Study of in situ CdCl2 treatment on CSS deposited CdTe films and CdS/CdTe solar cells

Effect of in situ CdCl₂ treatment on the morphological, structural and electrical properties of CdTe films as well as on solar cell characteristics of CdS/CdTe junction has been investigated. XRD measurements show that the presence of CdCl₂ vapours induces 111 oriented growth in the CdTe films. CdCl₂ concentration required for this oriented growth is found to be directly proportional to the substrate temperature. SEM measurements show enhanced grain growth in the presence of CdCl₂. Spectral response of the CdCl₂ treated CdS/CdTe solar cells shows an enhanced CdS diffusion in to the CdTe, which results in an improved spectral response in UV range and a consequent reduction in the interface states density. A drastic reduction in the deep levels due to the CdCl₂ treatment, as seen in the photo-capacitance studies, has results in CdS/CdTe solar cells having efficiency >8%.     

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 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.     

Comparison between the effects of CdCl2 heat treatment on CdTe films prepared by RF magnetron sputtering and close spaced sublimation methods

CdTe films were prepared on Fluorine-doped tin oxide substrate by RF magnetron sputtering and close spaced sublimation (CSS) methods, respectively. These CdTe films were then treated with a wet CdCl₂ heat process at different temperatures. The structural and optical properties of CdTe films were investigated by X-ray diffraction, scanning electron microscope and UV–Visible spectrophotometer. The results reveal that both types of CdTe films have a better crystalline and larger grain size after CdCl₂ heat treatment. However, the (422) peak has a more preferential orientation than (511) peak after CdCl₂ activation for CdTe films prepared by sputtering method, while these two peaks almost have the same intensity for CSS-prepared CdTe films. The transmittance of CdTe films prepared by CSS is apparently lower than sputtered CdTe films. Correspondingly, the efficiency of solar cells with CSS-prepared CdTe is 7.3, 2.6 % of sputtered CdTe films.     

硝磷酸腐蚀的CdTe太阳电池性能

CdTe薄膜的腐蚀是制作CdS/CdTe光伏电池的重要技术之一,本实验采用硝磷酸溶液（硝酸1%＋磷酸70%＋去离子水29%）腐蚀CdTe薄膜,通过XRD测试发现在CdTe膜上生成了碲层.随后,在腐蚀后的CdTe薄膜上分别沉积了几种结构的背接触层,并制备出相应结构的CdTe太阳能光伏电池.通过电池的光、暗I-V和C-V特性测试,以ZnTe/ZnTe：Cu/Ni为背接触的小面积太阳电池,其性能优于其它背接触的电池.实验结果表明器件性能与碲的生成和铜的扩散密切相关.     

衬底温度对碲化镉薄膜性质及太阳电池性能的影响

蒸汽输运法是制备高质量且大面积均匀的CdTe薄膜的一种优良的方法。采用自主研发的一套蒸汽输运沉积系统制备了CdTe多晶薄膜, 并研究了衬底温度对CdTe薄膜性质及太阳电池性能的影响。利用XRD、SEM、UV-Vis和Hall等测试手段研究了衬底温度对薄膜的结构、光学性质和电学性质的影响。结果表明, 蒸汽输运法制备的CdTe薄膜具有立方相结构, 且沿(111)方向高度择优。随着衬底温度的升高(520℃~640℃), CdTe薄膜的平均晶粒尺寸从2 μm增大到约6 μm, CdTe薄膜的载流子浓度也从1.93×10¹⁰ cm^-3提高到2.36×10¹³ cm^-3, 说明提高衬底温度能够降低CdTe薄膜的缺陷复合, 使薄膜的p型更强。实验进一步研究了衬底温度对CdTe薄膜太阳电池性能的影响, 结果表明适当提高衬底温度, 能够大幅度提高电池的效率、开路电压和填充因子, 但是过高的衬底温度又会降低电池的长波光谱响应, 导致电池转换效率的下降。经过参数优化, 在衬底温度为610℃、无背接触层小面积CdTe薄膜太阳电池的转换效率达到11.2%。     

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.     

