ZnS溅射功率对Cu2ZnSnS4薄膜附着性及太阳电池性能的影响

采用不同ZnS溅射功率,在钠钙玻璃(SLG)衬底上依次溅射Mo、ZnS、SnS及Cu,退火后制备出Cu_2ZnSnS_4(CZTS)薄膜。研究了溅射功率(50～140W)对ZnS薄膜和CZTS薄膜的微观形貌、微结构以及附着性的影响。结果表明,不同功率溅射的ZnS薄膜为(008)择优取向的纤锌矿六方晶系结构;功率较低时,ZnS薄膜结晶质量较差;随着功率从50W增加到140W,ZnS薄膜内的压应力增加了一个数量级;ZnS溅射功率低于80W或高于110W时,退火后的CZTS薄膜发生龟裂甚至脱落;ZnS溅射功率在80～110W时,退火后CZTS薄膜表面均匀平整;110W溅射后的CZTS薄膜出现较多的孔洞和二次相。采用80W功率溅射ZnS薄膜制备的CZTS/CdS太阳电池,开路电压达到572mV,短路电流密度为14.23mA/cm~2,光电转换效率为3.34%。     

电化学沉积法制备Cu_2ZnSnS_4薄膜电池

采用简单的两电极电化学沉积金属薄膜技术,在镀钼的钠钙玻璃衬底上共沉积Cu-Sn层后,再沉积Zn金属层,制备出Cu-Sn-Zn金属预制层。在不同的温度下进行低温退火后,以硫粉作为硫源高温硫化金属预制层,制备出晶体质量较好的Cu2ZnSnS4(CZTS)薄膜。通过X射线衍射仪(XRD)、扫描电镜(SEM)及能谱仪(EDS)对薄膜的晶体结构、表面形貌和薄膜组分进行分析表征,发现共沉积Cu-Sn层,再沉积Zn金属层得到的CZT预制层表面平整但晶粒尺寸较小,经过退火处理后晶粒尺寸得到改善,且硫化后所得到的CZTS薄膜不易从Mo衬底上脱落,粘附性较强。用其制备的CZTS薄膜太阳电池的开路电压Voc=569mV,短路电流密度Jsc=8.58mA/cm2,光电转换效率为1.40%。     

反应温度对LiCoO2薄膜性能的影响

采用水热电化学法在Ni基体上制备了LiCoO₂薄膜.反应温度影响薄膜的择优取向,80℃时制备的薄膜具有(003)取向,100℃制备的LiCoO₂薄膜具有(101)和(104)取向,150℃时制备的薄膜取向性不明显.其中以100℃制备的(101)取向LiCoO₂薄膜的电化学性能最好,其容量为143mAh/g;10次充放电后,薄膜电极容量衰减小.     

氮化铜薄膜的研究

氮化铜(Cu_3N)薄膜是一种新型的电、光学材料,它具有典型的反三氧化铼结构,由于Cu原子没有很好地占据(111)晶格面的紧密位置.在薄膜中掺杂之后,薄膜的电、光学性质会发生显著变化.Cu_3N在较低温度下会分解为Cu和N_2.介绍了Cu_3N的制备方法,总结了该膜制备方法和工艺参数对薄膜结构的影响,分析了在不同N_2分压下薄膜由(111)晶面转向(100)晶面择优生长和薄膜定向生长的原因,讨论了薄膜的电学、光学、热学等物理性质及其在相关方面的应用,并对该膜的物理性质与结构之间的关系作了简要分析.     

反应温度对LiCoO2薄膜性能的影响

采用水热电化学法在Ni基体上制备了LiCoO2薄膜.反应温度影响薄膜的择优取向,80℃时制备的薄膜具有(003)取向,100℃制备的LiCoO2薄膜具有(101)和(104)取向,150℃时制备的薄膜取向性不明显.其中以100℃制备的(101)取向LiCoO2薄膜的电化学性能最好,其容量为143mAh/g;10次充放电后,薄膜电极容量衰减小.     

