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.     

掺钨VO_2薄膜的电致相变特性

采用直流磁控溅射与后退火工艺相结合的方法,在掺氟SnO_2(FTO)导电玻璃基底上制备了高质量的掺钨VO_2薄膜,对薄膜的结构、表面形貌和光电特性进行测试,分析了钨掺杂对其相变性能的影响.结果表明,室温下掺钨VO_2薄膜的阈值电压为4.2 V,观察到阈值电压下约有两个数量级的电流突变.随着温度升高,相变的阈值电压降低,且电流突变幅度减小.当施加8 V电压时,分别在不同温度下测试了掺钨VO_2薄膜的透过率.温度为20和50℃时,掺钨VO_2薄膜相变前后的红外透过率差量分别为23%和27%.与未掺杂的VO_2薄膜相比,掺钨VO_2薄膜具有相变温度低、阈值电压低和电阻率小的特点,在高速光电器件中有广阔的应用前景.     

二氧化钒薄膜低温制备及其太赫兹调制特性研究

针对二氧化钒(VO2)薄膜在可调谐太赫兹功能器件中的应用,利用低温磁控溅射技术,在太赫兹和光学频段透明的BK7玻璃上制备出高质量的VO2薄膜.晶体结构和微观形貌分析显示薄膜为单相VO2单斜金红石结构,具有明显的(011)晶面择优取向,结构致密,表面平整.利用四探针技术和太赫兹时域光谱系统分析了薄膜的绝缘体-金属相变特性,发现相变过程中薄膜电阻率变化达到4个数量级,同时对太赫兹透射强度具有强烈的调制作用,调制深度高达89％.通过电学相变和太赫兹光学相变特性的对比研究,证实薄膜的电阻率突变主要与逾渗通路的形成有关,而太赫兹幅度的调制则来源于薄膜中载流子浓度的变化.该薄膜制备简单,成膜质量高,太赫兹调制性能优异,可应用于太赫兹开关和调制器等集成式太赫兹功能器件.     

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.     

电沉积Cu-In-Ga金属预制层的硒硫化研究

以H₂S气体作为硫源、固态蒸发硒蒸气作为硒源对电沉积Cu-In-Ga金属预制层进行硒硫化处理. 通过电沉积Cu-In-Ga金属预制层在不同衬底温度下硒化、硫化和硒硫化的对比实验,发现CuInS₂相和CuIn（S,Se）₂相优先生成,抑制了CuInSe₂相的生成,促使InSe相薄膜向内部扩散,减弱了薄膜两相分离现象. 采用先硒化后硒硫化处理工艺优化了Cu（In,Ga）（S,Se）₂薄膜的制备工艺,在250 ℃预硒化得到了开路电压为570 mV的太阳电池,在更高的预硒化温度得到了较大短路电流的太阳电池,最终优化得到了效率达到10.4%的电池器件. 关键词： 电化学沉积 Cu-In-Ga金属预制层 硒硫化处理 2薄膜')" href="#">Cu(In,Ga)(S,Se)₂薄膜     

玻璃衬底二氧化钒薄膜的宽频带太赫兹波调制特性

针对二氧化钒（VO2）薄膜在可调谐太赫兹功能器件中的应用, 采用磁控溅射法在K9玻璃衬底上制备了VO2薄膜, 并用X射线衍射（XRD）对薄膜的晶相进行表征。利用配备加热装置的太赫兹时域光谱系统（THz-TDS）研究了薄膜样品在变温过程中的THz反射、透射光谱特性及其变化规律。实验结果表明, 随着加热温度的升高, VO2薄膜发生半导体-金属相变并对宽频段THz波产生显著的调制作用。调制深度明显依赖于THz频率, 薄膜样品对THz波反射功率、透射率的幅度调制深度在0.3~0.5 THz范围波动较大;对THz波的透射率在低频处较大, 高频处较小, 调制深度在35%~65%之间变化。该薄膜制备简单, 质量高, 可应用于太赫兹开关和调制器等功能器件。     

Influence of deposition pressure and power on characteristics of RF-Sputtered Mo films and investigation of sodium diffusion in the films