Pathways to thin absorbers in CdTe solar cells

We present approaches to reduce the absorber thickness of CdTe solar cells. The investigations were done with CdTe absorber films deposited by the close-space sublimation (CSS) technique. Using these CdTe films, complete solar cells were produced in our own laboratory. The absorber thickness as the crucial parameter was varied between 1 and 11 µm in these experiments. It is analyzed how process steps following the CdTe layer deposition influence the structure of the absorber films as well as the solar cell properties. Three ways of back contact formation are compared. These include (i) the wet chemical etching of the CdTe surface, (ii) a plasma etching step, and (iii) the vacuum deposition of a thin intermediate copper layer. In the latter case, voids and shunts related to preferential etching at grain boundaries are avoided admitting the use of thinner absorber films. Thus, the solar-cell efficiencies were increased from below 9% to more than 10% while the CdTe film thickness was reduced from 11 µm to less than 4 µm.     

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.     

CdTe-CdS solar cells — Production in a new baseline and investigation of material properties

In this paper, we describe our new baseline for CSS-CdTe-CdS solar cells on 10 × 10 cm² substrates. The deposition of the p-n junction and all the following steps were performed at the Institut für Festkörperphysik (IFK) in Jena. Using the new baseline, we are already able to produce solar cells with similar properties as commercial ones. In the batch type process, all manufacturing steps can be investigated separately. We employ Rutherford backscattering spectrometry (RBS), X-ray diffraction (XRD) and external quantum efficiency (EQE) measurements to characterise the structure of the bulk materials and interfaces. It is demonstrated that by RBS the front contact becomes accessible for thinned CdTe films. At the back contact, RBS spectra show a tellurium accumulation which is due to etching. This tellurium rich layer is confirmed by XRD with Rietveld refinement. The intermixing at the CdS-CdTe interface caused by the activation step is quantified by a bandgap determination based on EQE measurements. From the bandgap energy of the CdTe_1 − xS_x compound, we calculated the sulphur fraction x at the interface. XRD measurements imply that the activation step induces a (111) texture in CdTe. With regard to an improved manufacturing process, our cells are compared to industrial cells produced by Antec Solar Energy.     

Characterization of CBD-CdS layers with different S/Cd ratios in the chemical bath and their relation with the efficiency of CdS/CdTe solar cells

In previous papers we have reported the improvement of the efficiency of CdS/CdTe solar cells by varying the thiourea/CdCl₂ ratio (R_tc) in the chemical bath solution used for the deposition of the CdS layers. In this work, a more complete study concerning the physical properties of Chemical Bath Deposited (CBD) CdS layers studied by photoluminescence, X-ray diffraction and optical spectroscopy are correlated to the I-V characteristics under AM 1.5 sunlight and the spectral response of CdS/CdTe solar cells. It is confirmed that the optimum R_tc for the CBD CdS films is R_tc = 5, since in this case the best solar cells were obtained and these films show the better optical and structural characteristics.     

Microstructural features of cadmium telluride photovoltaic thin film devices

In order to study the microstructure of cadmium telluride (CdTe) photovoltaic thin film solar cells, manufactured by an in-line manufacturing process, Scanning Electron Microscopy characterization (SEM) and X-ray diffraction (XRD) characterization were performed. SEM measurement showed that no substantial changes in the grain structure of CdTe layers occurred during the Cadmium Chloride (CdCl₂) treatment. No change in the cubic CdTe lattice parameter “a” was observed for the CdCl₂ treated sample. It is inferred that the primary effect of the CdCl₂ treatment in the devices studied is the passivation of grain boundaries and bulk defects. XRD studies show a loss of preferred orientation (as determined from the peak ratios) of planes during the copper compound treatment indicating recrystallization of the grains due to the Cu treatment. Also the Cu treated sample showed decrease in value of the lattice parameter “a”.     

