连续离子层吸附反应沉积后硫化法制备柔性铜锌锡硫薄膜太阳电池

在柔性钼箔衬底上采用连续离子层吸附反应法(successive ionic layer absorption and reaction)制备ZnS/Cu2SnSx叠层结构的预制层薄膜,预制层薄膜在蒸发硫气氛、550 C温度条件下进行退火得到Cu2ZnSnS4吸收层.分别采用EDS,XRD,Raman,SEM表征吸收层薄膜的成分、物相和表面形貌.结果表明,退火后薄膜结晶质量良好,表面形貌致密.用在普通钠钙玻璃上采用相同工艺制备的CZTS薄膜表征薄膜的光学和电学性能,表明退火后薄膜带隙宽度为1.49 eV,在可见光区光吸收系数大于104cm 1,载流子浓度与电阻率均满足薄膜太阳电池器件对吸收层的要求.用上述柔性衬底上的吸收层制备Mo foil/CZTS/CdS/i-ZnO/ZnO:Al/Ag结构的薄膜太阳电池得到2.42%的效率,是目前报道柔性CZTS太阳电池最高效率.     

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.     

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.     

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。     

Band gap tunable and improved microstructure characteristics of Cu2ZnSn(S1−x,Sex)4 thin films by annealing under atmosphere containing S and Se

Cu₂ZnSn(S_xS_1?x)₄ (CZTSSe) thin films were prepared by annealing a stacked precursor prepared on Mo coated glass substrates by the sputtering technique. The stacked precursor thin films were prepared from Cu, SnS₂, and ZnS targets at room temperature with stacking orders of Cu/SnS₂/ZnS. The stacked precursor thin films were annealed using a tubular two zone furnace system under a mixed N₂ (95%) + H₂S (5%) + Se vaporization atmosphere at 580 °C for 2 h. The effects of different Se vaporization temperature from 250 °C to 500 °C on the structural, morphological, chemical, and optical properties of the CZTSSe thin films were investigated. X-ray diffraction patterns, Raman spectroscopy, and X-ray photoelectron spectroscopy results showed that the annealed thin films had a single kesterite crystal structure without a secondary phase. The 2θ angle position for the peaks from the (112) plane in the annealed thin films decreased with increasing Se vaporization temperature. Energy dispersive X-ray results showed that the presence of Se in annealed thin films increased from 0 at% to 42.7 at% with increasing Se vaporization temperatures. UV–VIS spectroscopy results showed that the absorption coefficient of all the annealed thin films was over 10⁴ cm^?1 and that the optical band gap energy decreased from 1.5 eV to 1.05 eV with increasing Se vaporization temperature.     

Effect of cobalt doping and annealing on properties of titania thin films prepared by sol-gel process

Undoped and cobalt doped titania (TiO₂) thin films have been prepared on Si(1 0 0) monocrystal and quartz substrate using the sol-gel deposition method and annealed in air at 450, 550, 650, 750, 850, 950 and 1050 °C. Several experimental techniques (AFM, XRD, Raman spectroscopy, XRR, EDX, XPS, XAS, UV-VIS spectroscopy) have been used to characterize these films. Further more the degree of light induced hydrophilicity was estimated by measuring the contact angle of a water droplet on the film. Increase of the annealing temperature and in smaller degree also cobalt doping predispose titania crystallite growth. The rutile phase was detected at lower temperatures in the cobalt doped films than in the undoped titania films. Cobalt in the cobalt doped TiO₂ was seen to be in Co²⁺ oxidation state, mainly in CoTiO₃ phase when films were annealed at temperatures higher than 650 °C. Cobalt compounds segregated into the sub-surface region and to the surface of the titania, where they formed islands. Cobalt doping red-shifted the fundamental absorption edge further into the visible range, however it did not enhance the light induced hydrophilicity of the thin film surface as compared to the undoped titania thin films.     

A comparative study of the physical properties of Sb2S3 thin films treated with N2 AC plasma and thermal annealing in N2

As-deposited antimony sulfide thin films prepared by chemical bath deposition were treated with nitrogen AC plasma and thermal annealing in nitrogen atmosphere. The as-deposited, plasma treated, and thermally annealed antimony sulfide thin films have been characterized by X-ray diffraction (XRD), energy dispersive X-ray spectroscopy, scanning electron microscopy, atomic force microscopy, UV-vis spectroscopy, and electrical measurements. The results have shown that post-deposition treatments modify the crystalline structure, the morphology, and the optoelectronic properties of Sb₂S₃ thin films. X-ray diffraction studies showed that the crystallinity of the films was improved in both cases. Atomic force microscopy studies showed that the change in the film morphology depends on the post-deposition treatment used. Optical emission spectroscopy (OES) analysis revealed the plasma etching on the surface of the film, this fact was corroborated by the energy dispersive X-ray spectroscopy analysis. The optical band gap of the films (E_g) decreased after post-deposition treatments (from 2.36 to 1.75 eV) due to the improvement in the grain sizes. The electrical resistivity of the Sb₂S₃ thin films decreased from 10⁸ to 10⁶ Ω-cm after plasma treatments.     

