金属预置层后硒化法制备CIGS薄膜的研究进展

系统综述了国内外采用金属预置层后硒化法制备Cu(In,Ga)Se2(CIGS)薄膜的研究进展,重点从预置层制备过程中靶材的选择、叠层方式以及后硒化过程中硒源种类和硒化方式的选择等几个方面对各种工艺的优点、存在的问题和可能的解决方案进行讨论,并对金属预置层后硒化法的发展前景和趋势进行了展望。     

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CulnSe2,合金中过量Cu生成CuSe表面层,未反应的In转变为Cu36In9,形成Cu衬底／Cu16In9／CuInSe2／CuSe结构。     

溅射参数对CuInGa预制膜成分和结构的影响

作为CIGSe太阳能电池重要组成部分的CIGSe吸收层可以采用预制膜+硒化两步法制备.文中采用磁控溅射方法制备了成分均匀、具有一定成分比例的CuIn、CuGa、CuInGa预制膜.X射线荧光分析(XRF)结果显示随着溅射电流的增加,CuIn预制膜的Cu/In原子比减小,CuGa预制膜的Cu/Ga原子比保持不变;X射线衍射分析(XRD)结果表明CuIn、CuInGa预制膜主要由Cu2In、CuIn、In相组成,Ga元素以固溶的形式存在于CuInGa预制膜中.对于CuIn预制膜,随着溅射电流的增加,薄膜中的Cu2In相逐渐向CuIn转变.     

磁控溅射制备ZnO缓冲层薄膜的微观结构和光学性能

研究了衬底温度、溅射气压对磁控溅射沉积ZnO缓冲层薄膜的微观结构、表面形貌和光学性能的影响。结果表明,衬底温度、溅射气压对ZnO缓冲层薄膜表面形貌、晶粒尺寸、禁带宽度和光学透过率等有较大影响。综合分析得出最佳的制备ZnO缓冲层薄膜的工艺为250℃、0.6 Pa。在此工艺下制备的ZnO缓冲层薄膜具有很好的ZnO(002)面c轴择优取向,结构致密、尺寸均匀,禁带宽度为3.24 eV,可见光平均透过率为86.93%,符合作CIGS太阳能电池缓冲层的要求。     

SnS / ZnO 叠层太阳能电池的制备及性能研究

目的获得光电性能较佳的Sn S/Zn O叠层太阳能电池。方法通过磁控溅射法,采用不同的溅射参数在FTO玻璃上制备Sn S和Zn O薄膜,研究Sn S和Zn O薄膜的晶体结构、表面形貌和光学性能,最终获得制备叠层太阳能电池的最佳方案。结果沉积Sn S薄膜的溅射功率、沉积时间、工作气压为28W,40 min,2.5 Pa和36 W,25 min,2.3 Pa时,获得的两种Sn S薄膜均在(111)晶面具有良好的择优取向,晶粒较大,表面致密光滑,禁带宽度分别为1.48,1.83 e V。沉积Zn O薄膜的溅射功率、溅射时间、工作气压为100 W,10 min,2.5 Pa时,Zn O薄膜的结晶性能更优,透过率更大,适合作为太阳能电池的n层。以宽禁带Sn S(1.83 e V)为外p型吸收层,窄禁带宽度Sn S(1.48 e V)为内p型吸收层制备的FTO/n-Zn O/p-Sn S(1.83 e V)/n-Zn O/p-Sn S(1.48 e V)/Al叠层太阳能电池,其光电转化效率为0.108%,短路电流为0.90 m A,开路电压为0.40 V。结论制得的叠层太阳能电池性能较传统单层太阳能电池更优。     

联氨浓度对化学水浴沉积ZnS薄膜性能的影响

利用化学水浴法(CBD)在硫酸锌、氨水、联氨、硫脲的沉积体系下制备CIGS太阳能电池的ZnS缓冲层薄膜,研究了联氨浓度对缓冲层ZnS薄膜的生长过程、晶体结构及物理性能的影响。结果表明,联氨浓度能够显著影响ZnS薄膜的生长速度,联氨浓度越高,薄膜厚度越大,薄膜的致密性也随之提高;联氨浓度对薄膜的结晶性影响较小,CBD法制备的ZnS薄膜均为非晶薄膜;制备的ZnS薄膜有较高的透过率,禁带宽度为3.85 eV左右,能够使更多短波、高能量光子透过缓冲层到达CIGS吸收层,从而提高电池性能。     

CIGS基ZnS薄膜制备技术的研究

综述ZnS薄膜制备技术的特点.ZnS薄膜材料具有工艺容易控制、成本低等特点,极具市场发展潜力,尤其作为高阻层在CIGS太阳能电池的应用,有望替代传统使用的CdS膜.     