Photoluminescence studies of CdTe films and junctions

Device quality CdTe films and junctions have been studied using low-temperature photoluminescence (PL) measurements. The behavior of the PL was studied as a function of the measurement temperature and excitation intensity. The CdTe films and junctions were prepared under various deposition conditions to determine the effect of film deposition and solar cell fabrication parameters, such as the effect of oxygen, and chloride treatment. A PL band located at 1.232 eV has been attributed to the presence of oxygen. This band is present only in as-deposited samples excited at the CdTe surface. Samples annealed in the presence of CdCl₂ exhibit a single PL band located at 1.42 eV. A model explaining the behavior of these bands is presented.     

Solution-processed sintered nanocrystal solar cells via layer-by-layer assembly

Solar cells made by high temperature and vacuum processes from inorganic semiconductors are at a perceived cost disadvantage when compared with solution-processed systems such as organic and dye-sensitized solar cells. We demonstrate that totally solution processable solar cells can be fabricated from inorganic nanocrystal inks in air at temperature as low as 300 °C. Focusing on a CdTe/ZnO thin-film system, we report solar cells that achieve power conversion efficiencies of 6.9% with greater than 90% internal quantum efficiency. In our approach, nanocrystals are deposited from solution in a layer-by-layer process. Chemical and thermal treatments between layers induce large scale grain formation, turning the 4 nm CdTe particles into pinhole-free films with an optimized average crystallite size of ～70 nm. Through capacitance-voltage measurements we demonstrate that the CdTe layer is fully depleted which enables the charge carrier collection to be maximized.     

硝磷酸腐蚀对CdTe薄膜性能及背接触层的影响

采用硝磷酸(NP)背表面刻蚀工艺并结合真空共蒸发法分别沉积了几种背接触层材料,研究了NP腐蚀对CdTe薄膜性能及背接触层的影响.结果表明:NP腐蚀后在CdTe薄膜上产生了富碲层;退火后,碲容易与背接触材料中的铜反应生成CuxTe.通过严格控制和优化腐蚀工艺,选择ZnTe/ZnTe:Cu作为背接触层材料,可制备出优异性能的CdTe太阳电池.     

Effect of interdiffusion and impurities on thin film CdTe/CdS photovoltaic junctions

We have used low temperature photoluminescence (PL) to study thin film CdTe/CdS solar cell structures. The devices were produced by close space sublimation (CSS) and have undergone a post-growth treatment, a vital step in increasing device efficiency. The treatment consisted of evaporating a thin layer of CdCl₂ onto the back CdTe surface and heat treating in air at 400 °C for between 10 and 120 min. This produced a range of device efficiencies from 2% to 9%. The efficiency improvements are the result of a complex interaction between the CdCl₂, impurities and sulfur interdiffusion. The structures were prepared for PL by a chemical bevel etching technique which allows the luminescence emission to be studied as a function of depth throughout the sample. The main features in the PL spectra have been identified as being due to the Cl-A center and the Te-dislocation-related Y luminescence band. Using PL we have quantified the S diffusion into the CdTe which has a maximum of 20% at the interface in the most efficient samples. We have also obtained the profiles of recombination and non-radiative recombination centers in the device. We observe correlations between impurity centers and device efficiency which can help explain the effects of the CdCl₂ treatment on the optoelectronic properties of the CdTe/CdS junction.     

Development of low temperature approaches to device quality CdS: A modified geometry for solution growth of thin films and their characterisation

Cadmium sulphide thin films have been grown using a modified chemical bath deposition method with four innovative features: i) ethylenediamine was used as the complexing agent, enabling the use of low cadmium concentrations, ii) a rectangular bath geometry with heated glass plate walls was employed, iii) a low deposition temperature (30 °C) was used and iv) nitrogen gas was flowed over the substrate surface during growth. The latter two features eliminate the formation and adherence of gas bubbles on the substrate during growth, hence reducing pinhole formation. On inspection, films were found to be specularly reflective and homogeneous with no visible pinholes. Characterisation was performed by atomic force microscopy, grazing incidence X-ray diffraction, optical transmittance and photoluminescence spectroscopy. It was shown that films possessed a low surface roughness value of 5.2 nm, were highly crystalline, textured, had a grain size of 15 nm and a bandgap of 2.42 eV. Preliminary results from CdTe/CdS thin film photovoltaic devices demonstrate a notable efficiency of 9.8%.     