Carbon anode thin films for lithium batteries

This paper describes a simple method to create carbon anode films for potential applications to the research field of lithium batteries. Carbon films were prepared using DC magneton sputtering with post-annealing process in the range from room temperature (RT) to 700 °C. Half cells assembled with lithium foils as the counter electrode and 1 M LiPF₆ in EC:DMC (1:1 v/v) electrolytic solution was used to evaluate the discharging capacity of prepared anode thin films. We showed that carbon film deposited at RT can be more suitable for an anode material than that of higher temperature annealed films above 400 °C. A variety of analysis methods including X-ray diffraction spectrometry (XRD), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy were utilized to evaluate the defect density of the films; for example, the more defects on the film were identified when the carbon film was treated at a low temperature such as RT. It is envisioned that DC magnetron-sputtering with optimized process conditions can be useful for fabricating carbon based film anodes.     

Sulfurization temperature effects on the growth of Cu2ZnSnS4 thin film

We made Cu₂ZnSnS₄ (CZTS) thin films by sulfurization of Cu/Sn/Cu/Zn metallic films. Sulfurizations were carried out under different thermal annealing conditions, where maximum temperatures were 440 °C (LT-CZTS) and 550 °C (HT-CZTS). For LT-CZTS films, secondary phases such as SnS₂ and Cu_2?xS were observed, whereas for HT-CZTS films secondary impurities were not detected. Chemical composition of LT-CZTS film was observed to be very non-uniform. Highly Sn-rich and Zn-rich regions were found on the film surface of LT-CZTS. However, averaged chemical composition for larger area was close to stoichiometry. The HT-CZTS film showed homogeneous structural and chemical composition features. But, for HT-CZTS film, the Sn composition was observed to be decreased, which was due to the Sn-loss. By UV–Visible spectroscopy, optical band gaps of LT- and HT-CZTS films were measured to be ～1.33 eV and ～1.42 eV, respectively. The band gap of LT-CZTS film was also observed to be smaller by photoluminescence measurement. The depressed band gap of LT-CZTS film may be ascribed to some defects and low band gap impurities such as Cu₂SnS₃ and Cu_2-xS in the LT-CZTS film.     

Electrochemical deposition of quaternary Cu2ZnSnS4 thin films as?potential solar cell material

Quaternary compound semiconductor Cu₂ZnSnS₄ (CZTS), which appears to be a promising candidate for the absorber of a thin film type solar cell, was grown on polycrystalline Ag substrates by electrochemical epitaxial method. The elements were deposited in the following sequence: S/Sn/S/Cu/S/Zn/S/Cu… , the order being one cycle of SnS, one cycle of ZnS and two cycles of CuS. Morphology of the deposit has been characterized by field emission scanning electron microscopy (FE-SEM) with an energy dispersive X-ray (EDX) analyzer. X-ray diffraction (XRD) studies showed a (112) preferred orientation for the deposit. X-ray photoelectron spectroscopy (XPS) of the deposit indicated an approximate ratio 2:1:1:4 of Cu, Zn, Sn, and S, the expected stoichiometry for the deposit, and similar results have been obtained from EDX data. Near IR absorption measurements of the deposit at room temperature indicated a direct band gap of 1.5 eV, and open-circuit potential (OCP) studies indicated a good p-type property, both of which were suitable for fabricating a thin film solar cell.     

Influence of temperature annealing on optical properties of SrTiO3/BaTiO3 multilayered films on indium tin oxide

We have prepared SrTiO₃/BaTiO₃ thin films with multilayered structures deposited on indium tin oxide (ITO) coated glass by a sol-gel deposition and heating at 300-650 °C. The optical properties were obtained by UV-vis spectroscopy. The films show a high transmittance (approximately 85%) in the visible region. The optical band gap of the films is tunable in the 3.64-4.19 eV range by varying the annealing temperature. An abrupt decrease towards the bulk band gap value is observed at annealing temperatures above 600 °C. The multilayered film annealed at 650 ° C exhibited the maximum refractive index of 2.09-1.91 in the 450-750 nm wavelength range. The XRD and AFM results indicate that the films annealed above 600 ° C are substantially more crystalline than the films prepared at lower temperatures which were used to change their optical band gap and complex refractive index to an extent that depended on the annealing temperature.     

