等离子体活化硒对电沉积Cu-In-Ga金属预制层硒化的影响

使用等离子体活化硒源对电沉积制备的Cu-In-Ga金属预制层进行了硒化处理时, 发现等离子体功率对Cu(In_1-xGa_x)Se₂(CIGS)晶粒的生长有重要影响, 当等离子体功率为75 W时, 制备出单一Cu(In_0.7Ga_0.3)Se₂相的CIGS薄膜. 通过对不同衬底温度的等离子体活化硒源硒化的CIGS 薄膜进行了研究与分析, 并与普通硒化后的薄膜进行对比, 发现高活性硒在低温下会促进Ga-Se二元相的生成, 从而有利于Cu(In_0.7Ga_0.3)Se₂单相的生长. 对等离子体硒化后的CIGS薄膜进行了电池制备, 发现单相CIGS薄膜没有显著提高电池性能. 通过优化工艺, 所制备的CIGS电池效率达到了9.4%. 关键词： 0.7Ga_0.3)Se₂')" href="#">Cu(In_0.7Ga_0.3)Se₂ 电沉积 Cu-In-Ga金属预制层 等离子体活化硒     

硒化前后电沉积贫铜和富铜的Cu(In1-xGax)Se2薄膜成分及结构的比较

采用电沉积法获得了接近化学计量比的贫铜和富铜的Cu（In_1-xGa_x）Se₂（CIGS）预置层,研究比较了两种预置层及其硒化处理后的成分和结构特性.得到了明确的实验证据证明,硒化后富铜薄膜中的Cu_xSe相会聚集凝结成结晶颗粒分散在表面.研究表明：在固态源硒化处理后,薄膜成分基本不变;当预置层中原子比Cu/（In+Ga）<11时,硒化后薄膜表面存在大量的裂纹;而当Cu/（In+Ga） >12时,可以消除裂纹的产生,形成等轴状小晶粒;富铜预置层硒化时蒸发沉积少量In,Ga和Se后,电池效率已达到68%;而贫铜预置层硒化后直接制备的电池效率大于2%,值得进一步深入研究. 关键词： 1-xGa_x）Se₂薄膜')" href="#">Cu（In_1-xGa_x）Se₂薄膜 电沉积 硒化处理 贫铜或富铜薄膜     

硒化前后电沉积贫铜和富铜的Cu(In1-xGax)Se2薄膜成分及结构的比较

采用电沉积法获得了接近化学计量比的贫铜和富铜的Cu(In1-xGax)Se2(CIGS)预置层,研究比较了两种预置层及其硒化处理后的成分和结构特性.得到了明确的实验证据证明,硒化后富铜薄膜中的CuxSe相会聚集凝结成结晶颗粒分散在表面.研究表明:在固态源硒化处理后,薄膜成分基本不变;当预置层中原子比Cu/(In+Ga)<1.1时,硒化后薄膜表面存在大量的裂纹;而当Cu/(In+Ga) >1.2时,可以消除裂纹的产生,形成等轴状小晶粒;富铜预置层硒化时蒸发沉积少量In,Ga和Se后,电池效率已达到6.8%;而贫铜预置层硒化后直接制备的电池效率大于2%,值得进一步深入研究.     

溅射后硒化法制备的CIGS薄膜中Ga元素扩散研究

溅射后硒化制备Cu(In,Ga)Se2吸收层工艺过程中,Ga元素在吸收层底部富集现象是较为普遍的.本文从预制层工艺和硒化工艺两个方面研究了Ga元素在Cu(In,Ga)Se2吸收层中扩散的影响因素.结果表明,预制层中的Cu/(In+Ga)和硒化温度对Ga元素扩散的影响较为显著,而预制层中的Ga/(In+Ga)对Ga元素扩散的影响较小,Ga元素的扩散系数制约了其在Cu(In,Ga)Se2吸收层表面的含量.通过工艺优化提高吸收层表面的Ga含量,制备获得了光电转换效率为12.42%的Cu(In,Ga)Se2薄膜太阳能电池.     

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.     

