Growth mechanism of thermally processed Cu(In,Ga)S2 precursors for printed Cu(In,Ga)(S,Se)2 solar cells

We investigate a process used for the selenisation of particle‐based precursors to prepare low‐cost Cu(In,Ga)(S,Se)₂ (CIGS) solar cells. It is suitable for high throughput with a short optimum selenisation duration of 3–5 min and employs a rapid thermal annealing system with elemental selenium vapour. Homogeneous crack‐free Cu(In,Ga)S₂ precursor films of up to 1 µm are obtained via doctor blading. The high selenium vapour pressure in the selenisation reaction chamber results in the formation of a compact Cu(In,Ga)(S,Se)₂ layer on top of a carbon‐rich underlayer. In order to investigate the phase development in the film, the selenisation process was interrupted at different stages and the samples were monitored via XRD and surface‐sensitive Raman measurements. We find the formation of a polycrystalline Cu(In,Ga)Se₂ phase already after 1 s at the target temperature of 550 °C. Furthermore, the effect of initial precursor thickness on solar cell parameters is discussed. Complete solar cells are prepared by conventional methods, leading to conversion efficiencies well above 8%. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

电沉积Cu(In,Ga)Se_2预置层硫化退火制备Cu(In,Ga)(Se,S)_2薄膜及表征

在550℃下的H2S气氛中退火处理电沉积制备的Cu(In,Ga)Se2(CIGS)预置层,制备了太阳电池光吸收层Cu(In,Ga)(Se,S)2(CIGSS)薄膜.采用X射线能量色散谱、俄歇电子能谱、扫描电镜、X射线衍射和拉曼光谱对退火前后的薄膜进行表征.结果表明,H2S气氛下退火能够实现薄膜中O的去除和S的掺入,同时使得各元素的纵向分布更加均匀并可消除Cu-Se微相.此外,H2S退火还可改善薄膜的结晶性能,并使S和Ga进入黄铜矿结构,薄膜晶格参数变小.     

Excitons in PL Spectra of Cu(In,Ga)Se2 Single Crystals

Physics of the Solid State - A photoluminescence (PL) study of Cu(In,Ga)Se2 (CIGSe) single crystals, (grown by the vertical Bridgman technique) with the [Ga]/[Ga + In] ratio of 7 and 12% and the...     

Effect of CdS deposition temperature for thermally grown Cu(In,Ga)Se2 and two-step chalcogenized Cu(In,Ga)(S,Se)2 absorbers on solar cell performances

CdS buffer layer of varying thickness ranging from 23 to 58 nm deposited at different substrate temperature were prepared as n-type junction partner for thermally grown Cu(In,Ga)Se₂ and two-step chalcogenized Cu(In,Ga)(S,Se)₂ photovoltaic absorber films and the effect of deposition temperature and time on the CdS growth behavior and solar cell performance were evaluated. High deposition temperature resulted in a thicker CdS layer and more importantly lower density and shallower depth of open voids, which attributed to the improved open-circuit voltage and fill factor due to reduced interface recombination. The solar cell efficiency of thermally grown absorber saturated at about 30 nm thickness of CdS, while that of chalcogenized absorber gradually increased with CdS thickness up to 60 nm without significant loss of short-circuit current density.     

Cu(In,Ga)Se2太阳能电池快速热退火效应

利用光致发光（PL）分析快速热退火对Cu(In,Ga)Se2 (CIGS)电池的影响,研究退火对薄膜缺陷的影响。Cu(In,Ga)Se2电池的PL谱中总共有 7个峰,即2个可见波段峰和5个红外波段峰。退火温度较低,可减少薄膜体内缺陷,提高载流子浓度,改善薄膜质量;退火温度过高,则会引起正常格点处元素扩散,元素化学计量比改变,体内缺陷增加,吸收层带隙降低,反而会对CIGS薄膜造成破坏。     

Performance improvement of CdS/Cu（In,Ga）Se2 solar cells after rapid thermal annealing

