硒蒸气浓度对制备CIGS薄膜的影响

采用“预制层硒化法”制备CuIn_1-xGa_xSe₂ (CIGS)薄膜. 基于自主设计的“双层管式硒化装置”, 通过控制硒蒸气浓度优化退火工艺, 研究硒蒸气浓度对薄膜光电性能的影响. 利用俄歇电子能谱(AES)和X射线衍射分析(XRD)等手段对不同硒浓度氛围下生成的CIGS薄膜的成分和物相进行表征, 并在AM1.5、1000 W·m^-2的标准光照条件下比较相应CIGS电池器件的输出性能. 实验结果表明: 饱和硒蒸气下退火得到的样品, 基底钼膜遭到严重腐蚀破坏, 失去背电极功能; 在低浓度硒气氛下退火不能有效消除CIGS薄膜的偏析和缺陷, 以致光电转换效率低; 而在无硒惰性氛围下退火的样品, 生成了物相均一化的CIGS薄膜, 由此制备的CIGS电池取得了8.5%的转换效率.     

掺钠钼电极在硒化铜铟镓(CIGS)太阳能薄膜电池应用

适量钠元素对铜铟镓硒薄膜生长具有促进作用,本文主要研究了掺钠钼电极特性及其对铜铟镓硒薄膜太阳能电池性能的影响。利用磁控溅射方法制备不同厚度的钼钠/钼(Mo Na/Mo)薄膜作为背电极,并在(Mo Na/Mo)薄膜电极上蒸镀铜铟镓硒(CIGS)薄膜,并利用单质硒源硒化处理后制备CIGS薄膜电池。SEM和XRD结果表明采用三层叠层Mo/Mo/Mo Na薄膜做电极的Mo Na容易被氧化,电阻率增加,采用四层叠层Mo/Mo/Mo Na/Mo薄膜电极方式有效降低电阻率,阻止Mo Na被氧化,CIGS晶粒较大且致密。在同一条件下,在不同Mo Na/Mo厚度电极上制备CIGS薄膜电池,80 nm Mo Na厚度上的CIGS薄膜电池效率达6.54%。     

掺钠钼电极在硒化铜铟镓（CIGS）太阳能薄膜电池应用

适量钠元素对铜铟镓硒薄膜生长具有促进作用,本文主要研究了掺钠钼电极特性及其对铜铟镓硒薄膜太阳能电池性能的影响。利用磁控溅射方法制备不同厚度的钼钠/钼（MoNa/Mo）薄膜作为背电极,并在（MoNa/Mo）薄膜电极上蒸镀铜铟镓硒（CIGS）薄膜,并利用单质硒源硒化处理后制备CIGS薄膜电池。SEM和XRD结果表明采用三层叠层Mo/Mo/MoNa薄膜做电极的MoNa容易被氧化,电阻率增加,采用四层叠层Mo/Mo/MoNa/Mo薄膜电极方式有效降低电阻率,阻止MoNa被氧化,CIGS晶粒较大且致密。在同一条件下,在不同MoNa/Mo厚度电极上制备CIGS薄膜电池,80nmMoNa厚度上的CIGS薄膜电池效率达6.54%。     

一步法电化学沉积Cu(In1-x,Gax)Se2薄膜的特性

在CuCl2、InCl3、GaCl3及H2SeO3组成的酸性水溶液电沉积体系中, 对Mo/玻璃衬底上一步法电沉积Cu(In1-x, Gax)Se2(简写为CIGS)薄膜进行了研究. 为了稳定溶液的化学性质, 在溶液中加入邻苯二甲酸氢钾和氨基磺酸作为pH缓冲剂, 将溶液的pH值控制在约2.5, 并提高薄膜中Ga的含量. 通过大量实验优化了溶液组成及电沉积条件, 得到接近化学计量比贫Cu 的CIGS薄膜(当Cu与In+Ga的摩尔比为1时, 称为符合化学计量比的CIGS薄膜; 当其比值为0.8-1时, 称为贫Cu或富In的CIGS 薄膜)预置层, 薄膜表面光亮、致密、无裂纹. 利用循环伏安法初步研究了一步法电沉积CIGS薄膜的反应机理, 在沉积过程中, Se4+离子先还原生成单质Se, 再诱导Cu2+、Ga3+和In3+发生共沉积. 电沉积CIGS薄膜预置层在固态硒源280 ℃蒸发的硒气氛中进行硒化再结晶, 有效改善了薄膜的结晶结构, 且成份基本不发生变化,但是表面会产生大量的裂纹.     

