电沉积法制备铜锌锡硫薄膜太阳能电池吸收层的研究进展

直接禁带半导体材料铜锌锡硫(CZTS)四元硫化物是近年来研究较多的具有锌黄锡矿结构的化合物半导体,由于其光吸收系数较高,禁带宽度适中,是太阳能电池理想的候选材料,使其在薄膜太阳能电池中迅速崛起。由于目前报道的最高转换效率距离其理论转换效率还存在相当差距,因此,研究CZTS(Se)四元硫(硒)化物半导体仍然是当前的研究热点之一。简单介绍了CZTS薄膜太阳能电池的结构组成,并详细介绍了3种主要制备CZTS薄膜的电沉积方法,即分步沉积Cu/Sn/Zn金属层、连续沉积Cu-Zn-Sn金属层、一步沉积Cu-Zn-Sn-S(Se)制备CZTS薄膜太阳能电池吸收层的电化学技术及相应器件,对其研究进展进行了综述,指出了相应方法存在的问题。还将3种电沉积方法进行了分析比较,提出了优化方法,展望了未来的发展趋势。     

Cu_2ZnSnS_4薄膜的研究进展

Cu2ZnSnS4(CZTS)薄膜太阳能电池具有低成本、高效率、安全无毒等优点,是最具发展前景的太阳能电池之一,近几年来开始受到广泛关注。简要介绍了国内外几种制备Cu2ZnSnS4薄膜的方法,包括蒸发法、溅射法、脉冲激光沉积法、电化学沉积法、喷涂热解法、Sol-gel法、丝网印刷法,并阐述了这几种方法的优点及存在的问题,展望了今后CZTS薄膜的研究方向,认为通过溶剂热或热注入法制备出CZTS纳米晶体后,再通过丝网印刷法或旋涂等法制成CZTS薄膜能降低生产成本,在电池的工业化生产中具有很广阔的应用前景。     

磁控溅射制备Cu2ZnSnS4薄膜的研究进展

Cu_2ZnSnS_4(CZTS)薄膜由于其合适的禁带宽度、高的光吸收系数以及组分无毒、储量丰富等特性,被视为薄膜太阳能电池最佳的吸收层材料之一。磁控溅射是制备CZTS薄膜的主要方法之一,因为其制备过程相对简单且可以产业化,一直是太阳能电池领域的研究热点。从磁控溅射制备CZTS薄膜的3种路径出发,综述了近年来各种路径在制备CZTS薄膜方面的研究进展,比较了3种路径的优缺点,同时对磁控溅射制备CZTS薄膜的发展前景进行了展望。     

Electrodeposition and characterization of Cu2S thin films from aqueous solution

An electrodeposition method was used to prepare Cu ₂S thin film deposited on Ti substrate. The effect of deposition potential, concentration and deposition time was studied to determine the optimum condition for the electrodeposition process. Cyclic voltammetry was performed to elucidate the electrodic processes that occur while potentials for electrodeposition were applied to determine the optimum potential for electrodeposition. The thin films were characterized by X-ray diffractometry. Scanning electron microscopy was performed to observe the morphology, composition and structure of the deposits. Cu ₂S showed a cubic morphology.     

Electrodeposition of gold thin films from 1-butyl-1-methylpyrrolidinium dicyanamide Au solutions

The electrodeposition of gold from a HAuCl₄.3H₂O solution in 1-butyl-1-methyl-pyrrolidinium dicyanamide is reported in the present paper. A cyclic voltammetry study of the electrochemical behaviour of the plating solution showed that the reduction of gold occurs by a two-step process. Gold thin films were obtained by electrodeposition on nickel substrates under potentiostatic control at a constant potential of − 1 V, for temperatures from 293 to 353 K and deposition times of 1500 and 4500 s. The films prepared at 293 and 333 K consist of 9-15 nm diameter polyhedral particles aggregated in clusters 50-250 nm in diameter. The films deposited at 353 K consist of a quasi-continuous film of nanoparticles covered by nanosized dendrites. This morphology evolves towards a globular structure with increasing deposition time.     