Mo films deposited by DC sputtering are widely used as back contact in CIGS and CZTS based thin film solar cells. However, there have been only a few studies on the deposition of Mo films by RF sputtering method. In this context, Mo films on SLG substrates were prepared as a function of deposition pressure and power by using RF magnetron sputtering method to contribute to this shortcoming. Mo films were deposited at 250 °C substrate temperature by using 20, 15, 10 mTorr Ar pressures at 120 W RF power and 10 mTorr Ar pressure at 100 W RF power. Structural, morphological and reflectivity properties of RF-sputtered Mo films were clarified by XRD, AFM, FE-SEM and UV–Vis measurements. In addition, due to sodium incorporation from SLG substrate to the absorber layer through Mo back contact layer is so essential in terms of improving the conversion efficiency values of CIGS and CZTS thin film solar cell devices, the effects of Na diffusion in the films were analyzed with SIMS depth profile. The electrical properties of the films such as mobility, carrier density and resistivity were determined by Hall Effect measurements. It was found that Mo films prepared at 120 W, 10 mtorr and 250 °C substrate temperature and then annealed at 500 °C for 30 min, had resistivity as low as 10⁻⁵ Ω cm, as well as higher amount of Na incorporation than other films.     

On the preparation of CuInSe<Subscript>2</Subscript> thin films via two‒stage selenization

A two-stage selenization method for preparing CuInSe₂ thin films in a carrier-gas (nitrogen) flow is developed. The dependences between the morphology and structure of CuInSe₂ thin films and the selenization temperature are studied via electron microscopy and X-ray diffraction analysis. It is demonstrated that the film incorporates copper and indium selenides in the temperature range 300°C ≤ T < 400°C and a stoichiometric film with ordered chalcopyrite is formed at Т = 400°С. The possible mechanism whereby a CuInSe₂ thin film is generated with the participation of selenization centers, namely, Cu₂Se and In₂Se₃ grains, is discussed.     

磁控溅射制备W掺杂VO2/FTO复合薄膜及其性能分析

为了获得相变温度低且热致变色性能优越的光学材料, 室温下在F:SnO₂ (FTO)导电玻璃基板表面沉积钨钒金属膜, 再经空气气氛下的热氧化处理, 制备了W掺杂VO₂/FTO复合薄膜, 利用X射线光电子能谱、X射线衍射和扫描电镜对薄膜的结构和表面形貌进行了分析. 结果表明: 高温热氧化处理过程中没有生成W, F, V混合氧化物, W以替换V原子的方式掺杂. 与采用相同工艺和条件制备的纯VO₂/FTO复合薄膜相比, W掺杂VO₂薄膜没有改变晶面取向, 仍具有(110)晶面择优取向, 相变温度下降到35 ℃左右, 热滞回线收窄到4 ℃, 高低温下的近红外光透过率变化量提高到28%. 薄膜的结晶程度明显提高, 表面变得平滑致密, 具有很好的一致性, 对光电薄膜器件的设计开发和工业化生产具有重要意义. 关键词： W掺杂 2')" href="#">VO₂ FTO导电玻璃 磁控溅射     

基于FTO/VO2/FTO结构的VO2薄膜电压诱导相变光调制特性

采用直流磁控溅射和后退火工艺在掺氟的SnO₂(FTO)导电玻璃衬底上制备VO₂薄膜, 研究了不同退火时间和不同比例的氮氧气氛对VO₂薄膜性能的影响, 对VO₂薄膜的结晶取向、表面形貌、表面元素的相对含量和透过率随波长变化进行了测试分析, 结果表明在最佳工艺条件下制备得到了组分相对单一的VO₂薄膜. 基于FTO/VO₂/FTO结构在VO₂薄膜两侧的透明导电膜上施加电压并达到阈值电压时, 观察到了明显的电流突变. 当接触面积为3 mm×3 mm时, 阈值电压为1.7 V, 阈值电压随接触面积的增大而增大. 与不加电压的情况相比, FTO/VO₂/FTO结构在电压作用下高低温的红外透过率差值可达28%, 经反复施加电压, 该结构仍保持性能稳定, 具有较强的电致调控能力.     

