Nonlinear Shift of the Raman A1 Mode in Ga-Incorporated CuInSe2 Thin Films

Composition dependence of quaternary CuIn1-x GaxSe2 films on Ga content has been systematically investigated by Raman scattering. The dominant A1 mode shifts from 174cm^-1 for CuInSe2 to 185cm^-1 for CuGaSe2 in an approximately polynomial curve other than a linear curve, indicating existence of asymmetric distribution of Ga and In on a microscopic scale in films. With Ga content x 〉 0.3, the significantly broadening and intensity decrease of A1 modes suggest the degradation of crystalline quality of chalcopyrite phase. Additionally, the quenching of additional Raman band at 183cm^-1 for the Ga-rich films reveals that CuAu-ordered phase can coexist in nominal chalcopyrite CuInSe2 films but not in CuGaSe2, due to Ga inhibition effect.     

CuInSe2 Films Prepared by a Plasma-Assisted Selenization Process in Different Working Pressures

The effects of working pressure on the composition, structure and surface morphology properties of CuInSe2 （CIS） films selenized with a plasma-assisted selenization process is investigated. Higher selenium content, better crystalline quality and much more regular surface particles compared to the others are found in the CIS film with 40 Pa working pressure. A Cu（In,Ga）Se2 device fabricated with the optimized plasma-assisted selenization process is demonstrated to be better than our previous result. After discussion, the reason for these phenomena is attributed to the compromise of electron temperature and plasma density.     

Study on reaction mechanism of YBa2Cu3O7-x film by TFA-MOD process

This paper systematically investigates the intermediate phases of YBa2Cu3O7-x (YBCO) film prepared by metalorganic deposition method using trifluoroacetates (TFA-MOD). According to x-ray diffraction and Raman analyses, the precursor film decomposed in a mixture of BaF2, Y2O3 and CuO after the pyrolysis process. Then these intermediate phases converted into tetragonal YBa2Cu3O6.5 at about 725°C. The influence of water vapour pressure on the YBa2Cu3O7-x film growth on LaAlO3 single-crystal substrates was also studied. The films prepared at low water vapour pressures (40-140 hPa) showed poor electrical performance due to the a-axis grain structure and impurity phases. However, the films prepared at 190 hPa exhibited the highest critical temperature of 90 K and the highest Jc of 3.8 MA/cm2, which was attributed to the formation of a purer YBCO phase and stronger biaxial texture.     

Structural and Electrical Properties of Single Crystalline Ga-Doped ZnO Thin Films Grown by Molecular Beam Epitaxy

High-quality Ga-doped ZnO （ZnO：Ga） single crystalline films with various Ga concentrations are grown on a- plane sapphire substrates using molecular-beam epitaxy. The site configuration of doped Ga atoms is studied by means of x-ray absorption spectroscopy. It is found that nearly all Ga can substitute into ZnO lattice as electrically active donors, a generating high density of free carriers with about one electron per Ga dopant when the Ga concentration is no more than 2%. However, further increasing the Ga doping concentration leads to a decrease of the conductivity due to partial segregation of Ga atoms to the minor phase of the spinel ZnGa2O4 or other intermediate phase. It seems that the maximum solubility of Ga in the ZnO single crystalline film is about 2at.% and the lowest resistivity can reach 1.92 ×10-4Ω·cm at room temperature, close to the best value reported. In contrast to ZnO：Ga thin film with 1% or 2% Ga doping, the film with 4% Ga doping exhibits a metal semiconductor transition at 80 K. The scattering mechanism of conducting electrons in single crystalline ZnO：Ga thin film is discussed.     

