Photoluminescence study of disordering in the cation sublattice of Cu2ZnSnS4

In this study we investigated the influence of the degree of disordering in the cation sublattice on low temperature photoluminescence (PL) properties of Cu₂ZnSnS₄ (CZTS) polycrystals. The degree of disordering was changed by using different cooling rates after post-annealing at elevated temperatures. The results suggest that in the case of higher degree of cation sublattice disorder radiative recombination involving defect clusters dominates at T = 10 K. These defect clusters induce local band gap energy decrease in CZTS. The concentration of defect clusters can be reduced by giving more time for establishing ordering in the crystal lattice. As a result, radiative recombination mechanism changes and band-to-impurity recombination involving deep acceptor defect with ionization energy of about 200 meV starts to dominate in the low temperature PL spectra of CZTS polycrystals.     

Doctor-bladed Cu2ZnSnS4 light absorption layer for low-cost solar cell application

The doctor-blade method is investigated for the preparation of Cu₂ZnSnS₄ films for low-cost solar cell application. Cu₂ZnSnS₄ precursor powder, the main raw material for the doctor-blade paste, is synthesized by a simple ball-milling process. The doctor-bladed Cu₂ZnSnS₄ films are annealed in N₂ ambient under various conditions and characterized by X-ray diffraction, ultraviolent/vis spectrophotometry, scanning electron microscopy, and current-voltage (J-V) meansurement. Our experimental results indicate that (i) the X-ray diffraction peaks of the Cu₂ZnSnS₄ precursor powder each show a red shift of about 0.4°; (ii) the high-temperature annealing process can effectively improve the crystallinity of the doctor-bladed Cu₂ZnSnS₄, whereas an overlong annealing introduces defects; (iii) the band gap value of the doctor-bladed Cu₂ZnSnS₄ is around 1.41 eV; (iv) the short-circuit current density, the open-circuit voltage, the fill factor, and the efficiency of the best Cu₂ZnSnS₄ solar cell obtained with the superstrate structure of fluorine-doped tin oxide glass/TiO₂/In₂S₃/Cu₂ZnSnS₄/Mo are 7.82 mA/cm², 240 mV, 0.29, and 0.55%, respectively.     

First-principles study of elastic and thermo-physical properties of kesterite-type Cu2ZnSnS4

The lattice constants and elastic constants of the kesterite-type Cu₂ZnSnS₄ have been calculated using density-functional theory (DFT). The calculated lattice constants are in good agreement with the experimental data. The calculated elastic constants indicate that the bonding strength along the [1 0 0] and [0 1 0] directions is as strong as the one along the [0 0 1] direction. The high B/G ratio shows that the kesterite-type Cu₂ZnSnS₄ compound has ductile behavior. Finally, using the Debye model, the volume, bulk modulus and heat capacity as a function of temperature for the kesterite-type CZTS have been estimated at different pressures. The Debye temperature and Gruneisen parameter are 157 K and 2.28 at 300 K temperature, respectively. The present results can give some information for the design of the kesterite-type CZTS compounds, and these can also be used to stimulate future experimental and theoretical work.     

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.     

Electronic and optical properties of kesterite Cu2ZnSnS4 under in-plane biaxial strains: First-principles calculations

The electronic structures and optical properties of Cu₂ZnSnS₄ (CZTS) under in-plane biaxial strain were systematically investigated using first-principles calculations based on generalized gradient approximation and hybrid functional method, respectively. It is found that the fundamental bandgap at the Γ point decreases linearly with increasing tensile biaxial strain perpendicular to c-axis. However, a bandgap maximum occurs as the compressive biaxial strain is 1.5%. Further increase of compressive strain decreases the bandgap. In addition, the optical properties of CZTS under biaxial strain are also calculated, and the variation trend of optical bandgap with biaxial strain is consistent with the fundamental bandgap.     

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.     

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.     

Effects of Cu2−xS phase removal on surface potential of Cu2ZnSnS4 thin-films grown by electroplating

Cu₂ZnSnS₄ (CZTS) has an optical band gap of 1.4–1.5 eV, which is similar to that of Cu(In,Ga)Se₂ (CIGS), and a high absorption coefficient (>10⁴ cm⁻¹) in the visible light region. In previous reports, CIGS thin-film solar cells have been shown to improve the performance of the device since the secondary phase is removed by Potassium cyanide (KCN) etching treatment. Therefore, in this study we applied a KCN etching treatment on CZTS and measured the effects. We confirmed the removal of Cu_2−xS via Kelvin probe force microscopy (KPFM) and Raman scattering spectroscopy. The effects of the experiment indicate that we can define with precision the location of the secondary phases, and therefore the control of the secondary phases will be easier and more efficient. Such capabilities could improve the solar cell performance of CZTS thin-films.     

