Enhancement of photosensitivity in bismuth doped Cu2ZnSnS4 thin films

In this paper, the effect of bismuth doping on the structural, morphological, optical and electrical properties of Cu₂ZnSnS₄ (CZTS) films has been investigated. The undoped and bismuth doped CZTS films (0, 0.5, 1, 1.5 and 2 mol%) were deposited on glass substrates by solution based method. The XRD result shows a significant improvement in the crystallinity of the films with increase in bismuth concentration. The Raman spectra of the films show the dominant peak at 334 cm^–1 corresponding to A₁ vibrational mode of CZTS kesterite phase. The FESEM micrographs of the films show an enhancement in the grain size and densification with the addition of bismuth ion concentration. The optical bandgap of the films was found to vary (1.59–1.40 eV) with the doping of bismuth ions. The I –V characteristics indicate twofold increment in the photoconductivity for the bismuth doped CZTS films under 100 mW/cm² illumination suggesting their potential application in photovoltaic devices. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

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.

     

射频磁控溅射法制备ZnS多晶薄膜及其性质

实验采用射频磁控溅射法在玻璃衬底上沉积了ZnS多晶薄膜,研究了沉积气压、退火温度和衬底温度对ZnS薄膜质量的影响.利用X射线衍射(XRD)分析了薄膜的微结构,并计算了内应力值.通过紫外-可见光分光光度计测量了薄膜的透过谱,计算了Urbach能量和禁带宽度.利用扫描电子显微镜(SEM)观察了薄膜的表面形貌.结果表明: 衬底温度为室温时沉积的ZnS薄膜具有较大的压应力,并且内应力值随着工作气压增大而增大,在300 ℃下进行退火处理后内应力松弛,衬底温度为350 ℃时制备的ZnS薄膜内应力小,透过率高,经300 ℃退火处理后结晶质量有所提高. 关键词： ZnS薄膜 射频磁控溅射 内应力     

Nanostructured solar cell based on solution processed Cu2ZnSnS4 nanoparticles and vertically aligned ZnO nanorod array

Cu₂ZnSnS₄ (CZTS) has attracted intensive interest for application in photovoltaic technology due to its excellent semiconductor properties. We report a nanostructured CZTS solar cell which was fabricated by infiltrating of CZTS nanoparticles into CdS coated ZnO nanorod arrays. The well aligned ZnO nanorods facilitate the efficient infiltration of CZTS nanoparticles. A hole transport layer was deposited to facilitate the transport of holes. The nanostructured CZTS solar cell demonstrated a remarkably high short‐circuit current density (11.0 mA/cm²). As a result, a power conversion efficiency of 2.8% was obtained. (© 2014 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Improving Cu2ZnSnS4 (CZTS) solar cell performance by an ultrathin ZnO intermediate layer between CZTS absorber and Mo back contact

The effects of an ultrathin ZnO intermediate layer deposited at the CZTS/Mo interface on CZTS solar cell performance have been investigated in this work. The ZnO layer inhibits the generation of MoS₂ layer and the formation of voids in the CZTS absorber. Consequently, the incorporation of this layer reduces the series resistance and increases the shunt resistance, which boosts photovoltaic conversion efficiency from 1.13% to 4.3%. (© 2014 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

溶剂热法制备铜锌锡硫粉末及光学性能研究

以金属氯化物作为金属源,硫脲为硫源,乙二醇为溶剂,聚乙烯吡咯烷酮(PVP)为表面活性剂,采用溶剂热法在较低反应温度下合成了Cu2ZnSnS4(CZTS)粉末。利用X射线衍射仪(XRD)、拉曼光谱(Raman)、扫描电子显微镜(SEM)、高分辨透射电子显微镜(HRTEM)对样品的结构和形貌进行表征。利用紫外-可见光谱(UV-Vis)对样品的光学性能进行研究。结果表明,180℃反应25小时的样品均为锌黄锡矿CZTS颗粒,颗粒形貌为表面花状的微球。当体系中PVP含量为0.2g时,微球尺寸约为2.5μm。当体系中PVP含量为0.3g,0.4g,0.5g时,微球尺寸大约为1.1μm。其中,PVP含量为0.4g的样品分散性较好,在可见区有明显的吸收,用外延法得到其禁带宽度约为1.45eV,与太阳能电池所需的最佳禁带宽度接近。     

