聚酰亚胺衬底CIGS薄膜附着性的改善

为改善聚酰亚胺(PI)衬底Cu(In,Ga)Se2(CIGS)薄膜的附着性,提出在NaF沉积前预先在Mo层上蒸发沉积100nm厚的In-Ga-Se(IGS)薄膜的新掺Na工艺。结果表明:这种IGS-NaF-CIGS式新工艺可显著改善CIGS薄膜的附着,而且CIGS薄膜材料和器件特性没有显著退化;新工艺促进了NaInSe2的生成,减少了In-Se二元相的残余,但也造成薄膜电阻率的升高和电池填充因子的下降,进而导致制备的PI衬底CIGS电池的转换效率由9.8%降至9.0%。综合考虑附着性的改善和器件效率的轻微下降,新工艺利大于弊,有很好的应用前景。     

金属Cr阻挡层对柔性不锈钢衬底Cu(In,Ga)Se2太阳电池性能的影响

研究了Cr扩散阻挡层对柔性不锈钢衬底Cu(InxGa1-x)Se2(CIGS)太阳电池性能的影响.XRD和SEM分析表明,Cr阻挡层能够部分阻挡Fe等杂质从不锈钢衬底热扩散进入CIGS吸收层中,同时可以显著降低CIGS吸收层的粗糙度,提高薄膜结晶质量.从衬底扩散进入吸收层中的Fe元素以FeInSe2的形式存在,并形成FeCu等深能级缺陷,钝化了器件的性能.相同工艺条件下,在玻璃、不锈钢以及不锈钢/Cr阻挡层上所制备电池的(有效面积0.87cm2)转换效率分别为10.7%,7.95%和8.58%,不锈钢衬底电池效率的提高归因于Cr阻挡层的作用.     

金属Cr阻挡层对柔性不锈钢衬底Cu(In,Ga)Se2太阳电池性能的影响

研究了Cr扩散阻挡层对柔性不锈钢衬底Cu(InxGa1-x)Se2(CIGS)太阳电池性能的影响.XRD和SEM分析表明,Cr阻挡层能够部分阻挡Fe等杂质从不锈钢衬底热扩散进入CIGS吸收层中,同时可以显著降低CIGS吸收层的粗糙度,提高薄膜结晶质量.从衬底扩散进入吸收层中的Fe元素以FeInSe2的形式存在,并形成FeCu等深能级缺陷,钝化了器件的性能.相同工艺条件下,在玻璃、不锈钢以及不锈钢/Cr阻挡层上所制备电池的(有效面积0.87cm2)转换效率分别为10.7%,7.95%和8.58%,不锈钢衬底电池效率的提高归因于Cr阻挡层的作用.     

玻璃衬底上RF磁控溅射CIGS薄膜的研究

采用射频磁控溅射的工艺,在玻璃衬底上制备得到了铜铟镓硒(CIGS)薄膜。讨论了衬底温度、溅射气压、退火与否对CIGS薄膜与衬底结合力、显微形貌、晶化程度及电阻率的影响。通过能谱(EDS)测试证明了溅射的CIGS薄膜Ga组分比符合高效吸收层的要求,通过X射线衍射(XRD)与扫描电子显微镜(SEM)测试,证明了衬底加热溅射、溅射后450℃空气退火可以有效提高CIGS薄膜与衬底的结合并提高晶化程度。通过四探针法电阻率测试证明了低气压条件下溅射、溅射后退火可以有效降低CIGS的电阻率,通过透射光谱分析证明了CIGS薄膜对可见光有高吸收效率,适合作为太阳电池的高效吸收层。     

柔性衬底硅薄膜太阳电池中ZGO薄膜的应用

在室温下,采用孪生对靶直流磁控溅射工艺,在玻璃衬底上制备出高质量的Ga掺杂ZnO(ZnO:Ga)透明导电膜。研究了薄膜厚度对薄膜的结构、光学及电学特性的影响。制备的ZnO:Ga是具有六角纤锌矿结构的多晶薄膜,最佳择优取向为(002)方向。随着薄膜厚度的增加,衍射峰明显增强,晶粒增大。优化反应条件,薄膜的电阻率达到4.69×10-4Ω.cm,在可见光范围内平均透过率达到了85%以上。将不同厚度的ZnO:Ga薄膜(350～820 nm)在柔性聚酰亚胺衬底nip非晶硅(a-Si)薄膜太阳电池中,随厚度的增加,电池的填充因子和效率都得到了提高,得到聚酰亚胺衬底效率7.09%的a-Si薄膜太阳电池。     

共蒸发三步法制备CIGS薄膜的性质

采用PID温度控制器控制共蒸发设备中蒸发源及衬底加热的温度,以三步法工艺制备CIGS(Cu(In,Ga)Se2)薄膜,通过恒功率加热衬底测试温度的变化,可实现在线组分监测,得到CIGS薄膜的组成重现性很好.CIGS薄膜的表面光洁,粗糙度多数小于10nm.但是组成相同的CIGS薄膜,其结晶择优取向可能不同,主要有(112)和(220)/(204)两种;其结晶形貌也有很大的不同,晶粒粗大且成柱状的薄膜电池效率高,虽然从Cu/(In+Ga)＜1的组成可以认为CIGS薄膜为贫Cu结构,但Hall测试多数CIGS薄膜呈p型,少数呈n型.     