In this paper, we investigated the effect of rapid thermal annealing (RTA) on solar cell performance. An opto-electric conversion efficiency of 11.75% (Voc=0.64 V, Jsc = 25.88mA/cm2 , FF=72.08%) was obtained under AM 1.5G when the cell was annealed at 300℃ for 30s. The annealed solar cell showed an average absolute efficiency 1.5% higher than that of the as-deposited one. For the microstructure analysis and the physical phase confirmation, X-ray diffraction (XRD), Raman spectra, front surface reflection (FSR), internal quantum efficiency (IQE), and X-ray photoelectron spectroscopy (XPS) were respectively applied to distinguish the causes inducing the efficiency variation. All experimental results implied that the RTA eliminated recombination centers at the p-n junction, reduced the surface optical losses, enhanced the blue response of the CdS buffer layer, and improved the ohmic contact between Mo and Cu(In, Ga)Se2 (CIGS) layers. This leaded to the improved performance of CIGS solar cell.     

衬底对Cu(In,Ga)Se2薄膜织构的影响

分别在苏打石灰玻璃、Mo箔、无择优取向的Mo薄膜以及(110)择优取向的Mo薄膜四种不同衬底上,采用共蒸发工艺沉积约2μm厚的Cu(In,Ga)Se2薄膜,用X射线衍射仪测量薄膜的织构,研究衬底对Cu(In,Ga)Se2薄膜织构的影响.在以上四种衬底上沉积的Cu(In,Ga)Se2薄膜的(112)衍射峰强度依次逐渐减弱,(220/204)衍射峰从无到有且强度逐渐增强.在苏打石灰玻璃和Mo箔衬底上的Cu(In,Ga)Se2薄膜具有明显的(112)择优生长,而在(110)取向的Mo薄膜衬底上,Cu(In,Ga)Se2薄膜的织构为(220/204)取向.研究结果表明,只有(110)择优取向的Mo薄膜衬底对Cu(In,Ga)Se2薄膜(220/204)织构的形成有重要影响.     

Influence of Ga/(Ga + In) grading on deep‐defect states of Cu(In,Ga)Se2 solar cells

The benefits of gallium (Ga) grading on Cu(In,Ga)Se₂ (CIGS) solar cell performance are demonstrated by comparing with ungraded CIGS cells. Using drive‐level capacitance profiling (DLCP) and admittance spectroscopy (AS) analyses, we show the influence of Ga grading on the spatial variation of deep defects, free‐carrier densities in the CIGS absorber, and their impact on the cell's open‐circuit voltage V_oc. The parameter most constraining the cell's V_oc is found to be the deep‐defect density close to the space charge region (SCR). In ungraded devices, high deep‐defect concentrations (4.2 × 10¹⁶cm^–3) were observed near the SCR, offering a source for Shockley–Read–Hall recombination, reducing the cell's V_oc. In graded devices, the deep‐defect densities near the SCR decreased by one order of magnitude (2.5 × 10¹⁵ cm^–3) for back surface graded devices, and almost two orders of magnitude (8.6 × 10¹⁴ cm^–3) for double surface graded devices, enhancing the cell's V_oc. In compositionally graded devices, the free‐carrier density in the absorber's bulk decreased in tandem with the ratio of gallium to gallium plus indium ratio GGI = Ga/(Ga + In), increasing the activation energy, hindering the ionization of the defect states at room temperature and enhancing their role as recombination centers within the energy band. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Defect generation in polycrystalline Cu(In,Ga)Se2 by high-energy electron irradiation

We investigate the degradation of ZnO/CdS/ Cu(In,Ga)Se₂ heterojunction solar cells for space applications and the defect generation in polycrystalline Cu(In,Ga)Se₂ thin films by irradiation with 1-MeV electrons with fluences J_e up to J_e=5᎒¹⁸ cm^-2. Notable degradation of the solar cell performance starts at fluences of J_e=10¹⁷ cm^-2 where the open circuit voltage decreases by about 5% while short circuit current and fill factor remain essentially unaffected. Thus, Cu(In,Ga)Se₂ solar cells withstand electron fluences which are higher by one order of magnitude or more when compared to other technologies. A model describes the absolute open circuit voltage loss considering the increase of space charge recombination by electron irradiation-induced defects. Defect analysis by admittance spectroscopy shows that acceptor defects with an energy distance of approximately 300 meV from the valence band are generated at a rate %=0.017 (ǂ.01) cm^-1.     