Flexible Cu（In,Ga）Se2 Thin-Film Solar Cells on Polyimide Substrate by Low-Temperature Deposition Process

The electrical and structural properties of polycrystalline Cu（In, Ga）Se2 films grown on polyimide （PI） substrates below 400℃ via one-stage and three-stage co-evaporation process have been investigated by x-ray diffraction spectra （XRD）, scanning electron microscopy （SEM） and Hall effect measurement. As shown by XRD spectra, the stoichiometric CIGS films obtained by one-stage process exhibit the characteristic diffraction peaks of the （In0.68Ga0.32）2Se3 and Cu（In0.7Ga0.3）2Se. It is also found that the film structures indicate more columnar and compact than the three-stage process films from SEM images. The stoichiometric CIGS films obtained by three-stage process exhibit the coexistence of the secondary phase of （In0.68Ga0.32）2Se3, Cu2-xSe and Cu（In0.7Ga0.3）2Se. High net carrier concentration and sheet conductivity are also observed for this kind of film, related to the presence of Cu2-xSe phase. As a result, when the CIGS film growth temperature is below 400℃, the three-stage process is inefficient for solar cells. By using the one-stage co-evaporation process, the flexible CIGS solar cell on a PI substrate with the best conversion efficiency of 6.38% is demonstrated （active area 0.16cm^2）.     

LaGa-based bulk metallic glasses

We report the formation of La Ga-based bulk metallic glasses. Ternary La–Ga–Cu glassy rods of 2–3 mm in diameter can be easily formed in a wide composition range by the conventional copper mold casting method. With minor addition of extra elements such as Co, Ni, Fe, Nb, Y, and Zr, the critical diameter of the full glassy rods of the La–Ga–Cu matrix can be markedly enhanced to at least 5 mm. The characteristics and properties of these new La Ga-based bulk metallic glasses with excellent glass formation ability and low glass transition temperature are model systems for fundamental issues investigation and could have some potential applications in micromachining field.     

Developments of High-Efficiency Flexible Cu（In,Ga）Se2 Thin Film Solar Cells on a Polyimide Sheet by Sodium Incorporation

We present the fabrication of flexible Cu（In,Ga）Se2 （CIGS） solar cells on a polyimide （PI） sheet with and without Na incorporation. A sodium element is incorporated into the CIGS absorber by using a NaF precursor after Mo back contact deposition. X-ray diffraction patterns show that the （112） preferred orientation of the as-grown GIGS films is decreased by Na incorporation. The secondary phase of （Inx,Gal-x）zSe3 is observed for the CIGS films with Na. There is no significant difference in the grain size with and without Na incorporation from surface and cross-sectional SEM images. Additionally, the increase of carrier concentration and decrease of resistivity of CIGS absorber are induced by Na doping. Finally, the flexible CIGS solar cells on PI sheets with efficiency close to 11%, containing Na, are achieved. The improvement of cell efficiency can be attributed to the modified electrical properties of the CIGS film by Na incorporation.     

Model for increased efficiency of CIGS solar cells by a stepped distribution of carrier density and Ga in the absorber layer

In this paper, several structures for multilayer Cu(In1-xGax) Se2 (CIGS) thin film solar cells are proposed to achieve high conversion efficiency. All of the modeling and simulations were based on the actual data of experimentally produced CIGS cells reported in the literature. In standard CIGS cells with a single absorber layer, the effects of acceptor density and Ga content on device performance were studied, and then optimized for maximum conversion efficiency. The same procedure was performed for cells with two and three sectioned CIGS absorber layers in which Cu and/or Ga contents were varied within each consecutive section. This produces an internal additional electric field within the absorber layer, which resulted in an increase in carrier collection for longer wavelength photons, and hence, improvement in the conversion efficiency of the cell. An increase of approximately 3% in efficiency is predicted for cells with two layer absorbers. For multilayer cells in which Cu and Ga distribution were stepped simultaneously, the improvement could be approximately 3.5%. This improvement is due to; enhanced carrier collection for longer-wavelength photons, and reduced recombination at the heterojunction and back regions of the cell. These results are confirmed by the physics of the cells.     

