CuGaSe2 solar cells using atomic layer deposited Zn(O,S) and (Zn,Mg)O buffer layers

The band gap of Zn(O,S) and (Zn,Mg)O buffer layers are varied with the objective of changing the conduction band alignment at the buffer layer/CuGaSe₂ interface. To achieve this, alternative buffer layers are deposited using atomic layer deposition. The optimal compositions for CuGaSe₂ solar cells are found to be close to the same for (Zn,Mg)O and the same for Zn(O,S) as in the CuIn_0.7Ga_0.3Se₂ solar cell case. At the optimal compositions the solar cell conversion efficiency for (Zn,Mg)O buffer layers is 6.2% and for Zn(O,S) buffer layers it is 3.9% compared to the CdS reference cells which have 5-8% efficiency.     

CuInS2-based thin film solar cells with sputtered (Zn,Mg)O buffer

In a standard chalcopyrite-based thin film solar cell, the formation of the heterojunction is mediated by a thin buffer layer. This buffer is prepared by chemical bath deposition of CdS. The cell is completed by an undoped ZnO film followed by the highly doped transparent front contact. An alternative structure without any buffer layer where the undoped ZnO is replaced by (Zn,Mg)O has been suggested previously by Minemoto et al. [T. Minemoto, Y. Hashimoto, T. Satoh, T. Negami, H. Takakura, Y. Hamakawa, J. Appl. Phys. 89 (2001) 8327]. By adapting and applying this approach to CuInS₂ absorbers from industrial pilot production we achieved efficiencies of 8% for small area cells (as compared to 9.4% for a reference cell with CdS buffer) as well as monolithically integrated test structures.     

Optimization of ALD-(Zn,Mg)O buffer layers and (Zn,Mg)O/Cu(In,Ga)Se2 interfaces for thin film solar cells

(Zn,Mg)O films, fabricated by atomic layer deposition, ALD, are investigated as buffer layers in Cu(In,Ga)Se₂-based thin film solar cells. Optimization of the buffer layer is performed in terms of thickness, deposition temperature and composition. High efficiency devices are obtained for deposition at 105-135 °C, whereas losses in open circuit voltage are observed at higher deposition temperatures. The optimal compositional region for (Zn,Mg)O buffer layers in this study is for Mg/(Zn + Mg) contents of about 0.1-0.2, giving band gap values of 3.5-3.7 eV. These devices appear insensitive to thickness variations between 80 and 600 nm. Efficiencies of up to 16.2% are obtained for completely Cd- and S-free devices with (Zn,Mg)O buffer layers deposited with 1000 cycles at 120 °C and having a band gap of 3.6 eV.     

In situ monitoring the growth of thin-film ZnS/Zn(S,O) bilayer on Cu-chalcopyrite for high performance thin film solar cells

This paper highlights the crucial role that the control of the chemical bath deposition (CBD) process plays for buffer production of Cu-chalcopyrite solar-cell devices. ZnS/Zn(S,O) bilayer was deposited on CuInS₂ (CIS) and Cu(In,Ga)(SSe)₂ (CIGSSe) and monitored using turbidity measurements of the solution. The results were correlated to the X-ray photoemission spectra of the samples obtained by interruption of the process at sequential stages. Two different feature regimes were distinguished: In the first stage, a heterogeneous reaction takes place on the absorber resulting in the formation of pure ZnS. The second stage of the process is homogeneous, and the in-situ turbidity measurement shows a loss in the transmission of light through the CBD solution. The measured ZnL3M45M45 Auger-peaks, during this second stage of the process, show a shift of the kinetic energy from pure ZnS to a solid-solution ZnS/ZnO (“Zn(S,O)”) with decreasing amount of sulfur. These results are supported by the observations from Energy-filtered transmission electron microscopy. This paper also demonstrates that monitoring of the CBD process combined with the basic understanding using surface and interface analysis have contributed to improve the reproducibility and to enhance the photovoltaic performance of Cu-chalcopyrite thin-film solar modules.     

