth mechanisms and their impact on cell performance, we have systematically investigated the growth of CdTe thin films by Close Spaced Sublimation (CSS) using the integrated ultra-high vacuum system DAISY-SOL. CdTe thin films were deposited on TCO/CdS substrates (transparent conductive oxide) held at 270 °C to 560 °C. The properties of the films were determined before and after CdCl₂ treatment using X-ray diffraction and electron microscopy. In addition, solar cells were prepared to find correlations between material properties and cell efficiency. At low sample temperature the films tend to form compact layers with preferred (111) orientation which is lost at elevated temperatures above 450 °C. For CdS layers without (0001) texture there is in addition a low temperature regime (350 °C) with (111) texture loss. After activation treatment the (111) texture is lost for all deposited layers leading to strong recrystallisation of the grains. But the texture still depends on the previous growth history. The loss of (111) texture is evidently needed for higher performance. A clear correlation between cell efficiency and the texture of the CdTe film is observed.     

Efficiency simulations of thin film chalcogenide photovoltaic cells for different indoor lighting conditions

Photovoltaic (PV) energy is an efficient natural energy source for outdoor applications. However, for indoor applications, the efficiency of PV cells is much lower. Typically, the light intensity under artificial lighting conditions is less than 10 W/m² as compared to 100-1000 W/m² under outdoor conditions. Moreover, the spectrum is different from the outdoor solar spectrum. In this context, the question arises whether thin film chalcogenide photovoltaic cells are suitable for indoor use. This paper contributes to answering that question by comparing the power output of different thin film chalcogenide solar cells with the classical crystalline silicon cell as reference. The comparisons are done by efficiency simulation based on the quantum efficiencies of the solar cells and the light spectra of typical artificial light sources i.e. an LED lamp, a “warm” and a “cool” fluorescent tube and a common incandescent and halogen lamp, which are compared to the outdoor AM 1.5 spectrum as reference.