Cu2ZnSnSe4 thin films prepared by selenization of co-electroplated Cu-Zn-Sn precursors

A novel technique for growth of high quality Cu₂ZnSnSe₄ (CZTSe) thin films is reported in our work. The CZTSe thin films were fabricated onto Mo layers by co-electroplating Cu-Zn-Sn precursors followed by annealing in the selenium vapors at the substrate temperature of 550 °C. The morphology and structure of CZTSe thin films were characterized using scanning electron microscopy (SEM), energy dispersive spectrometer (EDS), X-ray diffraction (XRD) and Raman scattering spectrum, respectively. The results revealed that the single phase was in the CZTSe thin films, and the other impurities such as ZnSe and Cu₂SnSe₃ were not existed though they were difficult to distinguish both from EDS and XRD.     

n-ZnO:Al/i-ZnO/n-CdS/p-Cu2ZnSnS4太阳能电池光伏特性的分析

具有高光吸收系数的半导体Cu₂ZnSnS₄ (CZTS)薄膜是一种新型太阳能电池材料. 本文对n-ZnO:Al/i-ZnO/n-CdS/p-CZTS结构的CZTS薄膜太阳能电池进行分析, 讨论CZTS薄膜的掺杂浓度、厚度、缺陷态和CdS薄膜的掺杂浓度、 厚度对太阳能电池转换效率的影响以及太阳能电池的温度特性. 分析表明, CZTS薄膜作为太阳能电池的主要光吸收层, CZTS薄膜的掺杂浓度和厚度的取值对太阳能电池的转换效率有显著影响, CZTS薄膜结构缺陷态的存在会导致太阳能电池性能的下降. CdS缓冲层的掺杂浓度、厚度对太阳能电池光伏特性的影响较小. 经结构参数优化得到的n-ZnO:Al/i-ZnO/n-CdS/p-CZTS薄膜太阳能电池的最佳光 伏特性为开路电压1.127 V、短路电流密度27.39 mA/cm²、填充因子87.5%、 转换效率27.02%,转换效率温度系数为-0.14%/K.     

Investigations on co-evaporated Cu2SnSe3 and Cu2SnSe3-ZnSe thin films

Cu₂SnSe₃ is an important precursor material for the growth of Cu₂ZnSnSe₄, an emerging solar cell absorber layer via solid state reaction of Cu₂SnSe₃ and ZnSe. In this study, we have grown Cu₂SnSe₃ (CTSe) and Cu₂SnSe₃-ZnSe (20%) films onto soda-lime glass substrates held at 573 K by co-evaporation technique. The effect of annealing of these films at 723 K for an hour in selenium atmosphere is also investigated. XRD studies of as-deposited Cu₂SnSe₃ and Cu₂SnSe₃-ZnSe films indicated SnSe as secondary phase which disappeared on annealing. The direct optical band gap of annealed Cu₂SnSe₃ and Cu₂SnSe₃-ZnSe films were found to be 0.90 eV and 0.94 eV respectively. Raman spectroscopy studies were used to understand the effect of ZnSe on the properties of Cu₂SnSe₃.     

Study on the photovoltaic property of Cu4SnS4 synthesized by mechanochemical process

Photovoltaic property of Cu₄SnS₄ (CTS) is studied by employing a superstrate solar cell structure of Mo/CTS/In₂S₃/TiO₂/fluorine-doped tin oxide (FTO) glass for the first time. The CTS absorber layer was prepared by a combination of mechanochemical and doctor blade processes. The annealing effects on the structural, optical and electronic properties of the CTS absorber layer were investigated. The novel CTS absorber layer shows conversion efficiency as high as 2.34% under the standard AM 1.5 condition.     

Synthesis and characterization of Cu2ZnSnSe4 nanotube arrays on fluorine-doped tin oxide glass substrates

Highly ordered arrays of Cu₂ZnSnSe₄ nanotubes have been successfully synthesized on fluorine-doped tin oxide glass substrate using ZnO nanorod arrays as sacrificial templates. The structure, morphology and optical properties of the Cu₂ZnSnSe₄ arrays were characterized by X-ray diffraction, Raman spectrometry, field-emission scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray, and UV–Vis absorption spectroscopy. The diameter and length of the Cu₂ZnSnSe₄ nanotubes can be adjusted by tuning the diameter and length of the ZnO nanorods. In addition, the effect of the length on the performance of the photoelectrochemical cells was also investigated.     

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.     

Direct micron-sized LiMn2O4 particle coating on LiCoO2 cathode material using surfactant

Micron-sized LiMn₂O₄ particles were easily coated on LiCoO₂ cathodes using an amphoteric gelatin surfactant at pH4–5. The coated LiCoO₂ material showed a significantly higher thermal stability during charging and capacity retention on cycling at 4.6 V, compared to the bare LiCoO₂.     