Cu-accumulation at the interface between sputter-(Zn,Mg)O and Cu(In,Ga)(S,Se)2 — A key to understanding the need for buffer layers?

Zn_0.85Mg_0.15O buffer layers can replace both i-ZnO and CdS in n-ZnO/i-ZnO/CdS/Cu(In_xGa_1 − x)(S_ySe_1 − y)₂/Mo/glass (CIGSSe) solar cells without significant loss of efficiency. We found that the efficiency of Zn_0.85Mg_0.15O buffered solar cells decreased with increasing sample temperature when we sputter-deposited Zn_0.85Mg_0.15O directly onto the CIGSSe absorber surface, e.g. from 9.5% without deliberate heating to 6.5% at 240 °C. To find an explanation for this behavior we sputter-coated bare, KCN-etched CIGSSe absorbers with about 420 nm of Zn_0.85Mg_0.15O at different sample temperatures and subsequently removed the Zn_0.85Mg_0.15O layers by wet-chemical etching with dilute acetic acid. The exposed CIGSSe surfaces were examined by surface-sensitive X-ray photoelectron spectroscopy (XPS) and X-ray excited Auger electron spectroscopy (XAES). We found a strong increase in the [Cu]/([In] + [Cu]) ratio compared to a bare, Acetic-acid-etched CIGSSe reference. The surface of samples that had been sputter-coated at 150 °C changed from being initially Cu-poor to Cu-rich. The chemical shift of Cu Auger peaks from the same surface confirmed this finding. The increased Cu/In ratio and the chemical shift were reversed after KCN etch. These findings are discussed in the context of the model of a Cu-depleted, wide-band gap surface region in CIGSSe solar cells as a prerequisite for high efficiency.     

Cu(In,Ga)Se2 solar cells with double layered buffers grown by chemical bath deposition

In based mixture In_x(OH,S)_y buffer layers deposited by chemical bath deposition technique are a viable alternative to the traditional cadmium sulfide buffer layer in thin film solar cells. We report on the results of manipulating the absorber/buffer interface between the chalcopyrite Cu(In,Ga)Se₂ (CIGS) absorber and CdS or ZnS buffer by addition of a thin In based mixture layer. It is shown that the presence of thin In_x(OH,S)_y at the CIGS absorber/CdS or ZnS buffer interfaces greatly improve the solar cell performances. The performances of CIGS cells using dual buffer layers composed of In_x(OH,S)_y/CdS or In_x(OH,S)_y/ZnS increased by 22.4% and 51.6%, as compared to the single and standard CdS or ZnS buffered cells, respectively.     

Influence of absorber copper concentration on the Cu(In,Ga)Se2/(PVD)In2S3 and Cu(In,Ga)Se2/(CBD)CdS based solar cells performance

The present contribution deals with the influence of the copper concentration in Cu(In,Ga)Se₂ (CIGSe) on the solar cells based on CIGSe/(PVD)In₂S₃ and CIGSe/(CBD)CdS. We find that, depending on the buffer layer, the optimum open circuit voltage (Voc) is not reached for the same copper concentration. The values of Voc for the CIGSe/(CBD)CdS solar cells are higher when the copper content is very close to stoichiometry (25%), whereas, the Voc values for CIGSe/(PVD)In₂S₃ solar cells attain their maximum for lower copper contents. On the other hand, contrary to the case of the (CBD)CdS buffer, the Jsc is strongly hindered for the (PVD)In₂S₃ buffered cells when the copper content is lowered. The study has been made for different absorber gallium contents and the evolution is coherent with the presence of a cliff at the CIGSe/(PVD)In₂S₃ interface.     