低温超薄高效Cu(In,Ga)Se2太阳电池的实现

衬底温度保持恒定, 在Se气氛下按照一定的元素配比顺序蒸发Ga, In, Cu制备厚度约为0.7 μrm的Cu(In_0.7Ga_0.3)Se₂ (CIGS)薄膜. 利用X射线衍射仪分析薄膜的晶体结构及物相组成, 扫描电子显微镜表征薄膜形貌及结晶质量, 二次离子质谱仪测试薄膜内部元素分布, 拉曼散射谱 分析薄膜表面构成, 带积分球附件的分光光度计测量薄膜光学性能. 研究发现在Ga-In-Se预制层内, In主要通过晶界扩散引起Ga/(Ga+In)分布均匀化. 衬底温度高于450 ℃时, 薄膜呈现单一的Cu(In_0.7Ga_0.3)Se₂相; 低于400℃, 薄膜存在严重的Ga的两相分离现象, 且高含Ga相主要存在于薄膜的上下表面; 低于300 ℃, 薄膜结晶质量进一步恶化. 薄膜表层的高含Ga相Cu(In_0.5Ga_0.5)Se₂以小晶粒形式均匀分布于薄膜表面, 增加了薄膜的粗糙度, 在电池内形成陷光结构, 提高了超薄电池对光的吸收. 加上带隙值较小的低含Ga相的存在, 使电池短路电流密度得到较大改善. 衬底温度在550 ℃–350 ℃变化时, 短路电流密度J_SC是影响超薄电池转换效率的主要因素; 而衬底温度T_sub低于300 ℃时, 开路电压V_OC和填充因子FF降低已成为电池性能减退的主要原因. T_sub为350 ℃时制备的0.7 μm左右的超薄CIGS电池转换效率达到了10.3%. 关键词： 2薄膜')" href="#">Cu(In,Ga)Se₂薄膜 衬底温度 超薄 太阳电池     

预制层溅射气压对CIGS薄膜结构及器件的影响

研究了金属预制层制备过程中溅射气压对Cu(In_1-xGa_x)Se₂(CIGS)薄膜及电池器件性能的影响.通过调节溅射气压改变预制层的结晶状态及疏松度与粗糙度,在合适的预制层结构下,活性硒化热处理过程中,可使Ga有效地掺入到薄膜中形成优质的CIGS固溶体.高溅射气压会使预制层过于致密,呈现非晶态趋势.经活性硒化热处理后,CIGS薄膜容易产生CIS与CGS"两相分离"现象,从而导致CIGS薄膜太阳电池的开路电压和填充因子降低,电池转换效率由10.03%降低到5.02%.     

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2 μm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)Se_{2关键词： 择优取向 Cu(In 2}薄膜')" href="#">Ga)Se₂薄膜 太阳电池     

Metal Precursor Influence on Performance of CuIn1-xGaxSe2 Films

在镀有Mo的纳钙玻璃衬底上顺序溅射沉积CuGa/In/CuGa层,然后在真空下520 oC硒化40 min,制备成CIGS薄膜. 通 过调整预制层的底层和表层的溅射沉积CuGa层的厚度比,制备不同的CIGS薄膜. 通过X射线衍射谱、拉曼谱、电子能谱、平面和断面SEM的分析, 揭示出CIGS薄膜是黄铜矿相的结构, 晶粒0.5～2 μm,且由硒化CuGa/In/CuGa厚度比为7:20:3的金属预制层后的CIGS薄膜的结晶性最好. 拉曼光谱表明,没有In-Se二元化合物相和有序缺陷化合物相.     

Stage2沉积速率对低温生长CIGS薄膜特性及器件的影响

研究了三步法第二步沉积速率对低温生长Cu(In,Ga)Se₂薄膜结构、 电学特性和器件特性的影响. 通过改变第二步沉积速率发现, 提高沉积速率可以显著促进薄膜晶粒生长, 提高晶粒紧凑程度降低晶界复合, 同时有效改善两相分离现象, 提高电池的开路电压和短路电流, 有助于Cu(In,Ga)Se₂电池光电转换效率的提高. 但同时研究表明, 随着第二步沉积速率的增加, 会促进暂态Cu_2-xSe晶粒的生长, 引起Cu(In,Ga)Se₂薄膜表面粗糙度增大, 并阻碍Na向Cu(In,Ga)Se₂薄膜表面的扩散, 造成施主缺陷钝化效应降低, 薄膜载流子浓度下降和电阻率升高, 且过高的沉积速率会引起电池内部复合增加并产生分流路径, 造成开路电压下降进而引起电池效率恶化. 最终, 通过最佳化第二步沉积速率, 在衬底温度为420℃时, 得到最高转换效率为11.24%的Cu(In,Ga)Se₂薄膜太阳电池.     

Improvement in efficiency of solar cell by removing Cu2－xSe from CIGS film surface

CIGS thin films are deposited by sputtering and selenization. The synthesis of semiconducting polycrystalline thin films and characteristics of devices based on the CIGS absorbing layers are investigated. Their microstructures are characterized by x-ray diffraction and Raman spectroscopy. The results reveal that there exist metallic Cu_2-xSe compounds in CIGS film surfaces and the compounds are thought to be responsible for the degradation of the open circuit voltage of solar cells. The optimization of selenization temperature profile and copper content in the precursor surfaces is studied, concluding that the conversion efficiency may be improved by removing metallic Cu_2-xSe compounds from the surfaces of CIGS thin films.     

