Porous copper zinc tin sulfide thin film as photocathode for double junction photoelectrochemical solar cells

Porous copper zinc tin sulfide (CZTS) thin film was prepared via a solvothermal approach. Compared with conventional dye-sensitized solar cells (DSSCs), double junction photoelectrochemical cells using dye-sensitized n-type TiO(2) (DS-TiO(2)) as the photoanode and porous p-type CZTS film as the photocathode shows an increased short circuit current, external quantum efficiency and power conversion efficiency.     

Development of a selective chemical etch to improve the conversion efficiency of Zn-rich Cu2ZnSnS4 solar cells

Improvement of the efficiency of Cu(2)ZnSnS(4) (CZTS)-based solar cells requires the development of specific procedures to remove or avoid the formation of detrimental secondary phases. The presence of these phases is favored by the Zn-rich and Cu-poor conditions that are required to obtain device-grade layers. We have developed a selective chemical etching process based on the use of hydrochloric acid solutions to remove Zn-rich secondary phases from the CZTS film surface, which are partly responsible for the deterioration of the series resistance of the cells and, as a consequence, the conversion efficiency. Using this approach, we have obtained CZTS-based devices with 5.2% efficiency, which is nearly twice that of the devices we have prepared without this etching process.     

Development of dip-coated Cu2ZnSnS4 absorber material without sulphurisation

Journal of Sol-Gel Science and Technology - Quaternary semiconductor Cu2ZnSnS4 absorber material was synthesized by the sol-gel method deposited by the dip-coating technique on ordinary glass...     

Cu2ZnSnS4 (CZTS) nanoparticle based nontoxic and earth-abundant hybrid pn-junction solar cells

A heterojunction between a layer of CZTS nanoparticles and a layer of fullerene derivatives forms a pn-junction. We have used such an inorganic-organic hybrid pn-junction device for solar cell applications. As routes to optimize device performance, interdot separation has been reduced by replacing long-chain ligands of the quantum dots with short-chain ligands and thickness of the CZTS layer has been varied. We have shown that the CZTS-fullerene interface could dissociate photogenerated excitons due to the depletion region formed at the pn-junction. From capacitance-voltage characteristics, we have determined the width of the depletion region, and compared it with the parameters of devices based on the components of the heterojunction. The results demonstrate solar cell applications based on nontoxic and earth-abundant materials.     

Balance of catalytic activity and conductivity of Cu2ZnSnS4/graphene counter electrode for dye-sensitized solar cells: using hydrothermal-synthesized kesterite Cu2ZnSnS4 and graphene obtained by product line

Journal of Solid State Electrochemistry - The catalytic activity and conductivity of Cu2ZnSnS4/graphene counter electrode for dye-sensitized solar cells (DSSCs) was balanced using...     

Towards sustainable materials for solar energy conversion: Preparation and photoelectrochemical characterization of Cu2ZnSnS4

The feasibility of a new fabrication route for films of the attractive solar absorber Cu₂ZnSnS₄ (CZTS) has been studied, consisting of electrodeposition of metallic precursors followed by annealing in sulfur vapour. Photoelectrochemical measurements using a Eu³⁺ contact have been used to establish that the polycrystalline CZTS films are p-type with doping densities in the range (0.5–5) × 10¹⁶ cm⁻³ and band gaps of 1.49 ± 0.01 eV, making them suitable for terrestrial solar energy conversion. It has been shown that a somewhat Cu-poor composition favours good optoelectronic properties.     

Wurtzite Cu2ZnSnS4 nanocrystals: a novel quaternary semiconductor

A new wurtzite phase Cu(2)ZnSnS(4) was discovered and the corresponding nanocrystals have been successfully synthesized. They have been characterized in detail and showed the photoelectric response, which demonstrated their potential in the application of photovoltaic devices.     

Continuous production of Cu2ZnSnS4 nanocrystals in a flow reactor

A procedure for the continuous production of Cu(2)ZnSnS(4) (CZTS) nanoparticles with controlled composition is presented. CZTS nanoparticles were prepared through the reaction of the metals' amino complexes with elemental sulfur in a continuous-flow reactor at moderate temperatures (300-330 °C). High-resolution transmission electron microscopy and X-ray diffraction analysis showed the nanocrystals to have a crystallographic structure compatible with that of the kesterite. Chemical characterization of the materials showed the presence of the four elements in each individual nanocrystal. Composition control was achieved by adjusting the solution flow rate through the reactor and the proper choice of the nominal precursor concentration within the flowing solution. Single-particle analysis revealed a composition distribution within each sample, which was optimized at the highest synthesis temperatures used.     

