电镀法在氧化铟锡上制备铜锌锡硫薄膜的光谱特征

低成本、环境友好的铜锌锡硫替代含贵金属和有毒金属的铜铟镓硒,是薄膜太阳能电池的最佳选择。电镀法是一种无需真空设备和靶材的低成本方法。一种更简单的制膜方法是在水溶液中共电镀沉积Cu-Zn-Sn（CZT)合金于FTO衬底上。采用氩气保护气氛下在550 ℃硫化电镀法制得的CZT合金前驱体,成功制备了CZTS薄膜。采用三电极体系将CZT合金前驱体电镀在FTO上,其中FTO作为工作电极,铂（Pt）网和Ag/AgCl分别作为对电极和参比电极。电解质由CuSO₄,ZnSO₄,SnSO₄,络合剂-三乙醇胺（TEA）和柠檬酸钠组成。前驱体在氩气保护气氛下550℃硫化得到CZTS薄膜。采用X射线衍射（XRD）、拉曼光谱、扫描电子显微镜（SEM）、紫外可见光光谱仪和光电化学测量（PEC）等方法,表征了CZTS薄膜的结构、形貌、成分和光谱学性质。XRD和拉曼光谱证明了550 ℃硫化后的CZTS薄膜具有锌黄锡矿结构。一个Raman主峰位于342 cm-1,两个Raman次强峰分别位于289和370 cm-1,这些峰位与锌黄锡矿CZTS的峰位相吻合。SEM结果证明优化后CZTS薄膜成分接近CZTS的理想化学计量比,CZTS薄膜中Cu/(Zn+Sn）和 S/(Zn+Sn+Cu)分别为0.52和1.01,这表明CZTS薄膜中S的含量非常合适。PEC结果证实,采用前照射或后照射FTO/CZTS均产生光电流,并且两种照射下产生的光电流方向一致。通过紫外可见光光谱测量并由此计算出的CZTS能隙为1.45 eV。通过上述分析证明制备的CZTS薄膜具有高品质,可用于制备CZTS薄膜太阳能电池。     

Influence of solvent on solution processed Cu2ZnSnS4 nanocrystals and annealing induced changes in the optical,structural properties of CZTS film

The well-known quaternary Cu₂ZnSnS₄ (CZTS) chalcogenide thin films are playing an important role in modern technology. The CZTS nanocrystal were successfully prepared by solution method using water, ethylene glycol and ethylenediamine as different solvent. The pure phase material was used for thin film coating by thermal evaporation method. The prepared CZTS thin films were characterized by XRD, Raman spectroscopy, FESEM, XPS and FT-IR spectroscopy. The XRD and Raman spectroscopy analysis revealed the formation of polycrystalline CZTS thin film with tetragonal crystal structure after annealing at 450 ^°C. The oxidation state of the annealed film was studied by XPS. A direct band gap about 1.36 eV was estimated for the film from FT-IR studies, which is nearly close to the optimum value of band gap energy of CZTS materials for best solar cell efficiency. The CZTS annealed thin films are more suitable for using as a p-type absorber layer in a low-cost solar cell.     

碳化硅薄膜脉冲激光晶化特性研究

采用XeCl准分子激光对非晶碳化硅(a-SiC)薄膜的脉冲激光晶化特性进行了研究.通过原子力显微镜（AFM）和Raman光谱技术对退火前后薄膜样品的形貌、结构及物相特性进行了分析.结果表明，选用合适的激光能量采用激光退火技术能够实现a-SiC薄膜的纳米晶化.退火薄膜中的纳米颗粒大小随着激光能量密度的增加而增大；Raman谱分析结果显示了退火后的薄膜的晶态结构特性并给出了伴随退火过程存在的物相分凝现象.根据以上结果并结合激光退火特性，对a-SiC的脉冲激光晶化机理进行了讨论. 关键词： 激光退火 晶化 碳化硅     

Structural,morphological, compositional,and optical properties of single step electrodeposited Cu2ZnSnS4 (CZTS) thin films for solar cell application

We fabricate a Cu₂ZnSnS₄ (CZTS) absorber layer, by using single step electrodeposition of CZTS precursor, deposited at −1.05 V, followed by high temperature annealing in a sulfur atmosphere. X-ray diffraction pattern indicates that the as-grown sample is amorphous in nature, and polycrystalline CZTS thin films with kesterite crystal structure have been obtained by sulfurization from 450 to 580 °C. Surface morphologies of the as-grown sample show some voids with agglomerated particles. After sulfurization, the morphologies of the annealed samples become more uniform, and dense. EDAX study reveals that the sulfurized samples are nearly stoichiometric, being Cu-rich and S-deficient in composition. The band gaps of the annealed samples are found to be in the range from 1.9 to 1.5 eV.     