Compatibility and optoelectronic of ZnSe nano crystalline thin film

We report the room temperature synthesis of zinc selenide (ZnSe) nano crystalline thin film on quartz by using a relatively simple and low cost closed space sublimation process (CSSP). The compatibility of the prepared thin films for optoelectronic applications was assessed by X-ray diffraction (XRD), atomic force microscope (AFM), scanning electron microscope (SEM), Raman spectroscopy, photoluminescence, and Fourier transform infrared spectroscopy (FT-IR). The XRD confirmed that the films were polycrystalline with the preferential orientation along the (111) plane corresponding to the cubic phase (2θ = 27.28 ). The AFM indicated that the ZnSe film presented a smooth and compact morphology with RMS roughness 19.86 nm. The longitudinal optical phonon modes were observed at 247 cm 1 and 490 cm 1 attributed to the cubic structured ZnSe. The Zn-Se stretching band was confirmed by the FT-IR. The microstructure and compositional analysis was made with the SEM. The grain size, dislocation density, and strain calculated were co-related. All these properties manifested a good quality, high stability, finely adhesive, and closely packed structured ZnSe thin film for optoelectronic applications.     

Surface and bulk properties of CuGaSe2 thin films

Using complementary techniques, namely X-ray fluorescence (XRF) and X-ray photoelectron spectroscopy (XPS), we present a comparative study of the bulk and surface composition in device grade CuGaSe₂ (CGSe) thin films. The films were deposited in two stages by an open-tube chemical vapor deposition (CVD) process. The first stage leads to a nearly stoichiometric polycrystalline CGSe film of approximately 1.5 μm thickness. During the second stage the film is annealed in a Ga- and Se-rich atmosphere. While the XRF-data show a nearly stoichiometric integrated film composition, the surface composition, as determined by XPS analysis, is Cu-poor, pointing towards a highly non-stoichiometric surface layer. In addition, sodium was found at the film surfaces. The data are discussed in the framework of an ordered defect compound formation and the formation of a (Cu,Na)–Ga–Se compound at the surface of the CuGaSe₂ films. Complementary ultraviolet photoelectron- and inverse photoelectron spectroscopy investigations of the film surface derive a widening of the surface energy band gap up to 2.2 eV in comparison with a bulk energy band gap around 1.65 eV (obtained by optical transmission analysis). The observed data are consistent with our model of a two layer film structure containing a defect-rich near-surface region and a defect-poor bulk.     

Annealing effects on microstructural and optical properties of Nanostructured-TiO2 thin films prepared by sol-gel technique

In this paper we report on the effect of annealing on the microsctructural and optoelectronic properties of titanium dioxide (TiO₂) thin films prepared using sol-gel method onto silicon (Si) (100) and quartz substrates. The annealing temperatures range from 200 to 1000 °C. The Microstructural properties of annealed thin films were investigated by Thermal gravimetric analyses (TGA), X-ray diffraction (XRD) and Raman Spectroscopy. The surface morphology of the film was examined using Atomic Force Microscopy (AFM) method. The optical properties of TiO₂ thin films were characterized using UV-VIS and Spectroscopic ellipsometry. The results have shown that the TiO₂ thin films persist in the anatase phase even after annealing at 800 °C. The phase transformation from anatase to rutile occurred only when the films were annealed at 1000 °C. AFM studies revealed nanocrystalline structure where their shape and density depend strongly on the annealing temperatures. The elaborated nanostructured-TiO₂ thin films present a high transparency in the visible range. Spectroscopic ellipsometry (SE) study was used to determine the effect of annealing temperature on the thickness and on the optical constant of TiO₂ thin films. Spectroscopic ellipsometry and UV-VIS shows that the band gap of TiO₂ thin films was found to decrease when the annealing temperature increases. The Anatase phase was find to show higher photocatalytic activity than the rutile one.     

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.     

Influence of 120 MeV Si9+ ion irradiation on ZnTe semiconductor thin films

ABSTRACT

ZnTe (Zinc Telluride) is a potential semiconducting material for many optoelectronic devices like solar cells and back contact material for CdTe-based solar cells. In the present study, ZnTe thin films were prepared by thermal evaporation technique and then irradiated with 120?MeV Si⁹⁺ ions at different fluences. These films are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and UV–Visible spectroscopy techniques. XRD study confirms increased crystallinity and grain growth for post-irradiated ZnTe thin films for fluences, up to 1?×?10¹¹ ions cm^?2. However, the grain size and crystallinity decreased for higher fluence-exposed samples. SEM images confirm the observed structural properties. Modification of the surface morphology of the film due to the ion irradiation with different fluences is studied. Optical band gap of film is decreased from 2.31?eV (pristine) to 2.17?eV after irradiation of Si⁹⁺ ions.     

