Phase relations and optical properties of semiconducting ternary sulfides in the system Cu–Sn–S

The ternary system Cu–Sn–S was re-investigated and the phase diagram Cu₂S–SnS₂ studied in detail by differential thermal analysis and X-ray diffractometry. Three phases of composition Cu₄SnS₄, Cu₂SnS₃ and Cu₂Sn_3+xS_7+2x(0≤×≤1) were found exhibiting melting points at 833, 856 and 803 °C, respectively. Ellipsometric and diffuse reflectance measurements revealed that the latter two sulfides possess a fundamental band gap of 0.93 eV followed by a higher transitions. For the first time it could be demonstrated that Cu₂Sn₃S₇ has semiconducting properties and an absorption coefficients of the order 10⁵ cm⁻¹.     

Synthesis of earth-abundant Cu2SnS3 powder using solid state reaction

Cu₂SnS₃ (CTS) powder has been synthesized at 200 °C by solid state reaction of pastes consisting of Cu and Sn salts and different sulphur compounds in air. The compositions of the products is elucidated from XRD and only thiourea is found to yield CTS without any unwanted CuS_x or SnS_y. Rietveld analysis of Cu₂SnS₃ is carried out to determine the structure parameters. XPS shows that Cu and Sn are in oxidation states +1 and +4, respectively. Morphology of powder as revealed by SEM shows the powder to be polycrystalline with porous structure. The band gap of CTS powder is found to be 1.1 eV from diffuse reflectance spectroscopy. Cu₂SnS₃ pellets are p-type with electrical conductivity of 10⁻² S/cm. The thermal degradation and metal–ligand coordination in CTS precursor are studied with TGA/DSC and FT-IR, respectively, and a probable mechanism of formation of CTS has been suggested.     

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.     

Optical characterization of band gap graded ZnMgO films

We investigated the optical properties of compositionally graded Zn_1?xMg_xO (g-ZnMgO) films using spectroscopic ellipsometry. The g-ZnMgO and ZnO films were grown on Pt/Ti/SiO₂/Si substrates by ultrasonic spray pyrolysis. We simulated a uniformly graded optical band gap layer on the Pt substrate to reproduce the experimental result. The band gap of the bottommost layer of the g-ZnMgO film was estimated to be ～3.22 eV, the same as the undoped ZnO film. Then we considered a linearly increasing band gap with the film composition, and obtained a band gap of ～3.56 eV for the topmost layer of the film. In addition, the exciton peak showed a strong increase for the topmost layer of the film suggesting an important role of doping.     

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.     

一种印刷型薄膜太阳能电池p-n结调制技术

能带值为0.5~0.85 eV材料的稀缺是多结太阳能电池面临的一个主要挑战,本文使用非真空的机械化学法合成了能带值为0.83 eV的Cu₂SnS₃化合物,使用印刷技术将其制备成吸收层薄膜,并采用superstrate太阳能电池结构(Mo/Cu₂SnS₃/In₂S₃/TiO₂/FTO glass)对其光伏特性进行了研究.实验表明所制备的太阳能电池短路电流密度、开路电压、填充因子和转换效率分别为12.38 mA/cm²、320 mV、0.28和1.10%.此外,为更好地满足多结太阳能电池对电流匹配的需求,本文对所制备太阳能电池的Cu₂SnS₃/In₂S₃ p-n结进行了分析.通过在p-n结界面植入一层薄的疏松缓冲层,使调制后的太阳能电池短路电流密度从最初的12.38 mA/cm²增加到了23.15 mA/cm²,相应太阳能电池转换效率从1.1%增加到了1.92%.该p-n调制技术对印刷型薄膜太阳能电池具有重要借鉴意义.     

Microwave-assisted rapid synthesis of tetragonal Cu2SnS3 nanoparticles for solar photovoltaics

A simple and rapid process for the synthesis of Cu₂SnS₃ (CTS) nanoparticles by microwave heating of metal–organic precursor solution is described. X-ray diffraction and Raman spectroscopy confirm the formation of tetragonal CTS. X-ray photoelectron spectroscopy indicates the presence of Cu, Sn, S in +1, +4, ?2 oxidation states, respectively. Transmission electron microscopy divulges the formation of crystalline tetragonal CTS nanoparticles with sizes ranging 2–25 nm. Diffuse reflectance spectroscopy in the 300–2,400 nm wavelength range suggests a band gap of 1.1 eV. Pellets of CTS nanoparticles show p-type conduction and the carrier transport in temperature range of 250–425 K is thermally activated with activation energy of 0.16 eV. Thin film solar cell (TFSC) with architecture: graphite/Cu₂SnS₃/ZnO/ITO/SLG is fabricated by drop-casting dispersion of CTS nanoparticles which delivered a power conversion efficiency of 0.135 % with open circuit voltage, short circuit current and fill factor of 220 mV, 1.54 mA cm^?2, 0.40, respectively.     