共蒸发三步法制备CIGS薄膜的性质

采用PID温度控制器控制共蒸发设备中蒸发源及衬底加热的温度,以三步法工艺制备CIGS(Cu(In,Ga)Se2)薄膜,通过恒功率加热衬底测试温度的变化,可实现在线组分监测,得到CIGS薄膜的组成重现性很好.CIGS薄膜的表面光洁,粗糙度多数小于10nm.但是组成相同的CIGS薄膜,其结晶择优取向可能不同,主要有(112)和(220)/(204)两种;其结晶形貌也有很大的不同,晶粒粗大且成柱状的薄膜电池效率高,虽然从Cu/(In Ga)＜1的组成可以认为CIGS薄膜为贫Cu结构,但Hall测试多数CIGS薄膜呈p型,少数呈n型.     

激光刻蚀柔性薄膜太阳电池复合背反射层的研究

柔性聚酯膜衬底薄膜电池通过激光刻蚀等工艺形成集成串联,激光刻蚀柔性薄膜太阳电池复合背反射层(Ag/ZnO)是其中的重要工艺。首先对聚酰亚胺(PI)、Ag、ZnO材料的光学特性进行了分析,然后采用1 064nm脉冲激光与532nm脉冲激光分别对柔性薄膜太阳电池复合背反射层进行刻蚀研究。通过改变重复频率、激光功率、扫描速度和焦点位置等参数,分析了激光刻蚀物理机制,获得了好的刻蚀效果。结果表明,1 064nm纳秒脉冲激光更适合刻蚀柔性PI衬底复合背反射层Ag/ZnO,在激光功率860mW、刻蚀速度800mm/s和重复频率50kHz下,获得了底部平整、两侧无尖峰的刻线,刻线宽为32μm,满足柔性薄膜太阳电池集成串联组件的制备工艺要求。     

CdS薄膜的真空热蒸发制备及在CIGS薄膜太阳电池中的应用

采用真空热蒸发(VTE)的方法制备了CdS多晶薄膜,研究了不同衬底温度对其微观结构与光电性能的影响。结果显示,不同衬底温度下制备的CdS薄膜均属于六方相多晶结构且具有(002)择优取向;随着衬底温度的升高,(002)特征衍射峰强度增加,半高宽变小,相应薄膜结晶度增大;由CdS薄膜的透射光谱可知,在500~1 000nm波段平均透过率均超过80%,光学带隙随着衬底温度的升高而增大(2.44~2.56eV),表明真空热蒸发方法制备的CdS薄膜可以作为CIGS薄膜太阳电池的缓冲层。将真空热蒸发法制备CdS薄膜与磁控溅射法制备CIGS薄膜太阳电池相结合,在同一真空室内得到了CIGS薄膜太阳电池器件,为CIGS薄膜太阳电池的工业化推广提供了新途径。     

CdS薄膜的结构特性及其对Cu(In,Ga)Se2(CIGS)薄膜太阳电池的影响

报道了CdS薄膜的CBD法沉积及其结构特性,其中的水浴溶液包括硫脲、乙酸镉、乙酸铵和氨水溶液.研究了水浴溶液的pH值、温度、各反应物溶液的浓度和滴定硫脲与倾倒硫脲等基本工艺参数对CdS薄膜结构特性的影响.其中,溶液的pH值对CdS薄膜的特性起着关键的作用.XRD图显示了随着溶液pH值的变化,薄膜的晶相由六方相向立方相转变.CdS薄膜的这两种晶相对CIGS薄膜太阳电池性能的影响不相同.c-CdS(立方相的CdS)与CIGS之间的晶格失配和界面态密度分别为1.419%和8.507×1012cm-2,而h-CdS(六方相的CdS)与CIGS之间的晶格失配和界面态密度则分别为32.297%和2.792×1012cm-2.高效CIGS薄膜太阳电池需要的是立方相CdS薄膜.     