单靶溅射制备铜锌锡硫薄膜及原位退火研究

采用衬底加热溅射铜锌锡硫(CZTS)四元化合物单靶制备CZTS薄膜,并研究原位退火对制备薄膜的影响.结果表明:在溅射结束后快速升温并保持一段时间,所得到的样品相比于未原位退火的CZTS薄膜结晶质量更好,且表面更平整致密;原位退火后的CZTS薄膜太阳电池性能参数也相应地有所提升,其开路电压(V_(OC))为575 mV,短路电流密度(J_(SC))为8.32 mA/cm~2,光电转换效率达到1.82%.     

Enhancement of photosensitivity in bismuth doped Cu2ZnSnS4 thin films

In this paper, the effect of bismuth doping on the structural, morphological, optical and electrical properties of Cu₂ZnSnS₄ (CZTS) films has been investigated. The undoped and bismuth doped CZTS films (0, 0.5, 1, 1.5 and 2 mol%) were deposited on glass substrates by solution based method. The XRD result shows a significant improvement in the crystallinity of the films with increase in bismuth concentration. The Raman spectra of the films show the dominant peak at 334 cm^–1 corresponding to A₁ vibrational mode of CZTS kesterite phase. The FESEM micrographs of the films show an enhancement in the grain size and densification with the addition of bismuth ion concentration. The optical bandgap of the films was found to vary (1.59–1.40 eV) with the doping of bismuth ions. The I –V characteristics indicate twofold increment in the photoconductivity for the bismuth doped CZTS films under 100 mW/cm² illumination suggesting their potential application in photovoltaic devices. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Effect of complexing agent on the properties of electrochemically deposited Cu2ZnSnS4 (CZTS) thin films

The Cu₂ZnSnS₄ (CZTS) thin films have been electrochemically deposited on Mo-coated glass substrate from weak acidic medium (pH 4.5-5) at room temperature. The effect of complexing agent (tri-sodium citrate) on the structural, morphological and compositional properties of CZTS thin films has been investigated. The as-deposited and annealed thin films were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM),EDAX and X-ray photoelectron spectroscopy (XPS) techniques for their structural, morphological, compositional and chemical properties, respectively. XRD studies reveal that the amorphous nature of as-deposited thin film changes into polycrystalline with kesterite crystal structure after annealing in Ar atmosphere. The film prepared without complexing agent showed well-covered surface morphology on the substrate with some cracks on the surface of the film whereas those prepared using complexing agent, exhibited uneven and slightly porous and some overgrown particles on the surface of the films. After annealing, morphology changes into the flat grains, uniformly distributed over the entire surface of the substrate. The EDAX and XPS study reveals that the films deposited using 0.2 M tri-sodium citrate are nearly stoichiometric.     

Characterization of RuO2 thin films by Raman spectroscopy

Raman scattering has been used as a technique for the characterization of RuO₂ thin films deposited on different substrates by the metal-organic chemical vapor deposition method and reactive sputtering under various conditions. Red shift and broadening of the linewidth of the Raman peaks are analyzed by the spatial correlation model. The intrinsic linewidth for the RuO₂ films deposited at high and low temperatures has to be adjusted to different values to achieve a good fit for the features. The lineshape and position of the Raman features vary for films deposited on different substrates under the same condition. These differences indicate the existence of stress induced by lattice mismatch and the differential thermal expansion coefficients between RuO₂ and the substrates. After annealing at 650°C in an oxygen atmosphere for 3 h, the linewidth decreases significantly for the RuO₂ thin films deposited at lower temperatures. The results show the improvement of the crystallinity of the films during the annealing process.     

Preparing Cu₂ZnSnS₄ films using the co-electrodeposition method with ionic liquids

Cu₂ZnSnS4（CZTS） films are successfully prepared by co-electrodeposition in aqueous ionic solution and sulfurized in elemental sulfur vapor ambient at 400 C for 30 min using nitrogen as the protective gas.It is found that the CZTS film synthesized at Cu/（Zn+Sn）=0.71 has a kesterite structure,a bandgap of about 1.51 eV,and an absorption coefficient of the order of 10 4 cm 1.This indicates that the co-electrodeposition method with aqueous ionic solution is a viable process for the growth of CZTS films for application in photovoltaic devices.     

