双层预制膜对CIGS薄膜结构和形貌的影响

采用中频交流磁控溅射方法,在玻璃基底上依次沉积了Mo、CuIn、CuGa薄膜,制备了CuInGa（CIG）双层预制膜,采用固态硒化法制备获得了Cu（In1-xGax）Se2（CIGS）吸收层薄膜,考察了CuGa层制备过程中工作气压的改变,对CIGS薄膜结构和形貌的影响。采用SEM和EDS观察和分析了薄膜的表面形貌和成分,采用XRD表征了薄膜的组织结构。结果表明,改变溅射制备CuGa层的工作气压,所获得的CIG双层预制膜均由Cu11In9、CuIn和CuGa组成。在溅射制备CuGa层的工作气压为1．0Pa的条件下所获得的CIG双层预制膜经过硒化后,获得的CIGS薄膜致密。采用不同结构的双层预制膜,在不同的硒化时间下制备的CIGS薄膜,均具有黄铜矿相结构,薄膜具有（112）面的择优取向。     

电沉积制备CIS太阳能电池吸收层材料

在Cu衬底上用电沉积的方法沉积金属In,再通过硒蒸气硒化处理成功制备了CuInSe2薄膜.用X射线衍射(XRD)、扫描电镜(SEM)、X射线能谱(EDS)对制备的薄膜进行相组成、微观结构、表面形貌等分析,研究了制备工艺条件对薄膜性能的影响.结果表明:电沉积的In在低温热处理阶段与衬底Cu扩散形成Cu-In合金预制层,预制层在硒化阶段生成CuInSe2,合金中过量Cu生成CuSe表面层,未反应的In转变为Cu16In9,形成Cu衬底/Cu16In9/ CuInse2/CuSe结构.     

两步法制备的CulnGaSe2薄膜中Ga的富集现象

采用预制膜硒化两步法制备CIGSe薄膜,采用X射线衍射方法分析薄膜的结构,采用荧光光谱分析和俄歇电子能谱分析方法检测分析薄膜的成分.研究结果表明CIGSe薄膜中Ga元素以置换原子的形式存在于CuInSe2相中,并且Ga具有背电极富集现象.富集现象弱化了Ga元素对禁带宽度的提高作用,并且由于薄膜背电极侧Ga含量过高导致背...     

磁控溅射再硒化法制备Cu（In，Al）Se2薄膜

本文采用磁控溅射的方法制备Cu-In-Al薄膜，然后固态源硒化制成Cu（In，Al）Se2薄膜。采用EDX分析薄膜的成分，SEM观察薄膜的表面形貌，XRD表征薄膜的组织结构。结果表明，由CuIn相为主相的预制膜制成的Cu（In，Al）Se2薄膜具有单一的黄铜矿结构，且随着Al含量的增加，晶面间距减小。     

硒化温度对CuInSe2薄膜性能的影响

采用中频交流磁控溅射方法沉积Cu-In薄膜,并采用固态源硒化方法制备CuInSe2(CIS)薄膜,考察了硒化温度对CIS薄膜性能的影响.采用SEM和EDS观察和分析了它们的表面形貌和成分,采用XRD表征了薄膜的组织结构,采用霍尔测试仪测量了薄膜的载流子浓度和霍尔迁移率.结果表明,Cu-In薄膜由In和Cu11In9两相组成,在不同的硒化温度下制备的CIS薄膜,均具有单一的黄铜矿CuInSe2相结构.随着硒化温度的升高,CIS薄膜的晶粒直径增大,当硒化温度达到550℃时,晶粒直径已接近于2 μm.硒化温度继续升高,晶粒之间出现孔洞和缝隙等缺陷.530℃的硒化温度下制得的弱p型CIS薄膜,最符合CuInSe2的化学计量比,最适于制备太阳能电池吸收层.     

两步法电化学制备CuInSe2太阳能电池吸收层材料

采用先沉积In2Se3薄膜,再沉积CuInSe2的两步法电化学制备薄膜太阳能电池CuInSe2吸收层材料.通过XRD、SEM、EDX等分析手段检测了材料形貌、结构以及组分等,结果表明薄膜组分比为CuIn1.7Se2.2,其中In和Se的含量相对化学计量比有所增加.循环伏安法研究表明CuInSe的沉积属于诱导共沉积范畴.     

