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.

     

Comprehensive loss modeling in Cu2ZnSnS4 solar cells

Thin film solar cells based on Cu₂ZnSnS₄ (CZTS) absorber material suffers from performance issues arising due to the presence of a non-optimal back contact barrier, low carrier lifetime, acceptor/donor point defects in bulk, interface defects at the absorber-buffer junction and grain boundaries within the absorber. We perform comprehensive simulations enumerating the impact of these performance limiting factors on CZTS solar cells. These simulations capture the experimentally observed anomalies in current-voltage (I–V) characteristics and the open-circuit voltage (V_OC) pinning in CZTS solar cells. These cause-effect relationships as elaborated in the findings are expected to be of great interest to the experimentalists working in this field.     

Interfaces of high-efficiency kesterite Cu_2ZnSnS(e)_4 thin film solar cells

Cu_2ZnSnS(e)_4(CZTS(e)) solar cells have attracted much attention due to the elemental abundance and the nontoxicity.However,the record efficiency of 12.6% for Cu_2ZnSn(S,Se)_4(CZTSSe)solar cells is much lower than that of Cu(In,Ga)Se_2(CIGS)solar cells.One crucial reason is the recombination at interfaces.In recent years,large amount investigations have been done to analyze the interfacial problems and improve the interfacial properties via a variety of methods.This paper gives a review of progresses on interfaces of CZTS(e)solar cells,including:(i)the band alignment optimization at buffer/CZTS(e)interface,(ii)tailoring the thickness of MoS(e)_2 interfacial layers between CZTS(e)absorber and Mo back contact,(iii)the passivation of rear interface,(iv)the passivation of front interface,and(v)the etching of secondary phases.     

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)     

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.     

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)     

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.     

Effects of sulfur sources on properties of Cu2ZnSnS4 nanoparticles

Three Fe(β-diketonate)₃ compounds namely Fe(tmhd)₃ (tmhd = 2,2,6,6-tetramethyl-3,5-heptanedionato), Fe(hfac)₃ (hfac = hexafluoroacetylaceto), and Fe(dbm)₃ (dbm = dibenzoylmethane) were used as substitutes to Fe(acac)₃ (acac = acetyleacetonate) in the synthesis of FePt nanoparticles. The obtained superparamagnetic nanoparticles are 4–5 nm in diameter without showing a large size variation with substituent Fe(β-diketonate)₃. The synchrotron X-ray absorption spectroscopy confirmed the energy dispersive spectroscopy that as-synthesized nanoparticles were composed of iron oxides and metallic FePt₃ alloys. By employing Fe(hfac)₃, the Fe fraction was reduced and the magnetization was modest. The use of Fe(dbm)₃ as starting materials gave rise to densely packed FePt₃/Fe₂O₃ heterodimers. The replacements of Fe(acac)₃ by Fe(tmhd)₃ led to the long-range order of nanoparticle assembly with the narrowest size distribution.     

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.     

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。     

Synthesis and characterization of Cu2ZnSnS4 thin films by SILAR method

Semiconducting Cu₂ZnSnS₄ (CZTS) material has been receiving a great technological interest in the photovoltaic industry because of its low-cost non-toxic constituents, ideal direct band gap as a absorber layer and high absorption coefficient. CZTS thin films have been successfully deposited onto the fluorine-doped tin oxide/glass (glass/FTO) substrates coated glass substrates using successive ionic layer adsorption and reaction (SILAR) method and investigated for photoelectrochemical conversion (PEC) of light into electricity. The best solar cell sample showed an open-circuit voltage of 390 mV, a short-circuit current density of 636.9 μA/cm², a fill factor of 0.62 and an efficiency of 0.396% under irradiation of 30 mW/cm². Preliminary results obtained for solar cells fabricated with this material are promising.     

Investigation of Cu2ZnSnS4 thin-film solar cells with carrier concentration gradient

To investigate the effect of carrier concentration gradient on Cu₂ZnSnS₄ (CZTS) thin-film solar cells, the properties of CZTS solar cells were studied by numerical method. The photovoltaic performances of carrier concentration gradient CZTS solar cells were calculated by the solutions of Poisson's equation, continuity equation, and current density equation using AFors-Het v2.4 program. The carrier concentration gradient was changed to analyze its effect. Compared with CZTS solar cells without carrier concentration gradient, the photovoltaic performances of CZTS solar cells can be enhanced by using carrier concentration gradient absorber. The carrier concentration gradient can extend the distribution region of built-in electric field, which is beneficial to the drift of photo-generated carriers. However, the carrier concentration gradient also affects the recombination and series resistances of solar cells. When the defect density of CZTS layer is high, the photo-generated carriers are affected significantly by recombination, resulting in slight effect of carrier concentration gradient. Therefore, the defect density should be reduced to enhance the effect of carrier concentration gradient on improving conversion efficiency of CZTS thin-film solar cells.     

Two different effects of Na on Cu2ZnSnS4 thin-film solar cells

Among the many factors that affect the characteristics of Cu₂ZnSnS₄ thin-film solar cells, the effects of Na were examined. Because Na passivates the grain boundaries (GBs) in absorber layers, the GBs increase the minority carrier collection by providing a current pathway through which the minority carriers can reach the buffer and window layer and be collected. However, excess Na remains in the absorber layer and diffuses into the buffer and window layers, where it acts as an impurity and traps the minority carriers, thus decreasing the solar cell characteristics. By applying an annealing process after the deposition of the buffer and window layers, the Na content could be decreased. By improving the solar cell characteristics, a power conversion efficiency of 6.43% was achieved.     

Sulfurization temperature effects on the growth of Cu2ZnSnS4 thin film

We made Cu₂ZnSnS₄ (CZTS) thin films by sulfurization of Cu/Sn/Cu/Zn metallic films. Sulfurizations were carried out under different thermal annealing conditions, where maximum temperatures were 440 °C (LT-CZTS) and 550 °C (HT-CZTS). For LT-CZTS films, secondary phases such as SnS₂ and Cu_2?xS were observed, whereas for HT-CZTS films secondary impurities were not detected. Chemical composition of LT-CZTS film was observed to be very non-uniform. Highly Sn-rich and Zn-rich regions were found on the film surface of LT-CZTS. However, averaged chemical composition for larger area was close to stoichiometry. The HT-CZTS film showed homogeneous structural and chemical composition features. But, for HT-CZTS film, the Sn composition was observed to be decreased, which was due to the Sn-loss. By UV–Visible spectroscopy, optical band gaps of LT- and HT-CZTS films were measured to be ～1.33 eV and ～1.42 eV, respectively. The band gap of LT-CZTS film was also observed to be smaller by photoluminescence measurement. The depressed band gap of LT-CZTS film may be ascribed to some defects and low band gap impurities such as Cu₂SnS₃ and Cu_2-xS in the LT-CZTS film.