Element-specific electronic structure of Mn dopants and ferromagnetism of (Zn,Mn)O thin films

Element-specific electronic structure of (Zn,Mn)O thin films with various Mn concentrations has been investigated using X-ray absorption and emission spectroscopy. According to comparison between the experimental spectra and the density functional theory calculations (partial density of states and exchange interactions for various Mn defect configurations), the substitutional Mn impurities do not induce ferromagnetism in (Zn,Mn)O samples. The ferromagnetic properties can be obtained when defect configurations consisting of both substitutional and interstitial Mn atoms are present. The ferromagnetism in ZnO-based magnetic semiconductors is favored to be Ruderman-Kittel-Kasuya-Yoshida type and the established theoretical model is in a good agreement with the X-ray spectroscopic measurements.     

CIGS thin films, solar cells, and submodules fabricated using a rf-plasma cracked Se-radical beam source

Coevaporated Cu(In,Ga)Se₂ (CIGS) film growth using a rf-plasma cracked Se-radical beam (R-Se) source leads to a significant reduction in the amount of raw Se source material wasted during growth and exhibits unique film properties such as highly dense, smooth surfaces and large grain size. R-Se grown CIGS solar cells also show concomitant unique properties different from conventional evaporative Se (E-Se) source grown CIGS cells. In the present work, the impact of modified surfaces, interfaces, and bulk crystal properties of R-Se grown CIGS films on the solar cell performance was studied. When a R-Se source was used, Na diffusion into CIGS layers was enhanced while a remarkable diffusion of elemental Ga and Se into Mo back contact layers was observed. Improvements in the bulk crystal quality as manifested by large grain size and increased Na concentration with the use of a R-Se source is expected to be effective to improve photovoltaic performance. Using a R-Se source for the growth of CIGS absorber layers at a relatively low growth temperature, we have successfully demonstrated a monolithically integrated submodule efficiency of 15.0% (17 cells, aperture area of 76.5 cm²) on 0.25-mm thick soda-lime glass substrates.     

Bulk and interface properties of (Zn,Mg)O buffer layers sputtered in hydrogen-containing atmosphere

Sputtered (Zn,Mg)O buffer layers are one of the few promising options for completely dry and cadmium-free manufacturing of chalcopyrite-based solar cells. The performance of a heterojunction solar cell depends critically on the electrostatic charge contained in the interface. In chalcopyrite-based cells this charge can be influenced by redox treatments. In this work we have added hydrogen to the working gas when sputtering the buffer layer in an effort to optimize the interface charge. We report on the unexpectedly complex effects even at low hydrogen flow. They include a reduced deposition rate, significantly altered diffractograms and higher Mg/Zn-ratio in the film. X-ray photoelectron spectroscopy reveals the deposition of a thin layer of metallic zinc in the initial deposition stage which is not observed in the absence of hydrogen. Small hydrogen concentrations appear to be beneficial in terms of cell performance and reproducibility. However, higher concentrations typically cause a loss in blue response which indicates the formation of a homojunction buried within the chalcopyrite absorber.     

Zn(MAA)_2和Mg(MAA)_2用量对NBR/EPDM基柔性绝热层材料力学和烧蚀性能的影响(英文)

将少量Zn(MAA)2和Mg(MAA)2分别添加到EPDM/NBR橡胶中制成柔性绝热层材料,分别研究了其各自用量对绝热层材料交联密度、拉伸强度、断裂伸长率、硬度、密度和烧蚀速率等的影响。结果显示:随着Zn(MAA)2或Mg(MAA)2用量增加,绝热层材料的交联密度、拉伸强度、密度等均呈现增大趋势,而材料的硬度基本不变;沿纤维方向上绝热层的断裂伸长率先增加后降低,均在用量为3phr时出现最大值,而垂直于纤维方向上Zn(MAA)2增强的绝热层其断裂伸长率急剧下降,Mg(MAA)2增强的绝热层则缓慢下降;与Zn(MAA)2增强体系相比,Mg(MAA)2增强体系的交联密度、断裂伸长率均明显高于前者,材料密度、线烧蚀速率和质量烧蚀速率则低于前者,是柔性绝热层材料获得高伸长率、低烧蚀速率的理想添加剂;综合考虑绝热层材料的各项性能,Mg(MAA)的最佳用量以2～4phr为宜。     