Significant Enhancement of Hydrogen Production in MoS2/Cu2ZnSnS4 Nanoparticles

Hydrogen produced from water splitting is a renewable and clean energy source. Great efforts have been paid in searching for inexpensive and highly efficient photocatalysts. Here, significant enhancement of hydrogen production has been achieved by introducing ≈1 mol% of MoS₂ to Cu₂ZnSnS₄ nanoparticles. The MoS₂/Cu₂ZnSnS₄ nanoparticles showed a hydrogen evolution rate of ≈0.47 mmol g⁻¹ h⁻¹ in the presence of sacrificial agents, which is 7.8 times that of Cu₂ZnSnS₄ nanoparticles (0.06 mmol g⁻¹ h⁻¹). In addition, the MoS₂/Cu₂ZnSnS₄ nanoparticles exhibited high stability, and only ≈3% of catalytic activity was lost after a long time irradiation (72 h). Microstructure investigation on the MoS₂/Cu₂ZnSnS₄ nanoparticles reveals that the intimate contact between the nanostructured MoS₂ and Cu₂ZnSnS₄ nanoparticles provides an effective one‐way expressway for photogenerated electrons transferring from the conduction band of Cu₂ZnSnS₄ to MoS₂, thus boosting the lifetime of charge carriers, as well as reducing the recombination rate of electrons and holes.     

Low-temperature phase transformation of CZTS thin films

The low temperature phase transformation in the Cu_2ZnSnS_4(CZTS) films was investigated by laser annealing and low temperature thermal annealing.The Raman measurements show that a-high-power laser annealing could cause a red shift of the Raman scattering peaks of the kesterite(KS) structure and promotes the formation of the partially disordered kesterite(PD-KS) structure in the CZTS films,and the low-temperature thermal annealing only shifts the Raman scattering peak of KS phase by several wavenumber to low frequency and the broads Raman peaks in the low frequency region.Moreover,the above two processes were reversible.The Raman analyses of the CZTS samples prepared under different process show that the PD-KS structure tends to be found at low temperatures and low sulfur vapor pressures.Our results reveal that the control of the phase structure in CZTS films is feasible by adjusting the preparation process of the films.     

Cu2ZnSn(S1–xSex)4 thin film solar cells prepared by water‐based solution process

The kesterite Cu₂ZnSn(S_1–xSe_x)₄ (CZTSSe) thin film solar cell has been developed rapidly due to its excellence in structural and optical properties and its abundance in raw materials. Both vacuum‐based and solution‐based methods have been successfully employed to fabricate CZTSSe thin film solar cells. In this Letter, we report an environmentally friendly, water‐based, solution process for fabrication of high‐efficiency CZTSSe thin film solar cells. High quality CZTSSe thin film is obtained by selenization under high temperature and Se vapor. An efficiency of 6.2% is achieved on CZTSSe thin film solar cell fabricated by such water‐based solution process. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Preparation of boron carbon nitride thin films by radio frequency magnetron sputtering

Boron carbon nitride films were deposited by radio frequency magnetron sputtering using a composite target consisting of h-BN and graphite in an Ar-N₂ gas mixture. The samples were characterized by X-ray diffraction, Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. The results suggest that the films are atomic-level hybrids composed of B, C and N atoms. The boron carbon nitride films prepared in the present experiment have a disordered structure. The sputtering power varied from 80 W to 130 W. This sputtering power was shown to have regular effect on the composition of boron carbon nitride films. The samples deposited at 80 W and 130 W are close to the stoichiometry of BC₃N. The sample deposited at 110 W is close to the stoichiometry of BCN. The samples deposited at 100 W and 120 W approach to BC₂N. It is very significant for us to synthesize boron carbon nitride compound with controllable composition by changing the sputtering power.     

Raman scattering and disorder effect in Cu2ZnSnS4

The Raman spectra of surface regions of bulk Cu₂ZnSnS₄ (CZTS) samples with different Cu and Zn cation content were obtained and the differences in the spectra are attributed to statistical disorder effects in the cation sublattice. This disorder in the Cu and Zn sublattices may initiate a change of the crystal symmetry from kesterite‐type $({I\bar 4})$ to $({I\bar 42m})$ space group. The investigated CZTS crystals grown at high temperature are characterised by the co‐existence of regions with different composition ratio of Cu/(Zn + Sn) which results in kesterite and disordered kesterite phases. The presence of a disordered phase with ${I\bar 42m}$ symmetry is reflected in the appearance of a dominant broadened A‐symmetry peak at lower frequency than the peak of the main A‐symmetry kesterite mode at 337 cm^–1. We suppose that due to a small energy barrier between these phases the transition from one phase to the other can be stimulated by optical excitation of Cu₂ZnSnS₄. The analysis of the Raman spectra measured under different excitation conditions has allowed obtaining first (to our knowledge) experimental evidence of the existence of such optically induced structural transition in CZTS. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