Densification study of ITO films during high temperature annealing by GISAXS

Three thermal routes were treated on the sol-gel ITO films, i.e. conventional thermal annealing (CTA), rapid thermal annealing (RTA) and thermal cycle annealing (TCA). The near surface and internal structures of films were characterized by grazing incidence small angle X-ray scattering (GISAXS) technique. It is found that slit-like pores show fractal structures laterally and the near surface is sparser with bigger pores. Ordered pore structure normal to the film appears when films are annealed at high heating rate. The shrinkage of pores is mainly owing to structural relaxation and diffusion during the superheating process. However, the supercooling process has no significant effect on the structures. Furthermore, CTA samples have the greatest porosity and surface roughness due to the prevailing crystallization as well as the coarsening procedure. However small pores inside the films are eliminated at low temperature.     

The characteristic of Cu2ZnSnS4 thin film solar cells prepared by sputtering CuSn and CuZn alloy targets

Recent study shows that the main reason for limiting CZTS device performance lies in the low open circuit voltage, and crucial factor that could affect the V_oc is secondary phases like ZnS existing in absorber layer and its interfaces. In this work, the Cu₂ZnSnS₄ thin film solar cells were prepared by sputtering CuSn and CuZn alloy targets. Through tuning the Zn/Sn ratios of the CZTS thin films, the crystal structure, morphology, chemical composition and phase purity of CZTS thin films were characterized by X-Ray Diffraction (XRD), scanning electron microscopy (SEM) equipped with an energy dispersive spectrometer (EDS) and Raman spectroscopy. The statistics data show that the CZTS solar cell with a ratio of Zn/Sn = 1.2 have the best power convention efficiency of 5.07%. After HCl etching process, the CZTS thin film solar cell with the highest efficiency 5.41% was obtained, which demonstrated that CZTS film solar cells with high efficiency could be developed by sputtering CuSn and CuZn alloy targets.     

退火对ZnO薄膜光学特性的影响

用射频磁控溅射法在蓝宝石衬底上制备出ZnO薄膜,通过X射线衍射(XRD)、扫描电镜(SEM)和光致发光(PL)谱等研究了退火温度对ZnO薄膜结构和光学性质的影响。测量结果显示,所制备的ZnO薄膜为六角纤锌矿结构,具有沿c轴的择优取向;随着退火温度的升高,(002)XRD峰强度和平均晶粒尺寸增大,(002)XRD峰半高宽(FWHM)减小,光致发光紫外峰强度增强。结果证明,用射频磁控溅射法通过适当控制退火温度可得到高质量ZnO薄膜。     

Preparing Cu2ZnSnS4 films using the co-electro-deposition method with ionic liquids

Cu2ZnSnS4（CZTS） films are successfully prepared by co-electrodeposition in aqueous ionic solution and sulfurized in elemental sulfur vapor ambient at 400 C for 30 min using nitrogen as the protective gas.It is found that the CZTS film synthesized at Cu/（Zn＋Sn）=0.71 has a kesterite structure,a bandgap of about 1.51 eV,and an absorption coefficient of the order of 10 4 cm 1.This indicates that the co-electrodeposition method with aqueous ionic solution is a viable process for the growth of CZTS films for application in photovoltaic devices.     

钛-硅系快速热退火固相反应机制的研究

钛膜在10^-7Torr真空中用电子束蒸发沉积在硅单晶片上,以快速热退火方式进行团相反应。转靶X射线衍射分析发现,540—600℃退火后,有两个亚稳相Ti₅Si₄的衍射峰。延长退火时间,第一成核相Ti₅Si₄可持续存在到钛被消耗完,随即转变成稳定相TiSi₂。退火温度高于640℃,形成稳定相TiSi₂。薄层电阻和喇曼散射的测量研究结果表明,与X射线衍射有很好的对应。207和244cm^-1波数处的两个喇曼峰为TiSi₂的特征喇曼峰,而270,297和341cm^-1的三个喇曼峰似乎是由Ti₅Si₄引起。 关键词：     

Raman scattering study of ion implanted and C.W.-Laser annealed polycrystalline silicon

Recovery of crystallinity in ion-implanted and c.w.-laser annealed polycrystalline silicon films has been examined by the Raman spectroscopy. The variation of the Raman frequency and width with laser annealing and thermal annealing shows the presence of uniform strain in the laser annealed polysilicon. It is found that the subsequent thermal annealing releases the strain.     