Composition-induced structural modifications in the quaternary CuIn1-xGaxSe2 thin films： bond properties versus Ga content

In this paper the dependence of structural properties of the quaternary CuIn1-xGaxSe2 films with tetragonal structure on the Ga content has been systematically investigated by Raman scattering and x-ray diffraction spectra. The shift of the dominant A1 mode, unlike the lattice constants, does not follow the linear Vegard law with increasing Ga content x, whereas exhibits approximately polynomial change from 174 cm^-1 for CuInSe2 to 185 cm^-1 for CuGaSe2. Such behaviour should be indicative of presence of the asymmetric distribution of Ga and In on a microscopic scale in the films, due to Ga addition. The changes in the tetragonal distortion η lead to a significant variation in the anion displacement parameter U, which should be responsible for the evolution of bond parameters and resultant Raman bands with x.     

Columnar growth of crystalline silicon films on aluminium-coated glass by inductively coupled plasma CVD at room temperature

Silicon films were grown on aluminium-coated glass by inductively coupled plasma CVD at room temperature using a mixture of SiH₄ and H₂ as the source gas. The microstructure of the films was evaluated using Raman spectroscopy, scanning electron microscopy and atomic force microscopy. It was found that the films are composed of columnar grains and their surfaces show a random and uniform distribution of silicon nanocones. Such a microstructure is highly advantageous to the application of the films in solar cells and electron emission devices. Field electron emission measurement of the films demonstrated that the threshold field strength is as low as ～9.8V/μm and the electron emission characteristic is reproducible. In addition, a mechanism is suggested for the columnar growth of crystalline silicon films on aluminium-coated glass at room temperature.     

Characterization of Cu(In,Ga)Se2 thin films prepared by evaporationfrom ternary compounds

Thin films of Cu(In,Ga)Se₂ were fabricated by evaporation from ternary CuGaSe₂ and CuInSe₂ compounds for photovoltaic device applications and their properties were investigated. From XRF analysis, the Cu:(In+Ga):Se atomic ratio in all thin films was approximately 1:1:2. The Ga/(In+Ga) atomic ratio in the thin films changed linearly from 0 to 1.0 with increasing the [CGS]/([CGS]+[CIS]) mole ratio in the evaporating materials. However, for thin films prepared at the [CGS]/([CGS]+[CIS]) mole ratio above 0.4, the composition by EPMA analysis was not consistent with that by XRF analysis. The result of EPMA analysis showed that the surface of a thin film was Cu-rich. XRD studies demonstrated that the thin films prepared at the [CGS]/([CGS]+[CIS]) mole ratio under 0.2 had a chalcopyrite Cu(In,Ga)Se₂ structure and the preferred orientation to the 112 plane. On the other hand, XRD patterns of the thin films produced at the [CGS]/([CGS]+[CIS]) mole ratio above 0.6 showed the diffraction lines from a chalcopyrite Cu(In,Ga)Se₂ and a foreign phase. The separation of a peak was observed near 2θ=27°, indicative the graded Ga concentration in Cu(In,Ga)Se₂ thin film.     

Structural properties of CuInSe2 films prepared by selenization of metallic precursors on MoNx film substrates

The aim of this work was to study the effect of MoN_x film substrates on the structural properties of CuInSe₂ films prepared by selenization of metallic Cu-In alloy precursors. MoN_x films were prepared by reactive dc-magnetron sputtering. All the CuInSe₂ films exhibit single phase chalcopyrite structure with (1 1 2) preferred orientation, which can be explained by the reduction of lattice mismatch between CuInSe₂ and MoN_x. The bulk composition of selenized CuInSe₂ films are near stoichiometric, but the surface composition analysis suggests Cu deficiency on surface area. Furthermore, ordered defect compound, CuIn₂Se_3.5 is found on the surface of CuInSe₂ films. The results will be helpful for fabricating Cd-free ZnO buffer layer CuInSe₂ and Cu(In_1−xGa_x)Se₂ based thin film solar cells.     