单靶溅射制备铜锌锡硫薄膜及原位退火研究

采用衬底加热溅射铜锌锡硫(CZTS)四元化合物单靶制备CZTS薄膜,并研究原位退火对制备薄膜的影响.结果表明:在溅射结束后快速升温并保持一段时间,所得到的样品相比于未原位退火的CZTS薄膜结晶质量更好,且表面更平整致密;原位退火后的CZTS薄膜太阳电池性能参数也相应地有所提升,其开路电压(V_(OC))为575 mV,短路电流密度(J_(SC))为8.32 mA/cm~2,光电转换效率达到1.82%.     

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用射频等离子体增强非平衡磁控溅射在Si100基底上沉积了金属Cu膜。研究了偏压,射频功率和磁场等沉积参数对膜性能的影响。用扫描电子显微镜(SEM)、原子力显微镜(AFM)、X射线衍射(XRD)和电子能谱(EM)检测了膜的表面形貌,结构和成分。结果表明,射频放电有利于表面均匀光滑、电导率高的Cu沉积膜的形成;沉积参数对沉积膜的性能有重要的影响。     

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 Cu 2 ZnSnS 4,whereas an overlong annealing introduces defects;(iii) the band gap value of the doctor-bladed Cu 2 ZnSnS 4 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.     

Optical properties of p-type CuAlO2 thin film grown by rf magnetron sputtering

We report the structural and optical properties of copper aluminium oxide (CuAlO₂) thin films, which were prepared on c-plane sapphire substrates by the radio frequency magnetron sputtering method. X-ray photoelectron spectroscopy (XPS) along with X-ray diffraction (XRD) analysis confirms that the films consist of delafossite CuAlO₂ phase only. The optical absorption studies show the indirect and direct bandgap is 1.8 eV and 3.45 eV, respectively. Room temperature photoluminescence (PL) measurements show three emission peaks at 360 nm (3.45 eV), 470 nm (2.63 eV) and 590 nm (2.1 eV). The first one is near band edge emission while the other two are originated from defects.     

Colloidal Cu2ZnSnS4 nanocrystals generated by a facile route using ethylxanthate molecular precursors

We have demonstrated a flexible method for preparing Cu₂ZnSnS₄ (CZTS) nanocrystals by use of zinc ethylxanthate (Zn(ex)₂) and copper ethylxanthate (Cu(ex)₂). TEM, SEM, XRD, UV–vis, EDS, XPS and TG‐DTA indicate that the CZTS nanocrystals have been successfully synthesized. As air‐stable molecular precursors, Zn(ex)₂ and Cu(ex)₂ can optimize the synthesis of quaternary CZTS nanocrystals because Cu(ex)₂ and Zn(ex)₂ facilitate the formation of homogeneous precursor solutions including all precursors and then for the flexible production of CZTS nanocrystals in homogeneous reaction solutions. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

CZTS‐based materials and interfaces and their effects on the performance of thin film solar cells

Cu₂ZnSnS₄ (CZTS) and its related materials such as Cu₂ZnSnSe₄ (CZTSe) and Cu₂ZnSn(S,Se)₄ (CZTSSe) have attracted considerable attention as an absorber material for thin film solar cells due to the non‐toxicity, elemental abundance, and large production capacity of their constituents. Despite the similarities between CZTS‐based materials and Cu(In,Ga)Se₂(CIGS), the record efficiency of CZTS‐based solar cells remains significantly lower than that of CIGS solar cells. Considering that the difference between the two lies in the choice of the absorber material, the cause of the lower efficiency of CZTS‐based solar cells can be isolated to the issues associated with CZTS‐based materials and their related interfaces. Herein, these issues and the work done to understand and resolve them is reviewed. Unlike existing review papers, every unique region of CZTS‐based solar cells that contributes to its lower efficiency, namely: (1) the bulk of the absorber, (2) the grain boundaries of the absorber, (3) the absorber/buffer layer interface, and (4) the absorber/back contact interface are surveyed. This review also intends to identify the major unresolved issues and the potential improvement approaches of realizing sizable improvements in the solar cells' efficiency, thus providing a guide as to where research efforts should be focused. (© 2014 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)