Photoelectric properties of In/p-(Cu, Ag)Ga(Se, Te)2 surface-barrier structures

Based on single crystals of AgGaSe₂, AgGaTe₂, CuGaTe₂ of the p-type, surface-barrier structures were manufactured by vacuum thermal deposition on illumination of which the photovoltaic effect was observed. It is established that the longwave edge of the photosensitivity of such structures possesses several inflections attributable to photoactive absorption involving paracipation of levels of lattice defects. It is shown that In/p-(Cu, Ag)Ga(Se, Te)₂ surface-barrier structures can be used as wide-band transducers and photoanalyzers of linearily polarized radiation. Translated from Zhurrnal Prikladnoi Spektroskopii, Vol. 66, No. 1, pp. 141–144, January–February, 1999.     

Enhancements in specimen preparation of Cu(In,Ga)(S,Se)2 thin films

When producing slices from Cu(In,Ga)(S,Se)(2) thin films for solar cells by use of a focused ion beam (FIB), agglomerates form on the Cu(In,Ga)(S,Se)(2) surfaces, which deteriorate substantially the imaging and analysis in scanning electron microscopy. Similar problems are also experienced when depth-profiling Cu(In,Ga)(S,Se)(2) thin films by means of glow-discharge or secondary ion mass spectrometry. The present work shows that the agglomerates are composed of (mainly) Cu, and that their formation may be impeded considerably by either cooling of the sample or by use of reactive gases during the ion-beam sputtering. The introduction of XeF(2) during FIB slicing resulted in excellent images, in which the microstructures of most layers in the Cu(In,Ga)(S,Se)(2) thin film stack are visible, including the microstructure of the 20 nm thin MoSe(2) layer. Acquisition of high-quality two-dimensional and also three-dimensional electron backscatter diffraction data was possible. The present work gives a basis for enhanced SEM imaging and analysis not only in the case of Cu(In,Ga)(S,Se)(2) thin films but also when dealing with further material systems exhibiting similar formations of agglomerates.     

A new method of generating Ga slope in Cu(In,Ga)Se2 film by controlling Se content in a multi-stacked precursor

An appropriate Ga slope is required in Cu(In,Ga)Se₂ (CIGS) film to enhance the cell performance of CIGS thin-film solar cells. In the conventional three-stage-co-evaporation process, the Ga slope was obtained by controlling Ga/In flux during deposition process. However, in two-step process, where a precursor was deposited first and then annealed in a Se environment for mass production, the desirable Ga slope was not achievable with the Ga/In flux control. We observed that the Ga/(Ga + In) ratio was nearly flat in CIGS film for Se-rich precursor and the ratio was nearly zero at surface and very high on bottom side of CISG film for Se-deficient precursor. We were able to generate a CIGS film with a Ga non-zero Ga surface and desired slope in the bulk by devising a precursor with Se-rich layer on top and Se-deficient layer on bottom, resulting in the enhancement of Cell performance.     

Structural analysis of Cu(In,Ga)Se2 films fabricated by using sputtering and post-selenization

We made Cu(In,Ga)Se₂ (CIGS) films by using sputtering and post-selenization. First, we deposited stacked metallic films by using the sputtering method and then carried out post-selenization for the precursor stacked metals with different amounts of Se powder, 0.160 g, 0.321 g, 0.642 g, and 0.964 g. We found that with a small amount of Se, separated CuInSe₂ and CuGaSe₂ layers were formed, which was confirmed by X-ray diffraction (XRD), Raman spectroscopy, and energy-dispersive X-ray analysis. For larger Se amounts, the CIGS phase was observed in the results of XRD and Raman spectroscopy. These results indicate that the amount or the partial pressure of Se plays an important role in the reaction kinetics for stacked precursor metals to form the CIGS phase.     