X-ray line broadening and photoelectrochemical studies on CdSe thin films

Cadmium Selenide (CdSe) thin films have been prepared on Indium doped tin oxide coated conducting glass (ITO) substrates at various deposition potential and solution pH values using potentiostatic cathodic electrodeposition technique. The deposited films are characterized using X-ray diffraction, scanning electron microscopy, energy dispersive analysis by X-rays, optical absorption, and photoelectrochemical techniques, respectively. X-ray diffraction pattern revealed that the deposited films are found to exhibit hexagonal structure with preferential orientation along (002) plane. X-ray line profile analysis technique by the method of variance has been used to evaluate the microstructural parameters such as crystallite size, rms microstrain, dislocation density, and stacking fault probability. The variation of microstructural parameters with deposition potential, solution pH values, and annealing temperature are studied. Surface morphology and film composition are investigated by scanning electron microscopy and energy dispersive analysis by X-rays, respectively. Optical absorption analysis has been carried out to evaluate the optical parameters such as refractive index, extinction coefficient, real and imaginary dielectric constants, and packing density, respectively. Photoelectrochemical solar cells are constructed using as-deposited and annealed CdSe thin films as photocathode, and their power output characteristics are studied. The experimental observations are discussed in detail.     

Sulfurization time effects on the growth of Cu2ZnSnS4 thin films by solution method

Cu₂ZnSnS₄ (CZTS) films were obtained by sulfurizing (Cu, Sn) S/ZnS structured precursors prepared by a combination of the successive ionic layer absorption and reaction method and the chemical bath deposition method, respectively. The effect of sulfurization time on structure, composition and optical properties of these CZTS thin films was studied. The results of energy dispersive spectroscopy indicate that the annealed CZTS thin films are of Cu-poor and Zn-rich states. The X-ray diffraction studies reveal that Cu_2?x S phase exists in the annealed CZTS thin film prepared by sulfurization for 20 min, while the Raman spectroscopy analysis shows that there is a small Cu₂SnS₃ phase existing in those by sulfurization for 20 and 40 min. The band gap (E _g ) of the annealed CZTS thin films, which are determined by reflection spectroscopy, varies from 1.49 to 1.56 eV depending on sulfurization time. The best CZTS thin film is the one prepared by sulfurization for 80 min, exhibiting a single kesterite structure, dense morphology, ideal band gap (E _g  = 1.55 eV) and high optical absorption coefficient (>10⁴ cm^?1).     

Dependence of the properties of copper zinc tin sulfide thin films prepared by electrochemical deposition on sulfurization temperature

Copper zinc tin sulfide (CZTS, Cu₂ZnSnS₄) is a low band gap semiconductor that is attractive for use in solar cells. We investigated the dependence of the structure and properties of CZTS thin films on the temperature used to sulfurize precursor thin films composed of copper, zinc and tin fabricated by electrochemical deposition. The precursor films were sulfurized in a furnace with three zones, which allowed fine control of the sulfurization temperature between 250 and 400 °C. X-ray diffraction and Raman spectroscopic measurements confirmed that the films were composed of CZTS following sulfurization. The grain size and crystallinity of the films increased with sulfurization temperature. The composition of CZTS also varied with sulfurization temperature. The proportions of Cu and Zn increased while that of Sn decreased with increasing sulfurization temperature. Absorption and reflectance spectra revealed that the absorption coefficients and band gaps of the CZTS films varied with sulfurization temperature between 3–4.1 × 10⁴ cm^?1 and 1.4–1.53 eV, respectively. Solar cells containing CZTS sulfurized at 400 °C showed a maximum efficiency of 2.04 %, which was attributed to the higher crystallinity and larger grain size of CTZS compared with thin films sulfurized at lower temperatures. Our results show that control of sulfurization temperature is an important factor in optimizing the performance of CZTS thin films in solar cells.     

Deposition of thin cobalt films onto silicon by galvanostatic and potentiostatic techniques

In this study, thin cobalt films were electrodeposited directly onto n-Si (100) using two different electrodeposition techniques: galvanostatic and potentiostatic. The morphological difference between galvanostatic and potentiostatic deposits was observed by atomic force microscopy (AFM) and X-ray diffraction (XRD). Analysis of the deposits by an alternating gradient field magnetometer (AGFM) showed the influence of the electrodeposition process on the magnetic properties of the film.     

Application of Taguchi approach to optimize the sol–gel process of the quaternary Cu2ZnSnS4 with good optical properties

Present research deals with the optimal deposition parameters configuration for the synthesis of Cu₂ZnSnS₄ (CZTS) thin films using the sol–gel method associated to spin coating on ordinary glass substrates without sulfurization. The Taguchi design with a L9 (3⁴) orthogonal array, a signal-to-noise (S/N) ratio and an analysis of variance (ANOVA) are used to optimize the performance characteristic (optical band gap) of CZTS thin films. Four deposition parameters called factors namely the annealing temperature, the annealing time, the ratios Cu/(Zn + Sn) and Zn/Sn were chosen. To conduct the tests using the Taguchi method, three levels were chosen for each factor. The effects of the deposition parameters on structural and optical properties are studied. The determination of the most significant factors of the deposition process on optical properties of as-prepared films is also done. The results showed that the significant parameters are Zn/Sn ratio and the annealing temperature by applying the Taguchi method.     