Template-directed synthesis of ordered single-crystalline nanowires arrays of Cu2ZnSnS4 and Cu2ZnSnSe4

Highly ordered quaternary semiconductor Cu(2)ZnSnS(4) nanowires array have been prepared via a facile solvothermal approach using anodic aluminum oxide (AAO) as a hard template. The as-prepared nanowires are uniform and single crystalline. They grow along either the crystalline [110] or [111] direction. The structure, morphology, composition, and optical absorption properties of the as-prepared Cu(2)ZnSnS(4) samples were characterized using X-ray powder diffraction, transmission electron microscopy, energy dispersive X-ray spectrometry, scanning electron microscopy, and UV-vis spectrometry. A possible formation mechanism of the nanowire arrays is proposed. Governed by similar mechanism, we show that Cu(2)ZnSnSe(4) nanowire array with similar structural characteristics can also be obtained.     

Size control and quantum confinement in Cu2ZnSnS4 nanocrystals

Starting with metal dithiocarbamate complexes, we synthesize colloidal Cu(2)ZnSnS(4) (CZTS) nanocrystals with diameters ranging from 2 to 7 nm. Structural and Raman scattering data confirm that CZTS is obtained rather than other possible material phases. The optical absorption spectra of nanocrystals with diameters less than 3 nm show a shift to higher energy due to quantum confinement.     

太阳能电池材料-铜锌锡硫化合物薄膜制备及器件应用研究进展

锌黄锡矿结构的CZTS（铜锌锡硫）材料与目前在薄膜太阳能电池领域表现出色的黄铜矿结构的CIGS（铜铟镓硒）材料具有相似的晶体结构,且CZTS有着很好的光电性能,组成元素在地球上含量丰富,安全无毒,非常适合用来发展高效、廉价的太阳能电池.近期CZTS类太阳能电池的最高效率已达到12.6%,在科研和产业领域引起了广泛关注.在简介了“新星”太阳能电池材料CZTS的性质及薄膜太阳能电池器件的基本结构之后,重点总结了CZTS薄膜的制备方法（真空、非真空法）以及相应器件效率,其中对众多非真空制备法进行了独到的归类总结.最后,对CZTS薄膜的优化方法进行了分析,并对其未来发展方向做了展望.     

Efficient perovskite solar cells employing a solution-processable copper phthalocyanine as a hole-transporting material

The development of alternative low-cost and high-performing hole-transporting materials(HTMs) is of great significance for the potential large-scale application of perovskite solar cells(PSCs) in the future.Here,a facilely synthesized solution-processable copper tetra-(2,4-dimethyl-3-pentoxy) phthalocyanine(CuPc-DMP) via only two simple steps,has been incorporated as a hole-transporting material(HTM) in mesoscopic perovskite solar cells(PSCs).The optimized devices based on such a HTM afford a very competitive power conversion efficiency(PCE) of up to 17.1%measured at 100 mW cm~(-2) AM 1.5G irradiation,which is on par with that of the well-known 2,2',7,7'-tetrakis(N'N'-di-p-methoxyphenylamine)-9,9'-spirobifluorene(spiro-OMeTAD)(16.7%) under equivalent conditions.This is,to the best of our knowledge,the highest value reported so far for metal organic complex-based HTMs in PSCs.The advantages of this HTM observed,such as facile synthetic procedure,superior hole transport characteristic,high photovoltaic performance together with the feasibility of tailoring the molecular structure would make solution-processable copper phthalocyanines as a class of promising HTM that can be further explored in PSCs.The present finding highlights the potential application of solution processed metal organic complexes as HTMs for cost-effective and high-performing PSCs.     

Synthesis of Cu2ZnSnS4 thin films by dip-coating method without sulphurization

Quaternary Cu₂ZnSnS₄ (CZTS) thin films, a promising absorber material for solar cells has been successfully deposited on glass substrates by cost effective simple dip-coating method without using either polluting chemicals or expensive vacuum facilities. X-ray diffraction pattern reveals the formation of CZTS films with tetragonal type kesterite structure. The Raman spectra of the prepared films exhibited resonance peaks corresponding to the CZTS phase. The scanning electron microscopic image shows the formation of films with smooth surface. The surface topography studied using atomic force microscope gives an rms roughness of 1.6 nm. The Hall effect studies indicate that the prepared films are p-type with a carrier concentration of 4.77 × 10²⁰ cm^?3. The energy dispersive X-ray analysis result indicate the presence of Cu, Zn, Sn and S in the film. The absorption coefficient was found to be the order of 10⁴ cm^?1 and the band gap has been found to be 1.5 eV.     