Polyvinylpyrrolidone (PVP) assisted single‐step synthesis of kesterite Cu2ZnSnS4 nanoparticles by solvothermal process

Quaternary kesterite‐type Cu₂ZnSnS₄ (CZTS) nanoparticles (NPs) were successfully synthesized by a single‐step solvothermal process. Semiconductor CZTS nanoparticles were obtained from ethylene glycol (EG) and CZTS precursor after solvothermal process at 180 °C for 30 h in polyvinylpyrrolidone (PVP) medium. The synthesized CZTS NPs were further annealed at 450 °C in nitrogen atmosphere and used for further characterizations. The CZTS NPs were characterized using X‐ray powder diffraction (XRD), field emission scanning electron microscopy (FESEM), micro Raman spectroscopy, high resolution transmission electron microscopy (HRTEM) and X‐ray photoelectron spectroscopy (XPS). The optical properties of the CZTS NPs were recorded by UV–vis absorption spectroscopy. The results showed that the synthesized CZTS nanoparticles are kesterite‐type CZTS, with good crystallinity and a stoichiometric composition. Moreover, the prepared nanoparticles have a size ranging from 5–7 nm and a band gap of ～1.5 eV.

     

Influence of deposition conditions on nanostructured InSe thin films

In this study, nanostructured indium selenide (InSe) thin films were deposited on Indium tin oxide (ITO)-coated glass substrate using electrochemical deposition (ECD) from aqueous solution containing In(SO₄)₃.H₂O and SeO₂. The effects of deposition potential (−0.70 to −1.35 V), time (30-3600 s), temperature (25-80 °C) and pH (2.58 for A samples; 2 for B samples and 1.45 for C samples) on growth of the InSe thin films were examined in terms of their structural, morphological and optical properties. X-ray diffraction (XRD) analysis confirmed that the InSe thin films are in polycrystalline structure. It was found that the values of grain size decreased and the full width half maximum (FWHM) values increased with the increasing deposition potential. According to the absorption measurements, optical properties of the thin films varied with changes in deposition conditions. Based on the atomic force microscopy (AFM) and the scanning electron microscopy (SEM) images, surface morphology of the thin films was influenced by deposition potential and pH of the electrolyte, and non-homogeneous depositions distributed across the entire surface were observed. In addition, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and fourier transform infrared spectroscopy (FT-IR) analyses were used to further examine crystal quality, vibration, chemical binding conditions, In/Se orientation and structure of the prepared InSe thin films. When Raman results are examined, the B12 sample shows a more intensity and narrow peak at 248 cm⁻¹. XPS measurements sowed that A6 sample exhibited more growth in low potential for a long time and better film stoichiometry compared to the other three samples. Also, FT-IR studies prove the presence of InSe. According to the results, the film did not form at low temperatures and short times. However, the film formation began with the increasing deposition temperature and time at the low potential value of −0.730 V. But, it is clear that a high quality film can be obtained in cathodic potential with −1.3 V and shorter deposition time with 300 s at room temperature respectively. Overall results showed that the high quality thin films can be obtained by the ECD technique. However, deposition conditions must be sensitively adjusted to control morphology of the electrodeposited nanoparticles.     

Effect of Fe3+ doping on structural,optical and electrical properties δ-Bi2O3 thin films

Fe³⁺ doped δ-Bi₂O₃ thin films were prepared by sol–gel method on quartz glass substrate at room temperature and annealed at 800 °C. The thin films were then characterized for structural, surface morphological, optical and electrical properties by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), optical absorption measurements and d.c. two-probe, respectively. The XRD analyses revealed the formation δ-Bi₂O₃ followed by a mixture of Bi₂₅FeO₄₀ and Bi₂Fe₄O₉. SEM images showed reduction in grain sizes after doping and the optical studies showed a direct band gap which reduced from 2.39 eV for pure δ-Bi₂O₃ to 1.9 eV for 10% Fe³⁺ doped δ-Bi₂O₃ thin film. The electrical conductivity measurement showed the films are semiconductors.     

Properties of Cu2ZnSn(SxSe1−x)4 thin films prepared by one-step sulfo-selenization of alloyed metal precursors

The pentenary system, Cu₂ZnSn(S_xSe_1−x)₄ (CZTSSe), is a promising alternative for thin film solar cells. In this study, CZTSSe thin films were prepared using a two-stage process involving the thermal diffusion of sulfur (S) and selenium (Se) vapors into sputtered metallic precursors at approximately 450 °C. The effects of the sulfur content on the composition, structure, optical and electrical characteristics of the CZTSSe thin films were investigated. The films showed a kesterite structure with a predominant (112) orientation. X-ray diffraction and Raman spectroscopy confirmed the formation of a single phase CZTSSe compound. The band gap was dependent on the sulfur content and was calculated to be 1.25 eV, 1.33 eV and 1.40 eV for CZTSSe films with a S/(S + Se) ratio of 0.3, 0.5 and 0.7, respectively. All films exhibited p-type semiconductor properties.