Immobilization of glucose oxidase using CoFe2O4/SiO2 nanoparticles as carrier

Aminated-CoFe₂O₄/SiO₂ magnetic nanoparticles (NPs) were prepared from primary silica particles using modified StÖber method. Glucose oxidase (GOD) was immobilized on CoFe₂O₄/SiO₂ NPs via cross-linking with glutaraldehyde (GA). The optimal immobilization condition was achieved with 1% (v/v) GA, cross-linking time of 3 h, solution pH of 7.0 and 0.4 mg GOD (in 3.0 mg carrier). The immobilized GOD showed maximal catalytic activity at pH 6.5 and 40 °C. After immobilization, the GOD exhibited improved thermal, storage and operation stability. The immobilized GOD still maintained 80% of its initial activity after the incubation at 50 °C for 25 min, whereas free enzyme had only 20% of initial activity after the same incubation. After kept at 4 °C for 28 days, the immobilized and free enzyme retained 87% and 40% of initial activity, respectively. The immobilized GOD maintained approximately 57% of initial activity after reused 7 times. The K_M (Michaelis-Menten constant) values for immobilized GOD and free GOD were 14.6 mM and 27.1 mM, respectively.     

Luminescence of ZnWO4 and CdWO4 thin films prepared by spray pyrolysis

Thin films of ZnWO₄ and CdWO₄ were prepared by spray pyrolysis and the structural, optical, and luminescence properties were investigated. Both ZnWO₄ and CdWO₄ thin films showed a broad blue-green emission band. The broad band of ZnWO₄ films was centered at 495 nm (2.51 eV) consisted of three bands at 444 nm (2.80 eV), 495 nm (2.51 eV) and 540 nm (2.30 eV). The broad band of CdWO₄ films at 495 nm (2.51 eV) could be decomposed to three bands at 444 nm (2.80 eV), 495 nm (2.51 eV) and 545 nm (2.28 eV). These results are consistent with emission from the WO₆⁶⁻ molecular complex. The luminance and efficiency for ZnWO₄ film at 5 kV and 57 μA/cm² were 48 cd/m² and 0.22 lm/w, respectively, and for CdWO₄ film the values were 420 cd/m² and 1.9 lm/w.     

XPS investigation of diffusion of two-layer ZrO2/SiO2 and SiO2/ZrO2 sol–gel films

Two-layer ZrO₂/SiO₂ and SiO₂/ZrO₂ films were deposited on K9 glass substrates by sol–gel dip coating method. X-ray photoelectron spectroscopy (XPS) technique was used to investigate the diffusion of ZrO₂/SiO₂ and SiO₂/ZrO₂ films. To explain the difference of diffusion between ZrO₂/SiO₂ and SiO₂/ZrO₂ films, porous ratio and surface morphology of monolayer SiO₂ and ZrO₂ films were analyzed by using ellipsometry and atomic force microscopy (AFM). We found that for the ZrO₂/SiO₂ films there was a diffusion layer with a certain thickness and the atomic concentrations of Si and Zr changed rapidly; for the SiO₂/ZrO₂ films, the atomic concentrations of Si and Zr changed relatively slowly, and the ZrO₂ layer had diffused through the entire SiO₂ layer. The difference of diffusion between ZrO₂/SiO₂ and SiO₂/ZrO₂ films was influenced by the microstructure of SiO₂ and ZrO₂.     

Temperature induced band gap shrinkage in Cu2GeSe3: Role of electron-phonon interaction

The ternary semiconducting compound Cu₂GeSe₃ has been investigated for optical properties with photoacoustic spectroscopy. Optical absorption spectra of Cu₂GeSe₃ is obtained in the range of 0.76-0.81 eV photon-energy at temperatures between 80 and 300 K. The thermal variation of band gap energy has been examined from the optical absorption spectra at different temperatures. The temperature induced band gap shrinkage has been explained on the basis of electron-phonon interaction. Varshni's empirical relation in conjunction with Vina and Passler model is taken into consideration for data fitting. The Debye temperature was calculated approximately as 240 K. The acoustic phonons with a characteristic temperature as 160 K corresponding to effective mean frequency have been attributed to the thermal variation of the energy gap.     

Cathode luminescence characteristics of ZnGa2O4 phosphor thin films with the doped activator

The zincgallate (ZnGa₂O₄) phosphor thin film was grown using RF magnetron sputtering system at various process parameters. A ZnGa₂O₄ phosphor thin film was deposited on Si(1 0 0) substrate and annealed by a rapid thermal processor (RTP). The X-ray diffractometer (XRD) patterns indicate that the Mn-doped ZnGa₂O₄ phosphor thin film shows a (3 1 1) main peak and a spinel phase. A ZnGa₂O₄ phosphor thin film has better crystallization due to increased substrate, annealing temperature and deposition time. Also the ZnGa₂O₄:Mn phosphor thin film shows green emission (510 nm, ⁴T₁→⁶A₁), and the ZnGa₂O₄:Cr phosphor thin film shows red emission (705 nm, ⁴A₂→⁴T₂).