硫化物靶与单质靶制备Cu2ZnSnS4薄膜的比较研究

为了验证磁控溅射硫化物靶替代单质靶制备Cu₂ZnSnS₄(CZTS)薄膜及太阳电池的可行性与优越性, 采用多周期磁控溅射ZnS-Sn-CuS和Zn-Sn-Cu制备CZTS薄膜, 并分析了使用不同溅射靶材对薄膜晶体结构、相纯度、表面粗糙度、化学组分、表面、截面形貌及光电特性的影响。按SLG/Mo/CZTS/CdS/i-ZnO/ZnO:Al/Ni-Al结构制成完整的电池器件并测量了J-V曲线。结果显示采用ZnS-Sn-CuS靶制备的CZTS薄膜太阳电池开路电压为611 mV, 短路电流密度为21.28 mA/cm ², 光电转换效率达5.11%; 而以单质靶为基础制备的太阳电池开路电压为594 mV, 短路电流密度为18.56 mA/cm ², 光电转换效率为4.13%。这归因于采用ZnS-Sn-CuS制备的CZTS薄膜相比于单质靶更加平整致密, 纵向生长更好。证明了采用硫化物靶制备CZTS薄膜及太阳电池相较于单质靶的优越性。     

分段恒电位电化学沉积法制备CuInSe2吸收层

采用分段恒电位电沉积法在FTO导电玻璃上制备了CuInSe2 (CIS)薄膜.通过线性电位扫描分析了阴极的电化学反应,并通过电化学沉积法制备了CIS薄膜.结果表明,恒电位电化学沉积的薄膜与CIS的化学计量比相差较大,增加溶液中铟离子的浓度,可以提高铟在镀层的含量,使薄膜更接近CIS化学计量比.而采用分段恒电位法沉积薄膜,可以抑制铜硒化合物的生长,使薄膜更接近于CIS化学计量比.     

VO_2(M/R)复合薄膜的研究进展

VO2(M/R)薄膜相变前后的红外透过率、电阻率变化显著,在光学、电学开关等领域极具应用潜力。VO2(M/R)复合薄膜能克服纯相材料本身的不足,还可以引入新的性能和结构。综述了VO2(M/R)复合薄膜的特点和主要性能,总结了薄膜的复合方式,讨论了复合薄膜制备中存在的问题,并结合近年的相变机理、制备工艺、复合方式等报道展望了VO2(M/R)复合薄膜的研究发展前景。     

多孔TiO2薄膜的制备研究进展

综述了液相法(包括溶胶凝胶法、蒸发诱导自组装法等)、电化学法(包括阳极氧化法、微弧氧化法等)、物理气相法(包括磁控溅射法、电子束蒸发法等)、化学气相法等制备多孔TiO2薄膜的方法,介绍了相应的合成原理,指出不同方法制备的多孔TiO2薄膜在表面形貌、孔径尺寸、取向和孔壁厚度等方面存在很大差异.通过对比不同制备方法的优缺点并结合工业化生产成本,提出了今后多孔TiO2薄膜制备技术的发展方向,并展望了多孔TiO2薄膜广阔的应用前景.     

超级电容器高比容(RuO_2/SnO_2)·nH_2O复合薄膜电极的研究

采用电沉积工艺制备超级电容器用钽基(RuO2/SnO2)·nH2O复合薄膜,研究了初始沉积液中Sn2+与Ru3+浓度比以及热处理对制备(RuO2/SnO2)·nH2O复合薄膜性能的影响.借助扫描电镜、X射线衍射仪、红外光谱对薄膜的形貌和物相进行分析,用循环伏安法(CV)对该复合薄膜电容特性进行了测量.结果表明,以沉积液中Sn2+与Ru3+浓度比为2:1时电沉积出的样品,在温度为300℃、热处理2.5h后所制备出的复合电极薄膜材料的比电容达到385F/g.     