周期换向脉冲电沉积-硒化法制备铜铟镓硒薄膜

采用周期换向脉冲电沉积法于Mo/玻璃及ITO/玻璃衬底上制备铜铟镓硒薄膜。Mo/玻璃或ITO/玻璃为工作电极,饱和甘汞(SCE)为参比电极,大面积铂片作为阳极构成三电极体系,以氯化铜,三氯化铟,三氯化镓和亚硒酸的水溶液为电解液,制备Cu-In-Ga-Se合金预制膜,随后在硒蒸气中进行硒化处理,得到了黄铜矿结构的CuInGaSe2(CIGS)薄膜.分别用SEM,XRD和UV-吸收分析了合金预制膜和CuInGaSe2薄膜的表面形貌、相组成及紫外-可见吸收特性。结果表明,周期换向脉冲电沉积法可以制备表面平整、均匀致密的Cu-In-Ga-Se合金薄膜;利用脉冲电压的占空比可以提高预制膜中的In元素的比例,且随着In含量的增加,CIGS薄膜的结晶性变好;适当延长硒化退火的时间,可以使薄膜晶粒大小均匀,减小内应力,使薄膜的光吸收率提高,以利于制备更高效率的CIGS薄膜太阳电池.     

CIG前驱膜叠层方式对CIGS膜成分和结构的影响

采用中频交流磁控溅射方法制备了三种不同叠层方式的CuInGa（CIG）前驱膜。采用固态法硒化,获得了CIGS吸收层。采用SEM和XRD观察和分析了薄膜的成分、组织结构和表面形貌。着重分析不同叠层方式的CIG前驱膜对CIGs吸收层薄膜成分、晶体结构的影响。结果表明,三种叠层方式的前驱膜都可以获得成分均匀、结构一致的CIGS吸收层薄膜。Ga可以有效抑制In2Se挥发相生成,保持成分的稳定性。以CuGa（top）／CuIn（bottom）形式的前驱膜有利于形成紧密晶粒排列的CIGS。     

激光溅射沉积后硒化制备CIGS薄膜

采用脉冲激光溅射沉积法( PLD)制备了Cu - In - Ga双层预制膜,通过固态源硒化后热处理的方法获得了CuInl - xGaxSe2(CIGS)薄膜,研究制备预制膜的工艺参数以及热处理温度对CIGS薄膜特性的影响.采用台阶仪、SEM、EDS、XRD和紫外分光光度计研究了薄膜的厚度、表面形貌、成分、物相结构以及光...     

预制层结构成分对溅射后硒化制备CIGS薄膜的影响

采用磁控溅射法制备了不同结构成分的铜铟镓(CIG)预制层,对预制层进行硒化得到铜铟镓硒(CIGS)薄膜。采用XRD、SEM及EDS研究了CIG预制层的结构成分对CIGS薄膜的组织与结构的影响。结果表明,不同结构成分的CIG预制层经过硒化后得到的CIGS薄膜中各元素的成分比例差别不大;采用Ga浓度相对较高的CuGa靶制备的两层结构的CIG预制层经硒化后生成的CIGS薄膜,其(112)面择优取向比较明显,晶粒尺寸相对较大。     

Instantaneous preparation of CuInSe2 films from elemental In, Cu, Se particles precursor films in a non-vacuum process

CuInSe₂ (CIS) films are successfully prepared by means of non-vacuum, instantaneous, direct synthesis from elemental In, Cu, Se particles precursor films without prior synthesis of CIS nanoparticle precursors and without selenization with H₂Se or Se vapor. Our precursor films were prepared on metal substrates by spraying the solvent with added elemental In, Cu, and Se particles. Precursor films were instantaneously sintered using a spot welding machine. When the electric power was fixed to 0.6 kVA, elemental In, Cu, or Se peaks were not observed and only peaks of CIS are observed by X-ray diffraction (XRD) on the film sintered for 7/8 s. We can observe XRD peaks indicative of the chalcopyrite-type structure, such as (101), (103) and (211) diffraction peaks. We conclude that the synthesized CIS crystals have chalcopyrite-type structure with high crystallinity.     

CuInSe2 thin films formed by selenization of Cu–In precursors

CuInSe2 (CIS) thin films were grown by selenization of electro-deposited or electroless-deposited Cu–In precursors. Cu–In precursors were formed by layer-by-layer electro-deposition of Cu and In as well as by electroless co-deposition of Cu and In. The major phases in the precursors were found to be Cu11In9 and elemental In. It was found that the stoichiometric CIS phase (CuInSe2) may be formed by selenization of the precursors at temperatures higher than 500°C. The Cu–In precursors as well as CIS films were characterized by X-ray diffraction and scanning electron microscopy. The cubic CIS phase was formed when electroless-deposited Cu–In precursor was selenized, whereas the chalcopyrite CIS or the In-rich phase (CuIn2Se3.5) was formed when the layered precursors were selenized at a high temperature.     