退火温度对低温生长MgxZn1－xO薄膜光学性质的影响

用射频磁控溅射法在80℃衬底温度下制备出Mg_xZn_1-xO(x=0.16)薄膜，用X射线衍射(XRD)、光致发光(PL)和透射谱研究了退火温度对Mg_xZn_1-xO薄膜结构和光学性质的影响.测量结果显示，Mg_xZn_1-xO薄膜为单相六角纤锌矿结构，并且具有沿c轴的择优取向；随着退火温度的升高，(002)XRD峰强度、平均晶粒尺寸和紫外PL峰强度增大，(002)XRD峰半高宽(F 关键词： xZn_1-xO薄膜')" href="#">Mg_xZn_1-xO薄膜 射频磁控溅射 退火     

低温铝诱导晶化制备纳米晶硅薄膜的物相和光学性能研究

采用射频磁控溅射镀膜系统,在玻璃衬底上制备了非晶硅(α-Si)/铝(Al)复合薄膜,结合氮气(N₂)气氛中低温快速光热退火制备了纳米晶硅(nc-Si)薄膜;利用光学显微镜、共焦光学显微仪、X射线衍射(XRD)仪、拉曼散射光谱(Raman)仪和紫外-可见光-近红外分光光度计(UV-VIS-NIR)对纳米晶硅薄膜的表面形貌、物相及光学性能进行了表征,研究了退火工艺对薄膜性能的影响。结果表明： 300 ℃,25 min光热退火可使α-Si/Al膜晶化为纳米晶硅薄膜,晶化率为15.56%,晶粒尺寸为1.75 nm;退火温度从300 ℃逐渐升高到400 ℃,纳米晶硅薄膜晶粒尺寸、晶化率、带隙逐渐增加,表面均匀性、晶格畸变量逐渐减小;退火温度从400 ℃逐渐升高到500 ℃,纳米晶硅薄膜的晶粒尺寸、晶化率继续增加,带隙则逐渐降低;采用纳米晶硅薄膜的吸光模型验证了所制备的纳米晶硅薄膜的光学特性,其光学带隙的变化趋势与吸光模型得出的结果一致。     

The effect of thermal annealing and laser irradiation on the microstructure of vanadium oxide nanotubes

The microstructure of vanadium oxide nanotubes (VONTs) have been characterized using FTIR spectroscopy and Raman spectroscopy. The temperature effects on the VONTs were studies by changing the laser irradiation power and thermal annealing temperature in air. Raman spectroscopy studies showed that the VONTs could be decomposed even at low laser power irradiation. Also, together with scanning electron microscopy, it was found that thermal annealing in air could lead to the collapse of the tubular structure and convert the nanotubes into V₂O₅ nanoparticle. It was found that the thermal stability of VONTs was relatively low and the tubular morphology was destroyed at temperatures higher than 300 °C. The spectroscopic analyses showed that the Raman signature of the VONTs could be established for probing tubular structure.     

The effects of thermal annealing on the obliquely deposited Ag-Ge-S thin films

Obliquely deposited thin films of ternary Ag-Ge-S glasses are characterized in this work. Thin films are fabricated in a vacuum thermal evaporator at different evaporation angles and examined by Raman spectroscopy. The Raman mode frequency of GeS₄ corner-sharing (CS) structure of the as-deposited films display a red-shift as a function of Ag content due to reduced global connectivity, and therefore decreased network stress. Film thickness of normally deposited thin films is significantly less when compared against obliquely deposited ones. Sulfur-ring (S₈) modes are observed in thin films but not in corresponding bulk material. Thermal annealing of thin films results in the disappearance of Sulfur-ring (S₈) modes, while the temperature required for this phenomenon is deposition angle dependent. Thickness of the obliquely deposited films shrinks significantly after thermal annealing, which indicates a collapse of the micro-column structure introduced by oblique deposition.     

Raman scattering and disorder effect in Cu2ZnSnS4

The Raman spectra of surface regions of bulk Cu₂ZnSnS₄ (CZTS) samples with different Cu and Zn cation content were obtained and the differences in the spectra are attributed to statistical disorder effects in the cation sublattice. This disorder in the Cu and Zn sublattices may initiate a change of the crystal symmetry from kesterite‐type $({I\bar 4})$ to $({I\bar 42m})$ space group. The investigated CZTS crystals grown at high temperature are characterised by the co‐existence of regions with different composition ratio of Cu/(Zn + Sn) which results in kesterite and disordered kesterite phases. The presence of a disordered phase with ${I\bar 42m}$ symmetry is reflected in the appearance of a dominant broadened A‐symmetry peak at lower frequency than the peak of the main A‐symmetry kesterite mode at 337 cm^–1. We suppose that due to a small energy barrier between these phases the transition from one phase to the other can be stimulated by optical excitation of Cu₂ZnSnS₄. The analysis of the Raman spectra measured under different excitation conditions has allowed obtaining first (to our knowledge) experimental evidence of the existence of such optically induced structural transition in CZTS. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)