Effects of junction formation conditions on the photovoltaic properties of sintered CdS/CdTe solar cells

Microstructures and properties of sintered CdS films on glass substrates and sintered CdTe films on polycrystal CdS substrates have been investigated. The CdS films, which contained 9 wt % CdCl₂ as a sintering aid and were sintered at 650° C for 1 h in nitrogen, are transparent and have an average grain size of 15m and an electrical resistivity of 0.5cm. The CdTe films, which were coated on the sintered CdS substrate and were sintered above 610° C for 1 h in nitrogen, have a dense structure with an average grain size larger than 5m. All polycrystal CdS/CdTe solar cells were fabricated by this successive coating and sintering method. The sintering temperature of CdTe films on the sintered CdS films was varied from 585 to 700° C. Compositional interfaces and p-n juctions are formed during sintering. The highest solar efficiency (7.18%) was found in a solar cell made by sintering the composite layer of glass-CdS-CdTe at 625° C for 1 h. A fabrication temperature below 610° C resulted in poor solar cell efficiencies due to the porous structure of the CdTe films and above 650° C also resulted in poor efficiencies due to the formation of a CdS_1-x Te_x layer at the interface and a large p-n junction depth.     

A microstructural study on the surface and interface of CdTe/CdS solar cells

The surface and interface properties of CdTe/CdS solar cells, including interfacial mixing, surface and interface geometrical morphology, CdTe grain size and preferential crystal orientation of CdTe layers were studied using Auger electron spectroscopy (AES) depth profiling, atomic force microscopy (AFM), Fourier transform infrared (FTIR) spectroscopy, optical reflectance (OR) and X-ray diffraction (XRD) techniques. The correlation between the surface and interface properties and CdTe/CdS solar cell performance was also investigated. AES depth profiling was used to analyse the interdiffusion between the CdTe and CdS layers. Atomic force microscopy (AFM) suggests that the interfacial geometrical morphology has a significant influence on the photovoltaic property of CdTe/CdS solar cells. Rough interfaces tend to increase the photovoltaic conversion efficiency of solar cells because of multiple reflections. X-ray diffraction shows that polycrystalline CdTe/CdS solar cells with higher efficiencies appear to be orientated with more (1 1 1) planes of CdTe parallel to the macrosurface, but CdTe single crystals with differently indexed surface planes show almost the same reflection behaviour. Further theoretical and experimental analyses are therefore needed to clarify this observation. This revised version was published online in July 2006 with corrections to the Cover Date.     

Effects of CdCl2 in CdTe on the properties of sintered CdS/CdTe solar cells

Sintered CdS films on glass substrates with low electrical resistivity and high optical transmittance have been prepared by a coating and sintering method. All-polycrystalline CdS/CdTe solar cells with different microstructures and properties of the CdTe layer were fabricated by coating a number of CdTe slurries, which consisted of cadmium and tellurium powders, an appropriate amount of propylene glycol and various amounts of CdCl₂, on the sintered CdS films and by sintering the glass-CdS-(Cd + Te) composites at various temperatures. The presence of more than 5 wt% of CdCl₂ in the (Cd + Te) layer enhances the sintering of the CdTe film and the junction formation by a liquid-phase sintering mechanism. A low sintering temperature results in poor densification of the CdTe layer and the CdS-CdTe interface, whereas a high sintering temperature results in a deeply buried homojunction. The optimum temperature for the sintering of the CdTe layer and for junction formation decreases with increasing amount of CdCl₂. All-polycrystalline CdS/CdTe solar cells with an efficiency of 10.2% under solar irradiation have been fabricated by a coating and sintering method using cadmium and tellurium powders for the CdTe layer.