离子液体电沉积CuIn_xGa_(1-x)Se_2薄膜(英文)

采用循环伏安法(CV)对离子液体Reline中三元CuCl2+InCl3+SeCl4体系和四元CuCl2+InCl3+GaCl3+SeCl4体系的电化学行为进行了研究。研究表明,In3+并入三元CIS(Cu-In-Se)薄膜体系和Ga3+并入四元CIGS(Cu-In-Ga-Se)薄膜体系均有两种途径:一是发生共沉积,二是直接还原。利用电感耦合等离子体发射光谱(ICP)和扫描电镜(SEM)对沉积电势、镀液温度和主盐浓度对CIGS薄膜组成、镀层表面形貌的影响进行了测试,结果表明通过工艺参数的选择可以控制Ga/(Ga+In)和CIGS薄膜组成并得到化学计量比为Cu1.00In0.78Ga0.27Se2.13的薄膜。     

Ga和Cu/In衬底上电沉积金属Ga

在酸性水溶液中,分别在金属Ga和Cu/In衬底上进行了Ga电沉积的研究。用循环伏安法研究了导电盐、pH值对电沉积Ga的影响。系统研究了Ga的沉积过程,发现Ga会逐渐向薄膜内部扩散,在Cu/In界面上与CuIn合金反应生成CuGa₂合金。针对Cu/In薄膜和Ga薄膜是活泼金属的特点,在溶液中加入三乙醇胺有效地保护了Cu/In薄膜和Ga金属薄膜不被氧化,并且提高了Ga沉积的电流效率。在Cu/In薄膜上制备出了均匀光亮的金属Ga薄膜。对电沉积出Cu-In-Ga预置层进行了硒化处理,得到了质量较好的Cu(In_1-xGa_x)Se₂(CIGS)薄膜,并制备了太阳电池。电池效率达到了9.42%。     

激光刻蚀模板中电沉积特殊结构CIGS薄膜

本文利用激光刻蚀模板,在水溶液中电沉积制备金属铜薄膜,讨论了温度、电流、硫酸铜浓度对薄膜形貌的影响. 采用SEM对制备的铜薄膜进行表征,结果表明在沉积温度为30 ℃,沉积电流为4 A·dm^-2(表观工作电流密度),硫酸铜浓度在20 ~ 50 g·L^-1的水溶液中电沉积可以得到中空馒头状和开口碗状结构的铜薄膜. 利用激光刻蚀模板,在离子液体1-丁基-3-甲基咪唑三氟甲磺酸盐([BMI][TfO]) - 30 Vol%丙醇混合电解质中电沉积CIGS薄膜,研究了沉积电势、沉积时间对薄膜形貌的影响. SEM观察发现,在沉积电势为-1.8 V,沉积时间为1.5 h条件下电沉积可以得到近似柱状的簇状花束样的CIGS薄膜, 电沉积铜后再进一步电沉积CIGS,得到了均匀有序的鼓包柱状结构的Cu/CIGS复合薄膜. 用恒电势方波法对制备的薄膜真实表面积进行测试,计算结果表明,与无模板电沉积制备的CIGS薄膜相比,激光刻蚀模板法制备的Cu/CIGS复合薄膜的表面积提高了约8倍.     

金属铝诱导法低温制备多晶硅薄膜

以氢气稀释的硅烷(SiH₄)和硼烷(B₂H₆)为气源,利用等离子体增强化学气相沉积法(PECVD)制备出p型a-Si薄膜.采用铝诱导晶化技术对不同厚度的铝膜对a-Si薄膜晶化的影响进行了研究.实验中发现,铝膜溅射为10 s的非晶硅薄膜样品在450℃下退火10 min后,p型a-Si结构仍为非晶态,铝膜溅射为20 s的非晶硅薄膜在450℃下退火20 min后,p型a-Si薄膜开始晶化为poly-Si薄膜,并且铝膜厚度越厚,则a-Si薄膜晶化程度越强.     