电子束蒸镀法制备CuIn_(0.7)Ga_(0.3)Se_2薄膜太阳电池的性能

封装石英管真空熔炼合成CuIn_(0.7)Ga_(0.3)Se_2(CIGS)块体,再采用电子束蒸镀此块体,制备用于太阳电池吸收层的CIGS薄膜,然后对薄膜进行不同温度的真空退火处理。分别采用XRD、EDS、SEM及光谱分析等方法,研究CIGS块体和退火薄膜的表面形貌、晶体结构、成分或者光电性能。结果表明:在1200℃、保温2 h后,采用真空熔炼获得结晶性能较好、单一黄铜矿结构的CuIn_(0.7)Ga_(0.3)Se_2块体。随着退火温度的升高,薄膜中In-Se杂质相分解,从而获得单一相的CIGS薄膜;并且颗粒不断长大,达到1.0~3.5μm;成分和光学禁带不断得到优化。600℃退火薄膜是比较符合理想太阳电池要求的吸收层材料。     

类金刚石薄膜的紫外可见区光学特性研究

在类金刚石薄膜（DLC）光学特性的研究方面,主要工作集中在红外区光学特性,在可见区和紫外区光学特性研究方面存在空白;鉴于此详细研究了采用脉冲电弧沉积DLC薄膜在可见区和紫外区的光学特性。利用脉冲电弧离子镀技术,在石英基片上和不同工艺条件下制备了类金刚石薄膜,研究了类金刚石薄膜在紫外和可见区的光学常数、光学透过率和光学能隙。结果表明,主回路电压是薄膜的光学常数变化的主要影响因素,低主回路电压下制备的类金刚石薄膜具有较低消光系数和折射率;不同的工艺条件下制备的类金刚石折射率从2．56变化到1．89（波长400nm）;沉积速率对薄膜的折射率和消光系数没有明显的影响;DLC薄膜的光学能隙在3．95eV左右;紫外区和可见区的透过率谱和椭偏仪测得的光学常数相互一致。     

电沉积/硫化法制备CuInS_2薄膜微结构研究

以电沉积制备的Cu-In预制膜为衬底材料,硫粉为原料,尝试了Cu-In预制膜以一定速度移动的特殊硫化方法。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,并分析了硫化中的反应动力学过程。结果表明:Cu-In预制膜由CuIn和CuIn2混合相组成,由其形成的CIS薄膜中除了CuInS2相以外,还出现CuxS二元相。KCN刻蚀处理去除表层的CuxS相后,底层的CuInS2薄膜具有黄铜矿相结构,与基底附着性较好。当速度为3.3v0时,CuInS2薄膜高质量结晶,薄膜均匀、致密,组分接近化学计量比,沿(112)面择优取向生长,适合于制备CIS太阳能电池吸收层。     

Formation of CIGS thin absorption layer by sequential sputtering of CuGa/In/CuGa precursor on Mo/SLG with post selenization

Precursor structures of CuGa/In/CuGa stacking layers were prepared on Mo/soda-lime glass by sequential sputtering using intermetallic CuGa and metal In targets, with post selenization by Se evaporation at substrate temperature 500 °C. The selenized CIGS thin films were characterized by X-ray photo electron spectroscopy, X-ray diffraction, energy dispersive spectroscopy, Field emission scanning electron microscopy (FE-SEM), and Photoluminescence (PL). XPS survey spectra show that the constituent elements such as Cu, Ga, In, and Se appeared on the surface composition with corresponding photoelectron lines and a detailed study of the Se 3d signal in the CIGS absorption layer was discussed. The X-ray diffractograms of the CIGS films exhibited peaks revealing that the films are crystalline in nature with tetragonal chalcopyrite structure. FESEM images reveal that CIGS thin films yield granular nanostructure and a Mo back contact with a columnar structure. The CIGS thin films demonstrated intense near-band-edge PL and free-to-bound transitions were found and reported.     

Synthesis and characterization of Cu2ZnSnS4 thin films grown by PLD: Solar cells

As-deposited and annealed Cu₂ZnSnS₄ (CZTS) thin films have been synthesized onto Mo coated glass substrates at different deposition times using pulsed laser deposition (PLD) technique. The effect of deposition time (film thickness) and annealing onto the structural, morphological, compositional and optical properties of CZTS thin films have been investigated. The polycrystalline CZTS thin films with tetragonal crystal structure have been observed from structural analysis. FESEM and AFM images show the smooth, uniform, homogeneous and densely packed grains and increase in the grain size after annealing. The internal quantitative analysis has been carried out by XPS study which confirms the stoichiometry of the films. The optical band gap of CZTS films grown by PLD is about 1.54 eV, which suggests that CZTS films can be useful as an absorber layer in thin film solar cells. Device performance for deposited CZTS films has been studied.     