Alternative sodium sources for Cu(In,Ga)Se2 thin-film solar cells on flexible substrates

Sodium (Na) is an important doping element for Cu(In,Ga)Se₂ (CIGS) solar cells. However, when using Na-free flexible substrates like steel foil or polyimide film, it is necessary to ensure an efficient supply of sodium to achieve high cell efficiencies. The common incorporation methods for Na on these Na-free substrates are either to deposit a Na-containing precursor layer (e.g. NaF) onto the molybdenum (Mo) back contact prior to CIGS growth or to coevaporate a Na compound during CIGS growth. Another way is to incorporate sodium after CIGS growth by a post-deposition treatment with NaF. In this work, we tested two alternative Na doping methods which are well suited for a production line due to their easy controllability. One approach is to dope the molybdenum target with Na. With Na-doped Mo layers (Mo:Na) as the back contact, we could achieve efficiencies of 13.1% both on titanium (Ti) and stainless Cr steel foil using a single-stage inline CIGS process. With a low-temperature single-stage CIGS process on polyimide (PI) we reached an efficiency of 11.2% using a Mo:Na back contact. Another doping method involves sol-gel-deposited silicon oxide layers which contain Na (SiO_x:Na). We have successfully deposited these sol-gel layers onto stainless steel foil by a roll-to-roll (R2R) method with short annealing times as needed in production. With these SiO_x:Na layers we could achieve efficiencies of 13.7% on stainless steel foil and 11.5% on mild steel sheet using a single-stage inline CIGS process.     

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.     

Structural and chemical analyses of sputtered InxSy buffer layers in Cu(In,Ga)Se2 thin-film solar cells

Sputtered In_xS_y layers deposited on borosilicate glass and Si at substrate temperatures ranging from about 60 °C to 340 °C were analyzed by means of X-ray diffraction, energy-dispersive X-ray spectrometry, and optical transmission and reflection measurements. With increasing substrate temperature, the In_xS_y layers exhibit increasing sulfur concentration and also increasing absorption-edge energies. In_xS_y layers on Cu(In,Ga)Se₂(CIGS)/Mo/glass stacks were additionally studied by scanning and transmission electron microscopy. With increasing substrate temperature, Cu, Ga, and In interdiffusion between CIGS and In_xS_y becomes more enhanced. At 340 °C, CuIn₅S₈ forms instead of In_xS_y. The CuIn₅S₈ formation at elevated temperatures may be the reason for the very low efficiency of solar cells with indium sulfide buffers deposited at temperatures above about 250 °C by various techniques.     

Comparative study of Cu(In,Ga)Se2/(PVD)In2S3 and Cu(In,Ga)Se2/(CBD)CdS heterojunction based solar cells by admittance spectroscopy, current-voltage and spectral response measurements

Co-evaporated Cu(In,Ga)Se₂ (CIGSe) based solar cells with Physical Vapour Deposited (PVD) Indium Sulphide (In₂S₃) as buffer layer have been studied by admittance spectroscopy and current-voltage characteristics measurements. The results have been compared to those obtained with a reference CBD-CdS/CIGSe device. In darkness, the PVD-In₂S₃ buffer layer devices exhibit higher densities of trapping defects and low values of shunt resistance. However, under illumination we have observed an important improvement of the In₂S₃/CIGSe electronic transport properties. This behavior seems to be linked to the presence of a metastable defect with activation energy of 0.3 eV.     