Na‐induced efficiency boost for Se‐deficient Cu(In,Ga)Se2 solar cells

Among different process routes for Cu(In,Ga)Se₂ (CIGS) solar cells, sufficient Se supply is commonly required to obtain high‐quality CIGS films. However, supplying extra Se increases the cost and the complexity. In this work, we demonstrate that extra Na incorporation can substantially increase efficiency of Se‐deficient CIGS solar cells, fabricated by sputtering from a quaternary CIGS target without extra Se supply, from 1.5% to 11.0%. The Se‐deficient CIGS device without extra NaF reveals a roll‐over I–V curve at room temperature as well as significantly reduced J_sc and fill factor at low temperatures. The electrical characteristics of Se‐deficient CIGS films are well explained and modeled by the low p‐type doping due to high density of compensating donors and the presence of deep defects possibly originating from the anti‐bonding levels of Se vacancies. The significant improvement after extra Na incorporation is attributable to the Na‐induced passivation of Se vacancies and the increased p‐type doping. Our result suggests that extra Na addition can effectively compensate the Se deficiency in CIGS films, which provides a valuable tuning knob for compositional tolerance of absorbers, especially for the Se‐deficient CIGS films. We believe that our findings can shine light on the development of novel CIGS processes, distinct from previous ones fabricated in Se‐rich atmosphere. Copyright © 2015 John Wiley & Sons, Ltd.     

新型CIGS阻挡层多横向界面Mo的特性及对器件性能的影响

采用磁控溅射方法,在不锈钢箔上制备多横向界 面Mo(M-Mo,multi-transverse interface Mo)和单横向界面Mo(S-Mo)薄 膜,并利用共蒸发三步法分别在M-Mo和S-Mo薄膜上制备Cu(In,Ga)Se₂(CIGS)薄膜及 器件。通过二次离子质谱仪(SIMS)、X射线衍射仪(XRD)和扫描电子显微镜(SEM)研究了不同 结构的Mo薄膜对CIGS影响。通过I-V测试,表征M-Mo和S -Mo作为背电极的CIGS电池电学性能。XRD结果显示,M-Mo和S-Mo 薄膜均以(110)为择优取向。SEM结果显示,M-Mo薄膜相对 于S-Mo,薄膜晶粒 较小,粗糙度较大。J-V测试结果显示,M-Mo薄膜作为背 电极的电池的开路电压Voc、短路电流J sc和填充因子(FF)均有所提高。     

Preferred orientation of Cu(In,Ga)Se2 thin film deposited on stainless steel substrate

The influences of process parameters and Fe diffusing into Cu(In,Ga)Se₂ (CIGS) films on the orientation of CIGS absorbers grown on the stainless steel (SS) foils are investigated. The structural properties, morphology, and elemental profiles are characterized using X‐ray diffraction, scanning electron microscopy, and second ion mass spectroscopy, respectively. The orientation of CIGS thin films on the SS substrates strongly depends on the texture of the (In,Ga)₂Se₃ precursor, determined by the substrate temperature at the first stage (Ts1) and the flux ratio of Se to (In + Ga). Among these factors, Ts1 is the prerequisite to achieve [300]‐oriented IGS layer, which will yield [200]‐oriented CIGS thin film in the later process. The results indicate that through the comparison of CIGS thin films on the Mo/SS substrates and on the Mo/ZnO/SS substrates and combined with simply calculation, Fe diffusing into the CIGS layer will hinder the growth of the CIGS grains along [112] orientation. The grazing‐incidence X‐ray diffraction results suggest that the surface of the [220]‐textured CIGS thin film on the SS substrate still has [220] predominance, whereas the surface texture of the [220]‐texture CIGS thin film on the Mo/soda‐lime glass substrate became [112] predominant, which is due to the different compensation ability between Fe and Na elements. Finally, the relations between the device parameters and the degrees of the preferred orientation of CIGS absorbers are investigated. Copyright © 2012 John Wiley & Sons, Ltd.     

Texture and morphology variations in (In,Ga)2Se3 and Cu(In,Ga)Se2 thin films grown with various Se source conditions

Texture and morphology variations in co‐evaporated (In,Ga)₂Se₃ and Cu(In,Ga)Se₂ (CIGS) films grown with various Se source conditions during growth were studied. The Se species of simply evaporated, large molecular Se (E‐Se, low‐sticking coefficient), and RF‐plasma cracked atomic Se (R‐Se, high sticking coefficient) were used in the present work. (In,Ga)₂Se₃ precursor films, which were prepared during the first stage of CIGS film growth by the three‐stage process, showed systematic variations in texture and Na distribution profile with varying evaporative Se (E‐Se) flux. The properties of CIGS films and solar cells also showed systematic variations, and the open‐circuit voltage (V_oc) and fill factor were found to be especially sensitive to the E‐Se flux. R‐Se grown (In,Ga)₂Se₃ precursor films featured granular morphology with strong (105) and (301) peaks in the diffraction pattern, and the texture was very similar to an E‐Se grown film fabricated with a Se to group III metal (In + Ga) flux ratio (P_{[Se]/[In + Ga]}) of about 6, although the nominal P_{[Se]/[In + Ga]} used for an R‐Se source was very small and less than 0.5. The R‐Se grown CIGS films displayed, however, highly dense surfaces and larger grain sizes than E‐Se grown CIGS films. The controllability of film morphology and the Na diffusion profile in (In,Ga)₂Se₃ and CIGS films with various Se source conditions are discussed. Copyright © 2011 John Wiley & Sons, Ltd.     