利用Raman散射光谱研究铜铟镓硒薄膜表面的掺杂调节作用

主要研究了采用溅射后硒化方法制备CIGS(铜铟镓硒)薄膜太阳电池的吸收体材料中的表面层掺杂调节问题。并利用Raman散射谱分析研究了样品表面层特征峰的移用,研究结果表明: CIGS薄膜表面层由富In表面层调节为富CuGa表面层后,Raman特征峰位向高波数移动,表明薄膜表面的Ga含量随之变化,并导致表面能带的相应改变,经计算证实了富CuGa表面层样品较之富In表面层样品具有更高的表面能带,从而改善了以此材料为吸收层的太阳电池器件性能, V_oc提高了74 mV,填充因子上升8％,最终使器件转换效率η相应提高了约2％。提高了V_oc与FF。同时表明Raman散射谱作为一种灵敏的表面表征手段,在研究太阳电池吸收层表面状态时十分有力。     

用离子束增强沉积从V2O5粉末制备高热电阻温度系数VO_2薄膜

采用了一种用离子束增强沉积从V2O5粉末直接制备VO2薄膜的新方法,将纯度为997%的V2O5粉末压成溅射靶,在用Ar离子束溅射的同时,用氩氢混合束对沉积膜作高剂量离子注入,使沉积膜中V2O5的V—O键断裂,进而被注入的氢还原,退火后获得热电阻温度系数(TCR)高达4%的VO2薄膜.高剂量的氩氢混合束注入对薄膜引入应力,使薄膜的转换温度降低、电阻温度曲线斜率变大,是薄膜TCR增大的原因 关键词： 离子束增强沉积 VO2薄膜 热电阻温度系数     

Molybdenum thin film deposited by in-line DC magnetron sputtering as a back contact for Cu(In,Ga)Se2 solar cells

In this paper, we reported the effect of the power and the working pressure on the molybdenum (Mo) films deposited using an in-line direct current (DC) magnetron sputtering system. The electrical and the structural properties of Mo film were improved by increasing DC power from 1 to 3 kW. On the other side, the resistivity of the Mo films became higher with the increasing working pressure. However, the adhesion property was improved when the working pressure was higher. In this work, in order to obtain an optimal Mo film as a back metal contact of Cu(In,Ga)Se₂ (CIGS) solar cells, a bilayer Mo film was formed through the different film structures depending on the working pressure. The first layer was formed at a high pressure of 12 mTorr for a better adhesion and the second layer was formed at a low pressure of 3 mTorr for a lower resistivity.     

Effects of oxygen content on the microstructures and optical properties of thermochromic vanadium oxide thin films

Reactive direct current magnetron sputtering and in situ thermal oxidation were used to prepare vanadium oxide (VO _X ) thin films with different oxygen contents. X-ray diffraction, Fourier transform infrared spectroscopy and a field emission scanning electron microscope were employed to characterize the films. The optical properties of the VO _X films at room temperature and 90 °C were investigated by applying an spectroscopic ellipsometer with a three-layer model of BEMA/Brendel–Bormann oscillator/substrate. It was demonstrated that the vanadium–oxygen bonds were strengthened, the film thickness and roughness decreased, while the grain size increased with increasing oxygen content. The increase in oxygen content had the effect of decreasing the near-infrared reflectance and free-electron concentration of the film at 90°C due to the decrease in the amount of VO₂.     

Preparation and characterization of iron–molybdate thin films

Mixed Fe–Mo oxides are used in industrial catalytic processes of selective oxidation of methanol to formaldehyde. For better understanding of the structure-reactivity relationships of these catalysts we aim to prepare well-ordered iron–molybdate thin films as model catalysts. Here we have studied Mo deposition onto Fe₃O₄ (111) thin films produced on Pt(111) as a function of Mo coverage and annealing temperature using LEED, AES, STM and IRAS. At low temperatures, the iron oxide film is covered by Mo = O terminated molybdena nanoparticles. Upon oxidation at elevated temperatures (T > 900 K), Mo species migrate into the film and form new bonds with oxygen in the film. The resulting films maintain the crystal structure of Fe₃O₄, and the surface undergoes a (√3 × √3)R30° reconstruction. The structure is rationalized in terms of Fe substitution by Mo in the surface layers.     