Evaluation of electron beam induced current profiles of Cu(In,Ga)Se2 solar cells with different Ga-contents

The measurement of electron beam induced current profiles in junction configuration (JEBIC) is a settled method for several semiconductor devices. We discuss the JEBIC method in the light of the special conditions present in the case of thin film Cu(In,Ga)Se₂ solar cells.Our previously published results indicate that the charge state of defects close to or at the Cu(In,Ga)Se₂/CdS interface depends on the minority carrier distribution, which changes strongly during a scan of the cross section with an electron beam. The charge distribution influences the electrostatic potential and therewith the collection of minority carriers.Here, we present an evaluation method of JEBIC profiles that accounts for this effect. Monte Carlo simulations of the carrier generation help us to consider in detail the influence of surface recombination. We determine the diffusion length, space charge width, surface- and back contact recombination velocity of Cu(In_(1-r),Ga_r)Se₂ devices with different Ga-contents r from JEBIC line scans.     

细晶铈、镁复合稳定PSZ陶瓷的制备及性能研究

以工业ZrO2为主要原料,CeO2,MgO及α－Al2O3作为复合稳定剂及颗粒添加剂,采用机械球磨混合法制备粉料,进而在较低的固溶烧结温度（≤1550℃）下,经1100℃适当时间热处理,制备出具有较好力学性能的细晶PSZ陶瓷材料,其室浊度约655MPa,断裂韧性在15MPa.m^1/2左或,所制备细晶PSZ材料的临界热震温差△Tc在750℃左右,其中微裂纹增韧机制的存在对材料的抗热震性有积极作用,在（180℃,1MPa）水热条件下,采用CeO2作为复合稳定剂的PSZ陶瓷材料具有较好的抗水化性能。     

Effect of Reaction Temperature and Time on the Structural Properties of Cu（In,Ga）Se2 Thin Films Deposited by Sequential Elemental Layer Technique

Thin films of copper indium gallium selenide Cu（In,Ga）Se2 （CIGS） were prepared by sequential elemental layer deposition in vacuum at room temperature. The as-deposited films were heated in vacuum for compound formation, and were studied at temperature as high as 1250℃ for the first time. These films were concurrently studied for their structural properties by X-ray diffraction （XRD） technique. The XRD analyses include phase transition studies, grain size variation and microstrain measurements with the reaction temperature and time.It has been observed that there are three distinct regions of variation in all these parameters. These regions belong to three temperature regimes： 〈450℃, 450-950℃, and 〉950℃. It is also seen that the compound formation starts at 250℃, with ternary phases appearing at 350℃ or above. Whereas, there is another phase shift at 950℃ without any preference to the quaternary compound.     

铁氧体Ba(Zn0.65CO0.35)2Fe16O27/环氧树脂复合材料板吸波性能与优化

首先采用化学共沉和高温助熔工艺制备铁氧体Ba(Zn0.65CO0.35)2 Fe16O27粉体,用手糊工艺制备铁氧体/M-玻璃纤维/环氧树脂复合材料板,再用波导法测定复合材料的电磁参数.研究表明当铁氧体Ba(Zn0.65CO0.35)2 Fe16O(27)含量不变时,复合材料板的吸波性能随板厚度的增加而提升,且试样反射...     

Performance of CuIn1 − xGaxSe2/(PVD)In2S3 solar cells versus gallium content

The present work studies the influence of the Ga content (x = Ga / (Ga + In)) in the absorber on the solar cell performance for devices using (PVD)In₂S₃-based buffers. Input to the hypothesis of the relative conduction band positions can be found in the evolution of the device parameters with x. For experiments with x between 0 and 0.5 devices using (PVD)In₂S₃-based buffers are compared to reference devices using (CBD)CdS. Both buffers give similar cell characteristics for narrow band gap absorbers, typically E_gCIGSe < 1.1 eV. However, the parameters of the cells buffered with (PVD)In₂S₃ are degraded when the absorber gap is widened whereas (CBD)CdS reference devices are only slightly affected. Consequently, the solar cell efficiency is similar for both buffer layers at the lower x values and increases with x only in the case of (CBD)CdS. These evolutions are coherent with the existence of a conduction band cliff at the CIGSe/(PVD)In₂S₃ interface.