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.     

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.     

N掺杂Cu2O薄膜的光学性质及第一性原理分析

采用射频磁控溅射技术, 在不同温度下制备了N掺杂Cu₂O薄膜．透射光谱分析发现, N掺杂导致Cu₂O成为允许的带隙直接跃迁半导体, 并使Cu₂O的光学禁带宽度增加．不同温度下沉积的薄膜光学禁带宽度E_g=2.52± 0.03 eV．第一性原理计算表明, N掺杂导致Cu₂O的禁带宽度增加了约25%, 主要与价带顶下移和导带底上移有关, 与实验报道基本符合．N的2p电子态分布不同于O原子, 在价带顶附近具有较大的态密度是N掺杂Cu₂O变成允许的带隙直接跃迁半导体的根本原因．     

Oxide films of copper prepared by the oxidation of copper sulphide films

Copper sulphide films prepared by reactive evaporation, when heated in air at 500 K, oxidized to Cu₂O after a series of intermediate chemical transitions. Golden yellow coloured Cu₂O films showed a large absorption before the fundamental absorption edge. The optical band gap was found to be (2.29±0.02)eV. When these Cu₂O films were further heated they got converted to CuO and the optical band gap was found to be (2.17±0.02)eV.     

Preparation of Cu2ZnSnS4 thin films by hybrid sputtering

In order to fabricate Cu₂ZnSnS₄ thin films, hybrid sputtering system with two sputter sources and two effusion cells is used. The Cu₂ZnSnS₄ films are fabricated by the sequential deposition of metal elements and annealing in S flux, varying the substrate temperature. The Cu₂ZnSnS₄ films with stoichiometric composition are obtained at the substrate temperature up to 400 °C, whereas the film composition becomes quite Zn-pool at the substrate temperature above 450 °C. The Cu₂ZnSnS₄ film shows p-type conductivity, and the optical absorption coefficient and the band gap of the Cu₂ZnSnS₄ film prepared in this experiment are suitable for fabricating a thin film solar cell.     

Photoluminescence characterization of polycrystalline n-type Cu2O films

Electrodeposition was used to deposit Cu₂O thin films on ITO substrates. Photoresponse of the film clearly indicated n-type behavior of Cu₂O in photoelectrochemical cells. The temperature dependence of photoluminescence (PL) revealed that the spectra consist of donor-acceptor pair emissions and the recombination between electrons bound to donors and free holes. We observed that the dominant intrinsic defect, oxygen vacancies, creates a donor energy level at 0.38 eV below the bottom of the conduction band. As a result, this donor level acts as a center for both PL emissions and to produce n-type conductivity in the electrodeposited Cu₂O films. In addition, an acceptor energy level at 0.16 eV from the top of the valence band was observed.     

Optical and electrical investigations on Cu2SnS3 layers prepared by two-stage process

Cu₂SnS₃ thin films were prepared using a simple and phase-controlled two-stage process. Initially, Cu-Sn precursors were deposited by DC sputtering, followed by sulfurization at different temperatures (T_s) that vary in the range, 150 - 500 °C. An exhaustive study of the optical properties in relation to sulfurization temperature was performed using transmission and reflectance measurements. The estimated optical absorption coefficient for all the layers was very high and found to be > 10⁴ cm⁻¹. The optical band gap was determined using Tauc plots and it varied in the range, 1.49–2.34 eV with an increase of T_s. The refractive index (n) and the extinction coefficient (k) were also obtained. The optical properties like dispersion parameters, dielectric constant, dissipation factor, optical conductivity, surface energy loss function, volume energy loss function and optical haze were also calculated. Further, analysis of electrical properties such as electrical resistivity, mobility and carrier density of the prepared films with sulfurization temperature was made in order to verify the suitability of synthesized CTS layers for solar cell application.     

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.     

高活性氧化亚铜薄膜材料的绿色合成研究

本文采用一步脉冲雾化化学气相沉积法在250℃下制备了氧化亚铜薄膜催化剂.实验研究了前驱体中掺杂水对氧化铜薄膜表面形貌、拓扑结构、表面成分和光学特性的影响规律.结果表明所制得的催化剂为纯相的氧化亚铜.前驱体溶液中掺杂水会导致氧化亚铜的晶粒变小,从而使得共光学能隙从2.16 eV降至2.04 eV.原子力显微镜结果表明随着水的加入,氧化亚铜的表面粗糙度降低,表面更加均匀.此外,利用密度泛函理论计算得到了水和乙醇在氧化亚铜薄膜表面的吸附和反应特性,并提出了氧化亚铜的形成机理.本文开发了一种低成本且实际可行的薄膜制造方法,该方法在太阳能电池和半导体等领域具有潜在应用.     