Fabrication and characterization of thin-film Cu (In,Ga) Se2 solar cells on a PET plastic substrate using screen printing

Chalcopyrite copper indium gallium diselenide (CIGS) ink was prepared by dissolving copper, indium, gallium acetylacetonate and Se powder in oleylamine using the hot injection methods. CIGS films were deposited on a PET plastic substrate by a screen-printing technique using CIGS ink with a Ga content ranging from 0.3 to 0.6. X-ray diffraction patterns reveal that the films exhibit a chalcopyrite-type structure. The crystalline grain sizes of the films decrease with increasing Ga content. AFM data shows that the root mean square (RMS) surface roughness of the CIGS film decreases with increasing Ga content. The effects of the Ga content in the CIGS absorber layer on the optical properties of the corresponding thin films and solar cells were studied. The band-gap energies of the CIGS thin films increased with an increasing Ga/(In+Ga) ratio. The short-circuit current (I_SC) of the solar cell decreased linearly with the Ga/(In+Ga) ratio, while the open-circuit voltage (V_OC) increased with this ratio. The solar cell exhibited its highest efficiency of 4.122% at a Ga/(In+Ga) ratio of 0.3.     

Effect of processing parameter on structural,optical and electrical properties of photovoltaic chalcogenide nanostructured RF magnetron sputtered thin absorbing films

The aim of this work was to develop high quality of CuIn_1−xGa_xSe₂ thin absorbing films with x (Ga/In+Ga)<0.3 by sputtering without selenization process. CuIn_0.8Ga_0.2Se₂ (CIGS) thin absorbing films were deposited on soda lime glass substrate by RF magnetron sputtering using single quaternary chalcogenide (CIGS) target. The effect of substrate temperature, sputtering power & working pressure on structural, morphological, optical and electrical properties of deposited films were studied. CIGS thin films were characterised by X-ray diffraction (XRD), Field emission scanning electron microscope (FE-SEM), Energy dispersive X-ray spectroscopy (EDAX), Atomic force microscopy (AFM), UV–vis–NIR spectroscopy and four probe methods. It was observed that microstructure, surface morphology, elemental composition, transmittance as well as conductivity of thin films were strongly dependent on deposition parameters. The optimum parameters for CIGS thin films were obtained at a power 100 W, pressure 5 mT and substrate temperature 500 °C. XRD revealed that thin film deposited at above said parameters was polycrystalline in nature with larger crystallite size (32 nm) and low dislocation density (0.97×10¹⁵ lines m⁻²). The deposited film also showed preferred orientation along (112) plane. The morphology of the film depicted by FE-SEM was compact and uniform without any micro cracks and pits. The deposited film exhibited good stoichiometry (Ga/In+Ga=0.19 and In/In+Ga=0.8) with desired Cu/In+Ga ratio (0.92), which is essential for high efficiency solar cells. Transmittance of deposited film was found to be very low (1.09%). The absorption coefficient of film was ~10⁵ cm⁻¹ for high energy photon. The band gap of CIGS thin film evaluated from transmission data was found to be 1.13 eV which is optimum for solar cell application. The electrical conductivity (7.87 Ω⁻¹ cm⁻¹) of deposited CIGS thin film at optimum parameters was also high enough for practical purpose.     

Structural and electrical properties of co-evaporated In, Ga-rich CIGS thin films

The CIGS thin films are prepared by co-evaporation of elemental In, Ga and Se on the substrates of Mo-coated glasses at400℃ followed by co-evaporation of elemental Cu and Se at 550℃. We study the structural and electrical properties usingXRD, XRF and Hall effect measurements. In general, Cu(In,Cra)5Se8 phase exists when Cu/(In Ga) ratio is from 0.17 to0.27, Cu(In,Ga)3Se5 phase exists for Cu/(In Ga) ratio between 0.27 and 0.41, Cu2(In,Ga)4Se7 and Cu(In,Ga)2Se3.5 phasesexist for Cu/(In Ga) ratio between 0.41 and 0.61, and OVC(or ODC) and CuIn0.7Ga0.3 Se2 phases exist when Cu/(In Ga)ratio is from 0.61 to 0.88. With the increase of Cu/(In Ga) ratio, the carrier concentrations of the films gradually increase,but the electrical resistivity gradually decreases.