Electrodeposition of chalcopyrite films from ionic liquid electrolytes

An air and water stable room-temperature ionic liquid based on choline chloride/urea eutectic mixture has been investigated as a system for the electrodeposition of CuInSe₂ (CIS) and Cu(In,Ga)Se₂ (CIGS) films for photovoltaic applications. Deposition potentials and bath compositions were optimized to obtain Cu-In, Cu-In-Se and Cu-In-Ga-Se precursor films, which were selenized in a tube furnace at 500 °C for 30 min to form CIS and CI(G)S films. Photo-electrochemical measurements on these selenized films showed p-type photoconductivity with band gaps of 1.0 eV and 1.09 eV, respectively, for CIS and CIGS. The films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), photocurrent spectroscopy and electrolyte electro-reflectance spectroscopy (EER).     

Raman spectroscopy of CuIn1 − xGaxSe2 for in-situ monitoring of the composition ratio

Metal organic vapor deposition (MOCVD) is a well known method for preparing high quality and large area CuIn_1 − xGa_xSe₂ (CIGS) absorber layers. Some in-situ non-contact monitoring systems are needed when CIGS absorber layers are manufactured in industry. In this study, CuInSe₂ (CIS) and CIGS thin films with different composition ratios, [Cu]/[In + Ga], were prepared by MOCVD using [Me₂In(μ-SeMe)]₂, hexafluoroacetylacetonate Cu(I) (3,3-dimethyl-1-butene), trimethyl gallium and dimethyle diselenide as the In-Se single source, Cu, Ga and Se precursors, respectively. The Raman shift spectra of the films with various composition ratios were analyzed to produce a basic algorithm that can determine the composition ratios of CIS and CIGS thin films indirectly.     

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.     

High voltage Cu(In,Ga)S2 solar modules

Sulfurcell (SC) has been running a pilot production for thin-film solar modules using CuInS₂-chalcopyrite (CIS) as absorber material since 2004. Since then production technology has been constantly improved with module power values exceeding 64 W, corresponding to an aperture area efficiency level of about 9%. Small area (0.5 cm2) cells cut out of such CIS modules reach maximum efficiencies close to 11%. Strong efforts have been made to develop a new sequential Cu(In,Ga)S₂ (CIGS) process suitable for production of large-scale CIGS solar modules thereby enabling module efficiencies above 10%. CIGS-based solar cells are—quite similar to CIS-based modules—prepared from sputtered metals subsequently sulfurized using rapid thermal processing in sulfur vapor. Such Cu(In,Ga)S₂ solar cells reach material record efficiencies about 13%. The cells are characterized by high open-circuit voltages up to 890 mV. Based on the results of the “Helmholtz Zentrum Berlin” (HZB), Sulfurcell has successfully scaled this process to our typical module size of 125 cm × 65 cm and is currently piloting the process for mass production. This paper will give an overview of electrical and structural parameters of world's first large-scale CIGS modules. CIGS module and cell parameters will be compared with standard CIS module and cell parameters and measured CIGS efficiency temperature coefficients will be compared with typical temperature coefficients of modules based on established PV technologies.     

硒化方式对CuInSe2薄膜结构、成分和形貌的影响

采用直流磁控溅射技术,首先在玻璃衬底上制备Mo薄膜,然后制备CuIn预制层。以固态硒粉为硒源,采用硒薄膜法和硒蒸气法两种硒化工艺,经过三步升温硒化方式对CuIn预制膜进行硒化制备CuInSe2薄膜。通过X射线衍射、能量散射谱和扫描电镜测试分析手段,分析CuIn预制膜和每一步硒化热处理后薄膜结构和形貌的变化。结果表明:两种方法硒化后均形成具有单一黄铜矿相结构的CuInSe2薄膜,薄膜具有(112)面择优取向,硒蒸气法形成的晶粒较大,但均匀性差。     

铜铟硒光伏材料的制备技术

黄铜矿型的CulnSe_2(CIS)是CIS太阳能电池的核心材料,CIS材料的制备技术对太阳能电池的效率和成本有极大影响.CIS材料性能的理论研究推动了单晶制备工艺,而粉体材料制备技术因有望用于太阳能电池的低成本制备而逐渐受到重视,薄膜材料的制备工艺则随着薄膜太阳能电池的研究得到极大发展.阐述了单晶、粉体和薄膜等CIS光伏材料的制备方法,介绍了几种典型的制备技术,并总结了这几种方法的技术特点.     