SrS:Ce3+薄膜蓝色交流电致发光及其特性的研究

本文采用了SnO2/Y2O3/ZnS/SrS:Ce3+/ZnS/Y2O3/Al这种多层结构制备了SrS:Ce3+薄膜器件,并得到了较亮的蓝色交流电致发光。在5KHz正弦交流电压的激发下,该器件的最大亮度为100cd/m2左右。讨论了衬底温度与薄膜结晶完整性的关系,认为衬底温度在300—400℃之间有利于获得良好的结晶状态。本文还对SrS:Ce3+薄膜的光谱特性进行了讨论,比较了CeF3和CeCl3分别掺杂时,SrS薄膜的发光特性发现CeCl3掺杂较CeF3掺杂好。同时还看到,SrS:Ce3+薄膜的ACEL亮度和效率较ZnS:Ce3+薄膜要高,认为可能的原因是SrS基质提供了一种适合Ce3+激发的环境。     

Low temperature fabrication of vanadium oxide films for uncooled bolometric detectors

Vanadium oxide films with temperature coefficient of resistant of −2.6% K⁻¹ have been fabricated on Si₃N₄-film-coated Si substrates by ion beam sputtering in a controlled Ar/O₂ atmosphere, at a relatively low growth temperature of 200 °C. The as-deposited films show no semiconductor-to-metal phase transitions even heated up to 150 °C. X-ray diffractometry shows that the main compound of the VO_x film is a metastable phase of vanadium dioxide (VO₂(B)) and the VO₂(B) film can be transformed into VO₂ film by post-growth annealing at 450 °C in flowing Ar atmosphere.     

A comparative study of solution based CIGS thin film growth on different glass substrates

CuIn_xGa_1−xSe_yS_2−y (CIGS) thin films were synthesized on glass substrates by a paste coating of Cu, In, and Ga precursor solution with a three-step heat treatment process: oxidation, sulfurization, and selenization. In particular, morphological changes of CIGS films for each heat treatment step were investigated with respect to the kinds of glass substrates: bare, Mo-coated, and F-doped SnO₂ (FTO) soda-lime glasses. Very high quality CIGS film with large grains and low degree of porosity was obtained on the bare glass substrate. Similar morphology of CIGS film was also acquired on the Mo-coated glass except the formation of an undesired Mo oxide interfacial layer due to the partial oxidation of Mo layer during the first heat treatment under ambient conditions. On the other hand, CIGS film with much smaller grains and higher degree of porosity was gained when FTO glass was used as a substrate, resulting in slight solar to electricity conversion behavior (0.20%). Higher power conversion efficiency (1.32%) was attained by the device with the CIGS film grown on Mo-coated glass in spite of the presence of a Mo oxide impurity layer.     

钼掺杂氧化锌薄膜的结构、光学和表面等离子体特性研究

室温下,通过直流磁控反应溅射在石英衬底上制备一系列钼掺杂氧化锌薄膜。分别采用X射线衍射(XRD)、原子力显微镜(AFM)、分光光度计及拉曼光谱仪研究了钼掺杂浓度对氧化锌薄膜结构、表面形貌、光学性能和表面等离子体特性的影响。XRD测试结果表明,零掺杂氧化锌薄膜结晶良好,呈c轴择优取向,掺杂后薄膜缺陷增多,结晶质量下降,当掺杂浓度达到3.93 Wt%时,薄膜由c轴择优取向的晶态转变为非晶态。AFM测试结果表明非晶态掺钼氧化锌薄膜表面光滑,粗糙度最低可达489 pm。透射光谱表明所有薄膜样品在可见光范围(400～760 nm)平均透过率均达到80%,禁带宽度随着掺杂浓度的提高从3.28 eV单调增加至3.60 eV。吸收光谱表明氧化锌薄膜表面等离子体共振吸收峰随钼掺杂量的增大发生蓝移,而拉曼光谱表明Mo重掺杂时ZnO薄膜表面拉曼散射信号强度显著降低。通过Mo掺杂获得非晶态氧化锌薄膜,拓宽了氧化锌薄膜材料的应用领域,同时研究了Mo掺杂浓度对氧化锌薄膜表面等离子体的调控作用,这对制备氧化锌基光子器件具有重要参考价值。     

The metals chemical states in hydrated vanadium oxides

The X-ray photoelectron spectroscopy (XPS) spectra of hydrated vanadium oxides (VO)Mo(x)V(12-x).nH(2)O (x=0, 1, 2, 3) were studied to provide the vanadium ions reduction ratio (RR)=V(4+)/(V(4+)+V(5+)) dependence on the molybdenum ions concentration and thermal treatment. The vanadium valence does not depend on Mo doping (x相似文献