Cu2ZnSnS4 films by paste coating and their optoelectronic properties

Cu₂ZnSnS₄ (CZTS) thin films were prepared by a paste coating method as the absorb layer of solar cells. This method is more eco-friendly using ethanol as solvent and more convenient than traditional sol–gel method. The effects of sulfurization temperature on properties of thin film were studied. The results of X-ray diffraction and Raman spectroscopy showed the formation of kesterite structure of CZTS films. The scanning electron microscopy images revealed that CZTS thin film obtained at 550 °C were compact and uniform. The optical band gap of the CZTS film was about 1.5 eV, and the CZTS film had an obvious optoelectronic response. Moreover, CZTS solar cell was prepared with a conversion efficiency of 0.47 %.     

Electrodeposition and characterization of nano-crystalline antimony telluride thin films

Electrodeposition is a promising low-cost method to fabricate nanostructured thermoelectric thin films such as Sb₂Te₃. However, electrodeposition of crystalline Sb₂Te₃ without the need for additional processing and with good compositional control has presented a challenge. Here we report on the electrodeposition of crystalline Sb₂Te₃ thin films at room temperature from a tartaric-nitric acid electrolyte using a pulsed, potentiostatic process. The effects of synthesis conditions on the resulting microstructure and compositional homogeneity are investigated using x-ray diffraction, electron diffraction, electron microscopy, and energy dispersive x-ray spectroscopy. The composition of the Sb-Te films was found to be dependent on the interval between pulses, a result that is likely due to the slow kinetics associated with Sb₂Te₃ formation at the surface. We also observed a change in texture and microstructure with varied applied pulse duration: for short pulse durations a lamellar microstructure with a {000?} texture forms, whereas for longer pulse durations a more equiaxed and randomly oriented microstructure forms. The thermal conductivities of the pulsed electrodeposited films are surprisingly low at less than 2 W/K·m and are found to systematically decrease with reduced pulse time.     

Photoelectrochemical characterization of nanocrystalline thin-film Cu₂ZnSnS₄ photocathodes

Cu?ZnSnS? (CZTS) nanocrystals, synthesized by a hot injection solution method, have been fabricated into thin films by dip-casting onto fluorine doped tin oxide (FTO) substrates. The photoresponse of the CZTS nanocrystal films was evaluated using absorbance measurements along with photoelectrochemical methods in aqueous electrolytes. Photoelectrochemical characterization revealed a p-type photoresponse when the films were illuminated in an aqueous Eu(3+) redox electrolyte. The effects of CZTS stoichiometry, film thickness, and low-temperature annealing on the photocurrents from front and back illumination suggest that the minority carrier diffusion and recombination at the back contact (via reaction of photogenerated holes with Eu(2+) produced from photoreduction by minority carriers) are the main loss mechanisms in the cell. Low-temperature annealing resulted in significant increases in the photocurrents for films made from both Zn-rich and stoichiometric CZTS nanocrystals.     

Selenization of electrodeposited copper–indium alloy thin films for solar cell applications

Copper–Indium (Cu–In) alloys with sulfur and selenium have technological importance in the development of thin film solar cell technology. We have used potentiostatic electrochemical technique with three-electrode geometry for the deposition of Cu–In alloy thin films in an aqueous electrolyte. Cathodic voltammetry (CV) was thoroughly studied to optimize the electrodeposition parameters. The deposition potential for Cu–In alloy was found to be in the range ?0.70 to ?0.85 V versus Ag/AgCl reference electrode. Polycrystalline Cu_xIn_y thin films were electrodeposited from aqueous bath at room temperature and 45 °C. Effect of concentration of citric acid was extensively studied by CV measurements. The as-deposited Cu–In films were characterized with a range of characterization techniques to study the structural, morphological, compositional and electrical properties. Thin layers of Cu–In were selenized in a homemade tubular furnace at 400 ^°C, which reveals the formation of polycrystalline CuInSe₂ (CISe) thin films with tetragonal structure. The band gap of CISe thin film was estimated ~1.05 eV by optical absorption spectroscopy. Nearly stoichiometric CISe thin film, Cu = 25.25 %, In = 26.48 % and Se = 48.27 % was obtained after selenization. The linear behavior of current density–voltage (J–V) was observed for Cu–In alloy thin films whereas, the selenized Cu–In alloy films (CISe) possess rectifying properties.     