宽带隙Cu(In,Al)Se2薄膜的制备及表征

以特殊脉冲电沉积方法制备CuInSe2(CIS)前驱体薄膜, 通过真空蒸镀法在CIS薄膜上沉积Al膜, 经硒化退火后在氧化铟锡(ITO)基底上制备了Cu(InAl)Se2(CIAS)薄膜. 采用扫描电子显微镜(SEM)、X射线能谱(EDS)、X射线衍射(XRD)、X射线光电子能谱(XPS)、紫外-可见吸收光谱(UV-Vis)对其形貌、结构、成分及光学吸收性质进行了表征. 结果表明, 制备的CIAS薄膜颗粒均匀, 表面平整致密, 呈黄铜矿结构. 薄膜在可见光区具有良好的吸收, 带隙约为1.65 eV.     

高钐含量SmCo磁记录薄膜材料的研究

SmCo合金具有极高的单轴磁晶各向异性,成为未来高密度磁记录介质的候选材料之一.本文采用磁控溅射方法,在玻璃基片上制备了Cr(100nm)/SmCo(50 nm)/Cr(20 nm)结构的Smco薄膜,SmCo层中Sm含量为35%(原子分数).利用综合物性测试系统(PPMS)和X射线衍射(XRD)对薄膜的磁性能和晶体学结构进行了测试.结果表明,通过550℃退火20 min可以获得很好的硬磁性能,矫顽力R.达到了3183kA·m-1,XRD结果表明薄膜中同时存在磁性相SmCo5和非磁性相SmCo2等.高Sm古量的SmCo薄膜在退火温度为450℃时开始晶化,退火温度达到550℃时,晶化进行的比较完全.     

Controlled electrodeposition of Cu-Ga from a deep eutectic solvent for low cost fabrication of CuGaSe2 thin film solar cells

The electrochemical deposition of Ga and Cu-Ga alloys from the deep eutectic solvent choline chloride/urea (Reline) is investigated to prepare CuGaSe(2) (CGS) semiconductors for their use in thin film solar cells. Ga electrodeposition is difficult from aqueous solution due to its low standard potential and the interfering hydrogen evolution reaction (HER). Ionic liquid electrolytes offer a better thermal stability and larger potential window and thus eliminate the interference of solvent breakdown reactions during Ga deposition. We demonstrate that metallic Ga can be electrodeposited from Reline without HER interference with high plating efficiency on Mo and Cu electrodes. A new low cost synthetic route for the preparation of CuGaSe(2) absorber thin films is presented and involves the one-step electrodeposition of Cu-Ga precursors from Reline followed by thermal annealing. Rotating disk electrode (RDE) cyclic voltammetry (CV) is used in combination with viscosity measurements to determine the diffusion coefficients of gallium and copper ions in Reline. The composition of the codeposited Cu-Ga precursor layers can be controlled to form Cu/Ga thin films with precise stoichiometry, which is important for achieving good optoelectronic properties of the final CuGaSe(2) absorbers. The morphology, the chemical composition and the crystal structure of the deposited thin films are analysed by scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDX) and X-ray diffraction (XRD). Annealing of the Cu-Ga films in a selenium atmosphere allowed the formation of high quality CuGaSe(2) absorber layers. Completed CGS solar cells achieved a 4.1% total area power conversion efficiency.     

Synthesis of colloidal nanoscaled copper-indium-gallium-selenide (CIGS) particles for photovoltaic applications

In this work, Cu(In,Ga)Se(2) (CIGS) nanoparticles were synthesized using a wet chemical method. The method is based on a non-vacuum thermal process that does not use selenization. The effects of temperature, source materials, and growth conditions on the phase and particle size were investigated. X-ray diffraction results confirm the formation of a tetragonal CIGS structure as the main phase with the purity more than 99% obtained by energy-dispersive X-ray spectroscopy (EDX). The morphology and size of the samples were investigated by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Using these methods, 20-80nm particles were obtained. Through measurements of the absorption spectra of CIGS nanoparticles, the band gap of the synthesized material was determined to be about 1.44eV, which corresponds to an acceptable wavelength region for absorber layers in solar cells.     