Zn incorporation and (CuIn)1−xZn2xSe2 thin film formation during the selenization of evaporated Cu and In precursors on Al:ZnO coated glass substrates

CuInSe₂ thin films with typical 1.0 eV gap energy and tetragonal chalcopyrite structure have been obtained on soda–lime glass substrates by the reaction of sequentially evaporated Cu and In layers with elemental selenium vapor, at 500 °C in flowing Ar. When analogous deposition and reaction processes were performed on Al:ZnO coated glasses, some increment in the band gap energy and diminution in the crystalline interplanar spacings have been detected for the resulting films with an extent that depends on the Cu/In atomic ratio of the evaporated precursor layers. This fact has been related to Zn incorporation into the selenized film, with quaternary (CuIn)_1−xZn_2xSe₂ compound formation that is influenced by the presence of copper selenide phases during the reaction process. Such deductions are supported by the optical, structural and compositional characterizations that have been performed comparatively on samples prepared by selenization of evaporated metallic precursors with two different Cu/In ratios (0.9 and 1.1) on bare and Al:ZnO coated glass substrates.     

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.     

Structural and Optical Properties of Nanocrystal In2O3 Films by Thermal Oxidation of In2S3 Films

In₂S₃ nanocrystalline films are prepared on glass substrates by the spray pyrolysis technique using indium chloride and thiourea as precursors. The deposition is carried out at 350°C on glass substrates. The films are then annealed for two hour at 200, 400, 600, and 800°C in O₂ flow. This process allows the transformation of nanocrystal In₂O₃ films from In₂S₃ films and the reaction completes at 600°C. These results indicate that the In₂O₃ film prepared by this simple thermal oxidation method is a promising candidate for electro-optical and photovoltaic devices.     

Cu(In,Sn)Se2 thin films for absorption of energy from infrared radiation

In this study, we sought to lower the bandgap of thin film solar cells by replacing the Ga used in the absorber layer of Cu(In,Ga)Se₂ with Sn (bandgap of 0.07?eV) to form Cu(In,Sn)Se₂. The proposed scheme was shown to reduce the bandgap of the absorber layer from 1.0?eV to 0.88?eV. Sn films of various thicknesses were deposited using precursors of Sn–In–Cu metal in order to study the effects of Sn/(In?+?Sn) ratio (SIR) on the structure of the material and photoelectrical characteristics of the Cu(In,Sn)Se₂ absorber layer. Experiment results revealed that a higher SIR following selenization increased the grain size and surface roughness of the absorber layer. It increased the quantity of secondary phases of SnSe₂ and Cu₂SnSe₃ and improved the distribution of Cu and In in the absorber layer. A higher SIR was also shown to increase electron mobility while decreasing carrier concentration and conductivity. When SIR≧0.25, the replacement of In³⁺ with Sn⁴⁺in the Cu⁺ vacancies decreased the electron strength of In. We speculate that an increase in SIR caused a relative increase in the quantity of Sn²⁺ compared to Sn⁴⁺, thereby increasing the electron strength of Sn and switching the absorber layer from a p-type to an n-type semiconductor.     

Thin Film Deposition Methods for CuInSe 2 Solar Cells

CuInSe₂ and its alloys with Ga and/or S are among the most promising absorber materials for thin film solar cells. CuInSe₂-based solar cells have shown long-term stability and the highest conversion efficiencies of all thin film solar cells, above 19%. Solar cells based on these materials are also very stable, thus allowing long operational lifetimes. The preparation of a thin film solar cell is a multistage process where every step affects the resulting cell performance and the production cost. CuInSe₂ and other Cu chalcopyrites can be prepared by a variety of methods, ranging from physical vapor deposition methods such as evaporation and sputtering to low-temperature liquid phase methods such as electrodeposition. The present review discusses first the concept and operation principle of thin film solar cells, as well as the most important thin film solar cell materials. Next, the properties of CuInSe₂ and related compounds, as well as features of solar cells made thereof are reviewed. The last part of the text deals with deposition methods used for the preparation of CuInSe₂ and Cu(In,Ga)Se₂ thin film absorbers and solar cells. Although the emphasis here is on absorber preparation methods, buffer and conducting oxide preparation are discussed as well.     