Texture and electronic activity of grain boundaries in Cu(In,Ga)Se2 thin films

The influence of different film textures on the electronic properties of polycrystalline Cu(In,Ga)Se₂ absorbers is studied by measuring the laterally resolved optoelectronic properties of differently textured Cu(In,Ga)Se₂ films with Kelvin probe force microscopy and cathodoluminescence. The grain boundaries in (112)- and (220/204)-textured films behave differently. The work-function profile measured with the Kelvin probe across a grain boundary in (112)-textured films shows a dip indicating positive charges at the grain boundaries. In panchromatic cathodoluminescence mappings in a transmission electron microscope, such grain boundaries appear dark, i.e. the strongly reduced luminescence indicates that the grain boundaries represent strong non-radiative recombination centers. In contrast, grain boundaries in (220/204)-textured films give rise to a dip or a step in the work function indicating slightly negative charge or neutrality. Cathodoluminescence is reduced at such grain boundaries, but less dramatically than in the (112)-textured case. However, when Na is present in the (220/204)-textured films, the grain boundaries are almost invisible in cathodoluminescence mappings. This strong passivating action of Na occurs only in the (220/204)-textured films, due to a particular grain-boundary population. In (112)-textured films and films without pronounced texture, this passivation effect is much less noticeable. PACS 73.50.Gr; 73.61.Ga; 78.60.Hk; 87.64.Dt     

Diffusion of indium and gallium in Cu(In,Ga)Se2 thin film solar cells

The diffusion of indium and gallium in polycrystalline thin film Cu(In,Ga)Se₂ layers has been investigated. Bilayer structures of CuInSe₂ on top of CuGaSe₂ and vice versa have been fabricated in both a Cu-rich and Cu-poor process (in relation to the ideal stoichiometry). In each process molybdenum coated soda-lime glass with and without a sodium barrier was used. These bilayers were analyzed with secondary ion mass spectrometry, X-ray diffraction, scanning electron microscope and transmission electron microscope equipped with energy dispersive X-ray spectroscopy. It was found that the grain boundary diffusion was not significantly higher than the diffusion inside the grains, also for Cu-rich layers. The diffusion is suggested to mainly proceed via vacant metal sites in the lattice structure. In sodium free films a higher diffusion into the bottom layers, compared to films with sodium, was seen in all cases. This observation was explained with a larger number of vacancies, that facilitates indium and gallium diffusion, in the sodium free films. The difference in diffusion between indium in CGS layers and gallium in CIS layers, in both Cu-rich and Cu-poor processes, was small for layers with sodium.     

Junction configurations and their impacts on Cu(In,Ga)Se2 based solar cells performances

One dimension solar cells simulator package (SCAPS) is used to study the possibility of carrying out thin CIGS solar cells with high and stable efficiency. In the first step, we modified the conventional ZnO:B/i-ZnO/CdS/SDL/CIGS/Mo structure by substituting the SDL layer with the P?+?layer, having a wide bandgap from 1 to l.12?eV. Then, we simulated the J-V characteristics of this new structure and showed how the electrical parameters are affected. Conversion efficiency of 18.46% is founded by using 1.1?μm of P?+?layer thickness. Secondly, we analyze the effect of increase thickness and doping density of CIGS, CdS and P?+?layers on the electric parameters of this new structure. We show that only the short-circuit current density (J_SC) and efficiency are improved, reaching respectively 34.68?mA/cm² and 18.85%, with increasing of the acceptors density. Finally, we introduced 10?nm of various electron reflectors at the CIGS/Mo interface in the new structure to reduce the recombination of minority carriers at the back contact. High conversion efficiency of 23.34% and better stability are obtained when wide band-gap BSF is used.     

Investigation of local electronic transport and surface potential distribution of Cu(In,Ga)Se2 thin-films

Local current mapping and surface potential distributions on polycrystalline Cu(In,Ga)Se₂ (CIGS) films are investigated by conductive atomic force microscopy and Kelvin probe force microscopy. The two kinds of samples fabricated by co-evaporation had extremely different conversion efficiencies of 10% and 0.2% for stoichiometric and Cu- and Se-deficient compositions, respectively. We examined the microscopic reasons for the differences in the local electrical properties. Current mapping and current–voltage behaviors were measured at intragrain regions (IGs) and grain boundaries (GBs). Electronic transport between a Pt scanning probe and the CIGS layer is explained by the Schottky conduction mechanism. The surface potential distribution shows an intriguing relation with topological variation, inferring that a local built-in potential is possibly formed on positively charged GBs. The surface potential is about 100 mV, which shows energy band bending near GBs in the films. Exciton separation near GBs is explained by the bending of the conduction and valence bands, which is sensitive to compositional and structural inhomogeneities.