热裂解活化硒对CIGS太阳电池开路电压的影响

考察了通过自主研发的高温热裂解辅助硒化装置所产生的高活性硒对CIGS薄膜结构和器件性能的影响.通过调节高温裂解系统的温度可以有效调节不同的硒活性.研究发现, 第一台阶HC-Se气氛可以提高CIGS薄膜表面的Ga含量, 使得CIGS薄膜内的Ga分布更加平缓, 进而提高CIGS薄膜表面禁带宽度.而且HC-Se气氛可以消除CIGS"两相分离"现象.两种因素的共同作用使得CIGS薄膜太阳电池的开路电压提高了34.6%.电池转换效率从6.02%提升至8.76%, 增长了45.5%.     

Solar photovoltaics R&D at the tipping point: A 2005 technology overview

The status of current and coming solar photovoltaic technologies and their future development are presented. The emphasis is on R&D advances and cell and module performances, with indications of the limitations and strengths of crystalline (Si and GaAs) and thin film (a-Si:H, Si, Cu(In,Ga)(Se,S)₂, CdTe). The contributions and technological pathways for now and near-term technologies (silicon, III–Vs, and thin films) and status and forecasts for next-next generation photovoltaics (organics, nanotechnologies, multi-multiple junctions) are evaluated. Recent advances in concentrators, new directions for thin films, and materials/device technology issues are discussed in terms of technology evolution and progress. Insights to technical and other investments needed to tip photovoltaics to its next level of contribution as a significant clean-energy partner in the world energy portfolio.     

Preparation of Cu（In,Ga）Se2 Thin Film Solar Cells by Selenization of Metallic Precursors in an Ar Atmosphere

Cu（In, Ga）Se2 thin films are deposited on Mo-coated glass substrates by Se vapour selenization of sputtered metallic precursors in the atmosphere of Ar gas flow under a pressure of about 10 Pa. The in situ heat treatment of as-grown precursor leads to the formation of a better alloy. During selenization, the growth of CuInSe2 phase preferably proceeds through Se-poor phases as CuSe and InSe at relatively low substrate temperature of 250℃, due to the absence of In2Se3 at intermediate stage at low reactor pressure. Subsequently, the Cu（In,Ga）Se2 phase is produced by the reactive diffusion of CuInSe2 with a Se-poor GaSe phase at high temperature of up to 560℃. The final film exhibits smooth surface and large grain size. The absorber is used to fabricate a glass/Mo/Cu（In, Ga）Se2/CdS/ZnO cell with the total-area efficiency of about 7%. The low open-circuit voltage value of the cell fabricated should result from the nonuniform distribution of In and Ga in the absorber, due to the diffusion-controlled reaction during the phase formation. The films, as well as devices, are characterized.     

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)     

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.     

部分阳离子取代优化铜锌锡硫硒薄膜太阳能电池性能研究进展

作为无机化合物薄膜太阳能电池中具有代表性的一类电池,铜锌锡硫硒(Cu2ZnSn(S,Se)4,简称CZTSSe)薄膜太阳能电池因其组成元素地壳含量丰富、低毒等优点受到广泛关注.目前,吸收层的高缺陷密度和器件的低开路电压被认为是限制该类电池效率的两个关键因素.为了突破这两大困境,科研人员发展了阳离子取代方法,即通过引入其...     

铜锌锡硫薄膜材料及其器件应用研究进展

铜锌锡硫薄膜材料组成元素储量丰富, 环境友好, 成本低廉, 成为最具前景的薄膜材料之一. 目前, Cu₂ZnSn(S, Se)₄ (CZTSSe)薄膜太阳电池的最高转换效率已经达到12.6%. 本文总结了Cu₂ZnSnS₄ (CZTS)的发展历史, 依次介绍了CZTS薄膜材料的结构特性、光学特性、电学特性、界面特性和Na对CZTS 薄膜的影响, 详细介绍了CZTS薄膜的制备方法及器件应用的最新研究进展, 总结了目前CZTS薄膜太阳电池发展中存在的问题, 展望了今后的研究方向.     

新型硒化锑材料及其光伏器件研究进展

硒化锑(Sb₂Se₃)是一种二元单相化合物, 原料储量大、毒性低、价格便宜; 同时其禁带宽度合适(～1.15 eV), 吸光系数大(>10⁵ cm^-1), 长晶温度低, 非常适合制作新型低成本低毒的薄膜太阳能电池, 理论光电转换效率可达30%以上. 目前文献报道的Sb₂Se₃薄膜太阳能电池效率已达3.7%, 初步证明了Sb₂Se₃材料在薄膜太阳能电池应用方面的巨大潜力. 本文综述了近年来Sb₂Se₃太阳能电池的研究进展, 着重介绍了Sb₂Se₃的材料特性和薄膜制备及相关理论研究, 阐述了不同结构电池器件的研究进展, 并对其发展趋势进行了展望.