Cu(In,Ga)Se2 thin films and devices sputtered from a single target without additional selenization

Typically, Cu(In,Ga)Se₂ (CIGS) thin films for photovoltaic devices are deposited by co-evaporation or, alternately, by deposition of the metals with or followed by treatment in a selenium environment. In this article, we describe CIGS films that are instead deposited by RF magnetron sputtering from a single quaternary target without any additional selenization. Devices built with these films exhibit efficiencies as high as 8.9%. We demonstrate that deposition power can be varied in order to change the film morphology and improve device performance.     

基底温度对四元叠层硒化法制备铜铟镓硒(CIGS)薄膜的影响

利用四元叠层硒化法制备了铜铟镓硒(缩写为CIGS)薄膜,重点分析了在叠层法制备CIGS薄膜过程中,基底温度对CIGS薄膜的晶体结构,表面形貌以及各种元素沿深度分布的影响.实验结果表明,在叠层法制备CIGS薄膜时,发现在550℃的基底温度时,不经过退火便可以生成CIGS晶体,表面Ga的含量处于比较合适的范围.而基底温度为500℃,450℃时,只能生成铜铟硒(CIS)晶体,Ga元素表面的含量较少,主要分布在薄膜底部.     

Low-cost ZnO:Al transparent contact by reactive rotatable magnetron sputtering for Cu(In,Ga)Se2 solar modules

Sputtering ZnO as transparent front contact (TCO) is standard in today's industrial scale Cu(In,Ga)Se₂ (CIGS) module manufacturing. Although innovative concepts like rotatable magnetron sputtering from ceramic targets have been realised, costs are still high due to expensive ceramic targets. Significant cost reductions are expected by using reactive sputtering of metallic targets.Therefore, ZSW and industrial partners investigated the reactive sputtering of Al-doped zinc oxide (ZAO) as TCO on CIGS absorbers of high quality and industrial relevance. The reactive DC sputtering from rotatable magnetron targets is controlled in the transition mode by adjusting oxygen flow and discharge voltage. Optimisation leads to ZAO films with a TCO quality nearly comparable to standard films deposited by DC ceramic sputtering. Scanning electron microscopy, X-ray diffraction, and Hall analyses of the ZAO films are performed.Medium-size CIGS modules are coated with reactively sputtered ZAO, resulting in 12.8% module efficiency and surpassing the efficiency of the ceramic witness device. Cd-free buffered devices are also successfully coated with reactive TCO. Damp heat stability according to IEC61646 is met by all reactively sputtered devices.     

靶功率对溅射沉积CIGS薄膜的结构与光学性能的影响

采用单靶磁控溅射方法分别在玻璃和镀有Mo背电极的Soda-lime玻璃衬底上沉积Cu(In0.7Ga0.3)Se2(CIGS)薄膜。研究了靶功率变化对CIGS薄膜的晶体结构、表面形貌和光学性能的影响。采用XRD表征薄膜的组织结构,SEM和EDS观察和分析薄膜的表面形貌和成分,紫外-可见光分光光度计测试薄膜的透过率光谱。结果表明,在不同功率下制备的CIGS薄膜均具有(112)面择优取向。当溅射功率为300W时,CIGS薄膜的表面形貌最平整,结晶最均匀,n(Cu):n(In):n(Ga):n(Se)=30.00:15.01:3.97:51.03组分符合高效吸收层的要求。溅射沉积的CIGS薄膜对可见光的平均透过率低于2%,光学带隙约为1.4eV。