Cu2O薄膜的制备方法

氧化亚铜（Cu2O）薄膜在太阳能电池及其它光电器件上有重要应用,它具有无毒、制备成本低、材料广泛易得等优点。制备Cu2O薄膜的方法主要有热蒸发、溅射、化学气相沉积和电化学沉积等,本文对Cu2O薄膜的制备方法进行了综述与展望。     

Room temperature novel chemical synthesis of Cu2ZnSnS4 (CZTS) absorbing layer for photovoltaic application

Cu₂ZnSnS₄ (CZTS) thin films have been prepared by a novel chemical successive ionic layer adsorption and reaction (SILAR) method. These films were annealed in vacuum at 673 K and further characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), UV–vis spectroscopy, electrical, and wettability studies. The X-ray diffraction studies showed the formation of kesterite structure of CZTS films. Scanning electron micrograph revealed the formation of densely packed, compact and large grained CZTS films. The CZTS films showed high optical absorption (10⁴ cm^?1) exhibiting band gap energy of 1.55 eV. Wettability test revealed the hydrophilic nature of CZTS films. The CZTS thin films showed semiconducting behavior with p-type electrical conductivity. Further photovoltaic activity of these films was studied by forming the photoelectrochemical cell.     

Low-cost fabrication of Cu2ZnSnS4 thin films for solar cell absorber layers

A new and low-cost chemical method is used to fabricate Cu₂ZnSnS₄ (CZTS) thin films by annealing Cu–Sn metallic inks with spin-coating ZnO layers under H₂S. The obtained pure phase and smooth CZTS thin films are characterized by means of X-ray diffraction (XRD) and scanning electron microscopy (SEM). Further, the CZTS thin films are grown on n-type Si substrates to form proto-type CZTS/Si heterojunction solar cells that have photovoltaic properties, indicating the promising application of CZTS as the absorber layers in Si-based heterojunction solar cells.     

Effect of deposition parameters on microstructure of electrodeposited nickel thin films

Nickel thin films were prepared using electrodeposition process on a copper substrate. The effect of deposition parameters on film microstructure has been investigated with and without an organic additive (saccharin). Electrodeposition has been carried out using direct current electrodeposition (DCED) method and pulsed electrodeposition (PED) method. Significant reduction in crystallite size has been observed with the increase in saccharin concentration (~10 g/L) irrespective of the electrodeposition method. In PED, it has been observed that an increase in pulse width causes a drastic reduction in crystallite dimension (~15 nm) of the deposited Ni-film. Further PED process yielded needle-shaped Ni grains under controlled process conditions unlike in DCED, where spherical grain structure was observed in the micrographs. However, these needle-shaped grains change their microstructure on addition of saccharin to the bath. A phenomenological model is presented to explain the observed microstructural changes.     

ZnO薄膜气相法制备

ZnO薄膜具有压电、光电、压敏、气敏、发光等多种特性,应用十分广泛。介绍了ZnO薄膜气相法制备原理中的各类主要方法,包括脉冲激光沉积、磁控溅射、分子束外延、金属有机化合物化学气相沉积、单源化学气相沉积和等离子体增强化学气相沉积等技术;分析了这些方法的优缺点;展望了ZnO薄膜今后的研究方向。     

Electrodeposited ZnO films with high UV emission properties

We report here our results in the preparation of ZnO films with high UV band to band characteristic luminescence emission by potentiostatic electrodeposition. Zinc nitrate aqueous baths with different concentration and additives were employed for the preparation of the films on platinum substrates. We focused our research in determining how the electrodeposition bath composition, i.e. zinc nitrate concentration and addition of KCl or polyvinyl pyrolidone and applied overpotential influence the morphological and optical properties of the oxide films. Scanning electron microscopy was employed for characterizing the films in terms of morphology. Optical reflection, photoluminescence spectroscopy and cathodoluminescence were used for determining the optical characteristics of the samples. The morphology of the deposit varies from hexagonal prisms to platelets as a function of the deposition rate. This experimental parameter also influences the luminescence properties. We found that at low deposition rates high UV luminescent material is obtained.