Cu2ZnSnS4纳米晶的制备及其三阶非线性光学性能的研究

以乙酰丙酮铜、醋酸锌、二氯亚锡、油胺和硫粉为前驱体,采用one-pot法合成出了单分散的Cu2ZnSnS4(CZTS)纳米晶.所得样品采用X射线粉末衍射仪(XRD),能量色散谱仪(EDS),透射电子显微镜(TEM),高分辨透射电子显微镜(HRTEM),光电子能谱仪(XPS),紫外-可见光谱仪(UV-vis)和Z-扫描(Z-scan)技术对其结构组成、形貌、性能等进行了表征.结果表明:所获得的产物为四方相结构的六边形CZTS纳米颗粒,直径约为10 nm.计算出尺寸大小为10 nm,13 nm的纳米晶的三阶非线性光学折射率γ(-1.08×10-15,-9.08×10-17 m2·W-1),三阶非线性光学吸收系数β(6.5×10-9,3.69×10-11 m·W-1)以及三阶非线性光学极化率χ(3)(1.49×10-9,4.35×10-10 esu).并探讨了CZTS纳米晶可能的形成机理,及引起三阶光学非线性发生变化的原因。     

Colloidal synthesis of wurtzite Cu2ZnSnS4 nanorods and their perpendicular assembly

The quaternary copper chalcogenide Cu(2)ZnSnS(4) is an important emerging material for the development of low-cost and sustainable solar cells. Here we report a facile solution synthesis of stoichiometric Cu(2)ZnSnS(4) in size-controlled nanorod form (11 nm × 35 nm). The monodisperse nanorods have a band gap of 1.43 eV and can be assembled into perpendicularly aligned arrays by controlled evaporation from solution.     

溶剂热法制备球状Cu2ZnSnS4纳米晶及其表征

通过简单的溶剂热法合成了锌黄锡矿结构的Cu2ZnSnS4(CZTS)纳米晶,使用L-半胱氨酸作硫源和络合剂,以金属氯化物作前驱体,在180°C下反应16h成功获得了CZTS微球.使用X射线衍射(XRD)仪,场发射扫描电子显微镜(FESEM)、能量色散谱(EDS)、高分辨透射电子显微镜(HRTEM)、多功能X射线光电子能谱仪(XPS)、紫外-可见(UV-Vis)分光光度计对产物的物相、结构、形貌及光学性能进行表征.结果表明:所得的产物为纯相锌黄锡矿结构的CZTS纳米颗粒,CZTS微球直径为400-800nm,并可观察到微球是由大量厚度约20nm的纳米片构成;将CZTS颗粒均匀分散在异丙醇中,测试后估算其禁带宽度约1.58eV,与薄膜太阳能电池所需的最佳禁带宽度相近.并对其形成机理进行了初步探讨.     

Structure flexibility of the Cu2ZnSnS4 absorber in low-cost photovoltaic cells: from the stoichiometric to the copper-poor compounds

Here we present for the very first time a single-crystal investigation of the Cu-poor Zn-rich derivative of Cu(2)ZnSnS(4). Nowadays, this composition is considered as the one that delivers the best photovoltaic performances in the specific domain of Cu(2)ZnSnS(4)-based thin-film solar cells. The existence of this nonstoichiometric phase is definitely demonstrated here in an explicit and unequivocal manner on the basis of powder and single-crystal X-ray diffraction analyses coupled with electron microprobe analyses. Crystals are tetragonal, space group I ?4, Z = 2, with a = 5.43440(15) ? and c = 10.8382(6) ? for Cu(2)ZnSnS(4) and a = 5.43006(5) ? and c = 10.8222(2) ? for Cu(1.71)Zn(1.18)Sn(0.99)S(4).     

Photoelectrochemical conversion of toluene to methylcyclohexane as an organic hydride by Cu2ZnSnS4-based photoelectrode assemblies

Direct photoelectrochemical conversion of toluene (TL) to methylcyclohexane (MC) with water has been examined as an organic hydride conversion using light irradiation. The production of MC from TL was observed on Pt/CdS/Cu(2)ZnSnS(4)/Mo photoelectrodes with anion-type ionomer membrane assemblies. A cathodic photocurrent was observed below 0.7 V vs RHE (V(RHE)) in 0.1 M Na(2)SO(4)/NaOH (pH 9.5) aqueous solution, and an apparent photocurrent density of 0.5 mA cm(-2) was obtained at 0 V(RHE) under the irradiation of a 300 W Xe lamp with a 420 nm cutoff filter. The yield of MC was measured by gas chromatography, and an 88% faradaic efficiency was estimated. This study suggests the possibility of direct energy conversion from solar energy to MC as an energy carrier of organic hydrides.