Metal Precursor Influence on Performance of CuIn1-xGaxSe2 Films

CuIn_1-xGa_xSe₂ (CIGS) films were prepared by a two-stage method, in which Cu-In-Ga metallic precursors were firstly deposited on unheated Mo-coated soda lime glass substrates by direct current sputtering CuGa (20%Ga) and radio frequency sputtering In targets inan Ar atmosphere, followed by selenization at 520 oC for 40 min in Se vapor. By adjust-ing the sputtering thickness ratio of surface CuGa (20%Ga) and bottom CuGa (20%Ga) alloy layers in metal precursor, different CIGS thin films were fabricated. Through X-ray diffraction spectra, Raman spectra, local energy dispersive spectrometer, planar- and cross-sectional views of scanning electron microscopy measurements, it revealed that the CIGS thin films from selenization of metal precursor with CuGa:In:CuGa thickness ratio of 7:20:3 (sample-2-se) was of chalcopyrite structure with the preferred (112) orientation, and the grains sizes ranged from 0.5 μm to 2 μm, and sample-2-se had no binary compound phase of In-Se and order defect compound phase. Consequently, the results of illuminated current-voltage curve and quantum efficiency measurements showed that the CIGS film device made from sample-2-se had relative higher photo-electric conversion efficiency (3.59%) and good spectrum response.     

8.01% CuInGaSe2 solar cells fabricated by air-stable low-cost inks

CuInGaSe(2) (CIGS), a promising thin film solar cell material, has gained lots of attention in decades due to its high energy conversion efficiency and potential lower manufacture cost over conventional Si solar cells. As a cheaper processing method compared to vacuum-based techniques, solution-based deposition has been successfully applied to fabricate electronic devices, such as transistors and solar cells. In this paper, we reported CIGS thin film solar cells with an energy conversion efficiency reaching up to 8.01% using air-stable, low-cost inks. The newly developed inks consist of commercially available, low-cost compounds and solvents and can be processed using a variety of printing and coating techniques. More importantly, the inks can produce CIGS films free of copper selenides and amorphous carbon, two common by-products from solution-based CIGS processes. The mechanism for the transformation from metal salt precursor films to CIGS absorber thin films and the influence of selenium vapour pressure on absorber film quality and photovoltaic device performance were investigated and discussed. High-quality CIGS films with micrometer-sized crystals were obtained by using higher selenization partial pressure.     

C(膜)/Si(SiO2 )(纳米微粒)/C(膜)热处理的形态及结构分析

用直流辉光溅射+真空镀膜法制备了一种新型结构的硅基纳米发光材料- C(膜)/Si(SiO2)(纳米微粒)/C(膜)夹层膜,并对其进行了退火处理.用TEM、 SEM、 XRD和XPS对其进行了形态结构分析.TEM观察表明: Si(SiO2)纳米微粒基本呈球形,粒径在30 nm左右.SEM观察表明: 夹层膜样品总厚度约为50 μm,膜表面比较平整、致密.400℃退火后,样品表面变得凹凸不平,出现孔状结构; 650℃退火后,样品表面最平整、致密且颗粒均匀.XRD分析表明:制备出的夹层膜主要由SiO2和Si组成,在C原子的还原作用和氧气的氧化作用的共同作用下, SiO2和Si的含量随加热温度的升高而呈现交替变化: 400℃时, C的还原作用占主导地位, SiO2几乎全部被还原成了Si,此时Si含量最高; 400～650℃时,氧化作用占主导地位, Si又被氧化成SiO2, Si含量降低, SiO2含量逐渐上升,在650℃达到最高.XPS分析表明: 在加热过程中, C原子逐渐扩散进入Si(SiO2)微粒层,在650℃与Si反应生成了新的SiC.     

离子液体电沉积CuInxGa1-xSe2薄膜

采用循环伏安法(CV)对离子液体Reline中三元CuCl₂+InCl₃+SeCl₄体系和四元CuCl₂+InCl₃+GaCl₃+SeCl₄体系的电化学行为进行了研究。研究表明,In³⁺并入三元CIS(Cu-In-Se)薄膜体系和Ga³⁺并入四元CIGS(Cu-In-Ga-Se)薄膜体系均有两种途径：一是发生共沉积,二是直接还原。利用电感耦合等离子体发射光谱(ICP)和扫描电镜(SEM)对沉积电势、镀液温度和主盐浓度对CIGS薄膜组成、镀层表面形貌的影响进行了测试,结果表明通过工艺参数的选择可以控制Ga/(Ga+In)和CIGS薄膜组成并得到化学计量比为Cu_1.00In_0.78Ga_0.27Se_2.13的薄膜。