Preparation of Zn(In)Se films from alloyed precursors

Single-phase cubic Zn(In)Se thin film growth by Se vapor selenization of Zn(In) alloy precursors films is described. Depositing the Zn(In) precursor film at higher substrate temperatures changes the In/Zn composition and also yields highly crystalline Zn(In)Se films. The In/Zn ratio in the selenized film is higher in comparison to that of the precursor due to differential selenization kinetics and the complex In-Se and Zn-Se reaction chemistry. The resistivity of the Zn(In)Se film depends on the In/Zn ratio. Initially, the resistivity increases with increased indium incorporation due to increased defect concentration and then decreases at higher In/Zn ratios because of lower grain-boundary effects and reduced trap density owing to improvement in film crystallinity. Treatment with vapor-phase Zn compensates for Zn vacancies in the film, reduces electrically inactive defects, and increases doping efficiency, thereby lowering the resistivities to ∼1 Ω cm. Hot-probe and thermoelectric power measurements show that all low resistive ZnSe films are n-type.     

PdSe2半导体薄膜的真空硒化法制备研究

PdSe2薄膜主要通过机械剥离法和气相沉积法制得,本研究采用一种简单有效的可在SiO2/Si衬底上制备PdSe2薄膜的方法.通过高真空磁控溅射技术在SiO2/Si衬底上沉积一层Pd金属薄膜,将Pd金属薄膜与Se粉封在高真空的石英管中并在一定的温度下进行硒化,获得PdSe2薄膜.根据截面高分辨透射电镜(HRTEM)照片可...     

Preparation of CuInSe2 thin films by selenization of co-sputtered Cu–In precursors

CuInSe2 thin films have been prepared by high Se vapor selenization of co-sputtered Cu–In alloy precursors within a partially closed graphite container. Cu–In alloys with different compositions were investigated. X-ray diffraction (XRD) analysis of the films showed mainly CuIn2 and Cu11In9 phases and the Cu11In9 peak intensity was found to increase as the alloy composition tended towards Cu-rich. A linear dependence of the alloy composition on the Cu/In deposition power was observed from energy dispersive analysis by X-rays (EDX). A three-fold volume expansion was exhibited by all the CuInSe2 films after selenization at 500–550 °C. Scanning electron microscopy (SEM) analysis of the films showed large and densely packed crystal structures with sizes above 5 m. The CuInSe2 films exhibited single phase chalcopyrite structure with preferential orientation in the (1 1 2) direction. The EDX composition analyses of the films showed Cu/In ratio ranging from 0.43 to 1.2, and Se/(Cu+In) ratios from 0.92 to 1.47. The measured film resistivities varied from 10-1 to 105 cm. The Cu–In alloy precursors with Cu/In ratio less than 0.70 were found to form CuIn3Se5 a defect chalcopyrite compound. All films were Se rich, with the exception of samples with very high Cu content.© 1998 Kluwer Academic Publishers     

Cu-In合金硒化法制备CuInSe_2薄膜

采用三电极体系恒电压电沉积法制备了Cu-In薄膜,经硒化退火生成CuInSe_2薄膜.采用循环伏安法研究了电沉积Cu-In的循环伏安特性,确定其最佳沉积电位在-0.75V左右,Cu与In的化学计量比为1.1,达到了理想前驱体的Cu与In的化学计量比.研究了不同沉积电位下材料组成、结构与性能的影响.硒化后,Cu与In的化学计量比为1,1时形成了比较单一的CuInSe_2黄铜矿相结构.     

The optical and structural properties of polycrystalline Cu(In,Ga)(Se,S)2 absorber thin films

The pentenary compound semiconductor Cu(In,Ga)(Se,S)₂ is one of the most attractive materials for high-efficiency solar cells due to its tunable band gap to match well the solar spectrum. In this study, semiconducting Cu(In,Ga)(Se,S)₂ thin films were prepared by a classical two-step growth process, which involves the selenization and/or sulfurization of In/Cu–Ga precursor. During the precursor formation step metallic In/Cu–Ga alloys were deposited onto the Mo-coated soda-lime glass substrates by DC magnetron sputter process. The respective precursors were subsequently reacted with H₂Se and/or H₂S gasses, at elevated temperatures. By optimizing the selenization parameters, such as the gas concentrations, reaction time, reaction temperature, and the flow of H₂Se and H₂S, high quality, single phase pentenary films were obtained. The gallium and sulfur diffusion behaviors were found to depend strongly on the selenization/sulfurization profile. The surface morphology, phase structure, and composition of the layers were analyzed by scanning electron microscope, atomic force microscopy, X-ray diffraction, and electron diffraction spectroscopy. Photoluminescence measurements were performed to examine the optical properties of the films.     