通过氢还原热处理提升TiO2薄膜的抗菌性能

提升在可见光区间的抗菌效率一直是二氧化钛(TiO₂)抗菌性能研究的重要方向。采用脉冲激光沉积(PLD)制备TiO₂薄膜,并通过氢还原热处理的方法提升TiO₂表面的氧空位浓度从而增强其抗菌性能。结果发现,在以单晶氧化钇稳定的氧化锆(YSZ)为衬底时,生长的TiO₂薄膜为高度择优取向的锐钛矿相。生长温度越高,锐钛矿相的XRD衍射峰越强,薄膜越致密。将在600℃下生长的350 nm厚的TiO₂薄膜进行抗菌性能测试,发现其抗菌率约为86%。对样品进一步在4%H2氛围下进行还原处理,发现其抗菌率提升到约为97%。通过XPS、UV-Visible和PL测试,发现TiO₂经过还原热处理后在其表面形成更多的氧空位,在TiO₂带隙中形成氧空位缺陷能级,导致在可见光区域吸光性能增强,使其具有更高的抗菌性能。通过氢还原过程调控材料的缺陷组成,并研究TiO₂薄膜的光催化抗菌性能及抗菌机理。这种简易的调控TiO₂光吸...     

Yttria-stabilized zirconia thin films deposited by pulsed-laser deposition and magnetron sputtering

Yttria-stabilized zirconia (YSZ, ZrO₂:Y₂O₃) was deposited on (100) silicon by two physical vapor deposition techniques: pulsed laser deposition (PLD) and reactive magnetron sputtering (RMS). PLD thin films were grown on silicon substrates at 500 °C from the ablation of a 8YSZ ceramic target by a KrF excimer laser. RMS thin films were obtained by direct current magnetron sputtering of a Zr/Y metallic target in an oxygen/argon atmosphere. The deposition rate of the PLD technique using an UV excimer laser delivering pulses at a repetition rate of 40 Hz was found two orders of magnitude lower than the RMS method one. Both techniques led to the growth of crystalline films with a (111) preferential orientation. PLD films were dense and featureless whereas RMS ones exhibited well defined but compact columnar structure. Growth of a YSZ film of about 1 μm covering a rough and porous commercial anode support (NiO-YSZ cermet) was successfully carried out with both methods.     

Properties of multilayer gallium and aluminum doped ZnO(GZO/AZO) transparent thin films deposited by pulsed laser deposition process

Multilayer gallium and aluminum doped ZnO (GZO/AZO) films were fabricated by alternative deposition of Ga-doped zinc oxide(GZO) and Al-doped zinc oxide(AZO) thin film by using pulsed laser deposition(PLD) process. The electrical and optical properties of these GZO/AZO thin films were investigated and compared with those of GZO and AZO thin films. The GZO/AZO (1:1) thin film deposited at 400 °C shows the electrical resistivity of 4.18×10^?4 ωcm, an electron concentration of 7.5×10²⁰/cm³, and carrier mobility of 25.4 cm²/(V·s). The optical transmittances of GZO/AZO thin films are over 85%. The optical band gap energy of GZO/AZO thin films linearly decreases with increasing the Al ratio.     

铜铟镓硒薄膜太阳能电池的研究进展及发展前景

介绍了薄膜太阳能电池结构、性能特点以及目前在研究和生产过程中铜铟镓硒电池的制备方法;阐述了国内外在铜铟镓硒薄膜太阳能电池方面研究开发现状。最后探讨了铜铟镓硒太阳能电池存在的问题及今后研究方向。     

Effects of Deflection on the Sio2 Barrier Layer and Mo Back Electrode of Cu（In,Ga）Se2 Thin-Film Solar Cells on Stainless Steel Substrates

This paper studies the effects of deflection on the SiO2 barrier layer and molybdenum(Mo)back electrode of Cu(In,Ga)Se2 thin-film solar cells,prepared via magnetron sputtering on type SUS431 stainless steel substrates.The surface micro-cracks and sheet resistance of thin films had been observed and measured for in-situ bend tests.Experimental results show that increasing the thickness of the SiOx barrier has a better property to prevent cracks induced by bending stress.The sheet resistance of a Mo film increases alongside the bending of the curvature radius.The maximum allowed value of the curvature radius of the SiOx barrier layer,molybdenum electrodes,and the thin film CIGS absorbing layer should be 16 mm,20 mm,and 26 mm,respectively.Therefore,the maximum curvature radius limit should be 26 mm or less for CIGS thin-film solar cells prepared via sputtering on type SUS431 stainless steel substrates.     

Characterization of CuInS2 thin films prepared by sulfurization of Cu-In precursor

CuInS2 thin films were prepared by sulfurization of Cu-In precursors. The influences of the deposition sequence of Cu and In layers, such as Cu/In, Cu/In/In, and In/Cu/In, on structure, topography, and optical properties of CuInS2 thin films were investigated. X-ray diffraction results show that the deposition sequence of Cu and In layers affects the crystalline quality of CuInS2 films. Atomic force microstructure images reveal that the grain size and surface roughness are related to the deposition sequence used. When the deposition sequence of precursor is In/Cu/In, the CuInS2 thin films show a single-phase chalcopyrite structure with （112） preferred orientation. The surface morphology of CIS films is uniform and compacted. The absorption coefficient is larger than 10^4 cm^-1 with optical band gap Egclose to 1.4 eV.