硒化前后电沉积贫铜和富铜的Cu(In1-xGax)Se2薄膜成分及结构的比较

采用电沉积法获得了接近化学计量比的贫铜和富铜的Cu（In_1-xGa_x）Se₂（CIGS）预置层,研究比较了两种预置层及其硒化处理后的成分和结构特性.得到了明确的实验证据证明,硒化后富铜薄膜中的Cu_xSe相会聚集凝结成结晶颗粒分散在表面.研究表明：在固态源硒化处理后,薄膜成分基本不变;当预置层中原子比Cu/（In+Ga）<11时,硒化后薄膜表面存在大量的裂纹;而当Cu/（In+Ga） >12时,可以消除裂纹的产生,形成等轴状小晶粒;富铜预置层硒化时蒸发沉积少量In,Ga和Se后,电池效率已达到68%;而贫铜预置层硒化后直接制备的电池效率大于2%,值得进一步深入研究. 关键词： 1-xGa_x）Se₂薄膜')" href="#">Cu（In_1-xGa_x）Se₂薄膜 电沉积 硒化处理 贫铜或富铜薄膜     

In situ investigation of the formation of Cu(In,Ga)Se2 from selenised metallic precursors by X-ray diffraction—The impact of Gallium, Sodium and Selenium excess

The chemical reactions during rapid thermal processing of stacked elemental layers were investigated by angle-dispersive in situ X-ray diffraction. With a time resolution of 5 diffractograms per minute four different solid state reactions resulting in ternary chalcopyrites were identified: (A) CuSe+InSe→CuInSe₂, (B) Cu₂Se+2InSe+Se→2CuInSe₂, (C) Cu₂Se+In2Se₃→2CuInSe₂, (D) Cu₂Se+Ga2Se₃→2CuGaSe₂. All these reactions form pure tenary chalcopyrites. The reaction resulting in the mixed crystal Cu(In,Ga)Se₂ starts not before (B) has begun. The reaction speed of (A) and the fraction of CuInSe₂ formed by (B) depend on Na-doping and Se-pressure, (C) takes place only, if the reaction paths (A) and (B) are suppressed. Reaction (D) is observed only, if 25% In is replaced by Ga in the precursor. The diffractograms were evaluated by Rietveld refinement to give the phase contents of the samples as a function of reaction time.     

低温超薄高效Cu(In,Ga)Se2太阳电池的实现

衬底温度保持恒定, 在Se气氛下按照一定的元素配比顺序蒸发Ga, In, Cu制备厚度约为0.7 μrm的Cu(In_0.7Ga_0.3)Se₂ (CIGS)薄膜. 利用X射线衍射仪分析薄膜的晶体结构及物相组成, 扫描电子显微镜表征薄膜形貌及结晶质量, 二次离子质谱仪测试薄膜内部元素分布, 拉曼散射谱 分析薄膜表面构成, 带积分球附件的分光光度计测量薄膜光学性能. 研究发现在Ga-In-Se预制层内, In主要通过晶界扩散引起Ga/(Ga+In)分布均匀化. 衬底温度高于450 ℃时, 薄膜呈现单一的Cu(In_0.7Ga_0.3)Se₂相; 低于400℃, 薄膜存在严重的Ga的两相分离现象, 且高含Ga相主要存在于薄膜的上下表面; 低于300 ℃, 薄膜结晶质量进一步恶化. 薄膜表层的高含Ga相Cu(In_0.5Ga_0.5)Se₂以小晶粒形式均匀分布于薄膜表面, 增加了薄膜的粗糙度, 在电池内形成陷光结构, 提高了超薄电池对光的吸收. 加上带隙值较小的低含Ga相的存在, 使电池短路电流密度得到较大改善. 衬底温度在550 ℃–350 ℃变化时, 短路电流密度J_SC是影响超薄电池转换效率的主要因素; 而衬底温度T_sub低于300 ℃时, 开路电压V_OC和填充因子FF降低已成为电池性能减退的主要原因. T_sub为350 ℃时制备的0.7 μm左右的超薄CIGS电池转换效率达到了10.3%. 关键词： 2薄膜')" href="#">Cu(In,Ga)Se₂薄膜 衬底温度 超薄 太阳电池