Structural and optical properties of the Cu2ZnSnSe4 thin films grown by nano-ink coating and selenization

Quaternary semiconductor Cu₂ZnSnSe₄ (CZTSe) is a very promising alternative to semiconductors based on indium (In) and gallium (Ga) as solar absorber material due to its direct band gap, inherent high absorption coefficient (>10⁴ cm^?1) and abundance of cheap elements zinc (Zn) and tin (Sn). In this study, high quality CZTSe thin films were successfully synthesized by a green and low-cost solution based non-vacuum method, which involves spin coating non-toxic solvent-based CZTSe nano-inks onto Mo coated soda lime glass substrates followed by selenization with elemental Se vapor. The effect of selenization temperature on structural, morphological, compositional and optical properties of CZTSe films are investigated using X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and photoluminescence spectroscopy. XRD and Raman analysis indicates that a tetragonal stannite-type structured CZTSe is formed. Depend on the selenization temperature, the dense and compact films with grain sizes from 200 nm (500 °C) up to about 1 μm (580 °C) are obtained. EDS measurement indicates that the composition ratios of the prepared CZTSe films are copper-poor and zinc-rich nature. The CZTSe films are p-type conductivity confirmed by a hot point probe method. Photoluminescence spectrum shows slightly asymmetric narrow bands with a maximum of intensity at 0.92 eV. The dependence of the photoluminescence on the excitation temperature reveals a decrease in the intensity of the photoluminescence bands. An absorption coefficient exceeding 10⁴ cm^?1 and the band gap energy about 0.87 eV of the studied films are determined by an absorption spectroscopy.     

Adjustment of the selenium amount during ion beam sputtering deposition of CIS thin films

CuInSe₂ (CIS) films were prepared by ion beam sputtering depositing Cu, In and Se layers sequentially on BK7 glass substrates and annealing the 3-layer film in the same vacuum chamber. The adjustment of the Se amount in the film was achieved by controlling the sputtering time of the Se target. X-ray diffraction pattern shows CIS films have chalcopyrite structure and preferential (112) orientation when the sputtering of the Se layer is between 60 and 180 min. It also can be seen that the most intense and narrow peak indicates the highest crystallinity for the sample with sputtering Se of 60 min, which is in agreement with the Raman measurement. The content of Cu, In and Se in the film deviates from 1, 1 and 2 with increasing the sputtering time of the Se target. Direct band gap energy between 0.96 and 1.05 eV, depending on the Se amount, and a high absorption coefficient of 10⁵ cm⁻¹ are found. The measured film resistivities vary from 0.01 to 0.05 Ω cm. Thus, the structural, optical and electrical characteristics of the CIS thin films were dependent on the Se amount during the fabrication of films and after fitting the sputtering time of Se, an optimization of the properties and a saving of Se consumption were achieved.     

Influence of GaSe deposition temperature on the structural properties and in-depth compositional features of two-step grown Cu(In,Ga)Se2 thin films

In this study, Cu(In,Ga)Se₂ thin films were prepared by a classical two-stage growth process, which involved the selenization of thermally evaporated InSe/Cu/GaSe precursors. During the precursor-formation step the InSe and Cu were always deposited at 200 °C, while the GaSe layers were deposited at temperatures between 200 °C and 400 °C. The respective precursors were simultaneously selenized under identical conditions in elemental Se vapor. In cases where the GaSe layers were deposited at low temperatures around 200 °C, X-ray fluorescence (XRF) analysis revealed a large variation in element concentration with sample depth after selenization. In correspondence, X-ray diffraction (XRD) studies revealed the presence of separate CuInSe₂ and CuGaSe₂ phases in these specific samples. Optimum structural properties were obtained when the GaSe films were deposited at 300 °C, followed by selenization. In general, these films were uniform and dense and XRD studies revealed single-phase Cu(In,Ga)Se₂ material. Even more importantly, XRF analysis revealed a remarkable improvement in in-depth compositional uniformity when the GaSe films were deposited at or above 300 °C. An increase in GaSe deposition temperature to 400 °C, however, resulted in a deterioration in the structural features of the Cu(In,Ga)Se₂ thin films. In contradiction with other reports, these results indicated that the in-depth composition uniformity and especially the Ga diffusion profile in two-step grown Cu(In,Ga)Se₂ thin films can be controlled. The crucial factor influencing the depth profile of these films is the GaSe deposition temperature during the precursor formation step.