Growth, structural and optical properties of CdxZn1−xS thin films deposited using spray pyrolysis technique

Cd_xZn_(1−x)S (x = 0, 0.2, 0.4, 0.6, 0.8, and 1) thin films were deposited by the chemical spray pyrolysis technique using a less used combination of chemicals. Depositions were done at 573 K on cleaned glass substrates. The composition, surface morphology and structural properties of deposited films were studied using EDAX, SEM and X-ray diffraction technique. XRD studies reveal that all the films are crystalline with hexagonal (wurtzite) structure and inclusion of Cd into the structure of ZnS improved the crystallinity of the films. The value of lattice constant ‘a’ and ‘c’ have been observed to vary with composition from 0.382 to 0.415 nm and 0.625 to 0.675 nm, respectively. The band gap of the thin films varied from 3.32 to 2.41 eV as composition varied from x = 0.0–1.0. It was observed that presence of small amount of cadmium results in marked changes in the optical band gap of ZnS.     

I–V characteristics of ZnO/Cu2O thin film n–i–p heterojunction

ZnO/Cu₂O thin film n–i–p heterojunctions were fabricated by magnetron sputtering. The microstructure, optical, and electrical properties of n-type (n‐) ZnO, insulating (i‐) ZnO, and p-type (p‐) Cu₂O films deposited on glass substrates were characterized by X-Ray diffraction (XRD), spectrophotometer, and the van der Pauw method, respectively. XRD results show that the mean grain size of i-ZnO film is much larger than that of n-ZnO film. The optical band gap energies of n-ZnO, i-ZnO, and p-Cu₂O film are 3.27, 3.47, and 2.00 eV, respectively. The carrier concentration of n-ZnO film is two orders of magnitude larger than that of p-Cu₂O film. The current–voltage (I–V) characteristics of ZnO/Cu₂O thin film n–i–p heterojunctions with different i-ZnO film thicknesses were investigated. Results show that ZnO/Cu₂O n–i–p heterojunctions have well-defined rectifying behavior. All ideality factors of these n–i–p heterojunctions are larger than 2.0. The forward bias threshold voltage and ideality factor increase when i-ZnO layer thickness increases from 100 to 200 nm. An energy band diagram was proposed to analyze the I–V characteristics of these n–i–p heterojunctions.     

Electrochemical deposition and characterization of cadmium indium telluride thin films for photovoltaic application

Cd–In–Te films were electro-deposited potentiostatically over SnO₂:F coated glass substrates from aqueous acidic solutions containing CdSO₄, InCl₃ and TeO₂ at 85 °C. Cyclic voltammetric studies were carried out to study the growth process and the potential range for ternary Cd–In–Te thin film deposition. Crystalline structure and surface morphological studies were carried out and correlated with the deposition potential. The deposited film showed cubic structure having a high degree of (1 1 1) orientation. Optical transmission studies showed a direct band structure and the band gap of the deposited film change with the deposition potential. A typical decrease from 1.2 to 1.1 eV in the optical band gap was observed on increasing the cathodic deposition potential from −0.5 to −0.54 V (SCE).     

Polyethylene glycol-assisted growth of Cu2SnS3 promising absorbers for thin film solar cell applications

In this paper, we report, for the first time, the results of the polyethylene glycol- (PEG) assisted preparation and characterization of high-quality and well-crystallized Cu₂SnS₃ (CTS) thin films obtained using sol–gel spin-coating method and a subsequent annealing in a sulphur atmosphere. Structural, morphological, compositional, electrical and optical investigations were carried out. The X-ray diffraction patterns of the samples proved the polycrystalline nature and preferred crystallization of the films. No peak referring to other binary or ternary phases were detected in the patterns. The intensity of the preferred orientation and crystallite size of the films increased with increasing PEG content. This trend yielded an improvement in photo-transient currents of the PEG-assisted growth of CTS films. The scanning electron microscopy images revealed that the CTS films have continuous, dense and agglomeration-like morphology. Through energy dispersive X-ray spectroscopy studies, it has been deduced that the samples consist of Cu, Sn and S of which atomic percentages were consistent with Cu/Sn and S/metal initial ratios. The agglomerated morphology of the samples has been attributed to increasing PEG content. A remarkable enhancement was observed in photo-transient currents of p-n junction of the produced films along with increasing PEG content. Through resistivity-temperature measurements, three impurity level electrical activation energy values for each film were found. Optical band gap values of the films were estimated via absorbance-wavelength behaviours and decreased with increasing PEG content. It has been revealed that PEG-assisted growth of CTS thin films is a promising way to improve its photovoltaic characteristics.