Wurtzite copper-zinc-tin sulfide as a superior counter electrode material for dye-sensitized solar cells

Wurtzite and kesterite Cu₂ZnSnS₄ (CZTS) nanocrystals were employed as counter electrode (CE) materials for dye-sensitized solar cells (DSSCs). Compared to kesterite CZTS, the wurtzite CZTS exhibited higher electrocatalytic activity for catalyzing reduction of iodide electrolyte and better conductivity. Accordingly, the DSSC with wurtzite CZTS CE generated higher power conversion efficiency (6.89%) than that of Pt (6.23%) and kesterite CZTS (4.89%) CEs.     

The effect of the Zn/Sn ratio on the formation of single phase kesterite Cu2ZnSnS4 solar cell material

The effect of the Zn/Sn ratio in the solution on the properties of Cu₂ZnSnS₄ films prepared by sol-gel method has been investigated. As the Zn/Sn ratio in the solution increases to a certain value, a pure single phase kesterite CZTS is obtained and confirmed by XRD, XPS and Raman. Through controlling the Zn/Sn ratio in the solution, secondary phases such as SnO₂ can be avoided and an optimal condition for single phase kesterite CZTS can be achieved. Surface SEM images of the CZTS films are investigated and the optical band gap of the optimized CZTS film is found to be 1.23 eV.     

Facile mechano-chemical synthesis and enhanced photocatalytic performance of Cu2ZnSnS4 nanopowder

In the present study, Cu₂ZnSnS₄ (CZTS) powder was synthesized by the mechano-chemical method from its elemental constituents. X-ray diffraction (XRD), Energy-dispersive X-ray spectroscopy (EDS), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy and diffusion reflectance spectroscopy (DRS) were used for characterization of structural, morphological and optical properties. XRD result confirmed that a highly crystalline CZTS phase corresponding to the kesterite structure was formed after 50 h ball milling. Raman analysis confirmed the existence of single phase CZTS without any other phases. FESEM and TEM images reveal the irregular CZTS nanoparticles with an average size of 90 nm. The elemental mapping of the CZTS nanopowder showed the uniform distribution in agreement with the stoichiometry. DRS result showed a band gap value of 1.53 eV. XPS result revealed the oxidation states as Cu⁺, Zn²⁺, Sn⁴⁺ and S²⁻. The photocatalytic activity of CZTS has been investigated through photodegradation of methylene blue (MB) and methyl orange (MO) dyes solution with different concentrations under visible light irradiation. Although the CZTS decomposed MO only 81% until 210 min, the MB solution was completely photodegraded after 100 min. A kinetic study by Langmuir-Hinshelwood (L-H) model indicated about 3.7 times faster degradation of MB than MO and also higher adsorption capacity for MB by CZTS. Furthermore, the prepared CZTS was reusable and can be repeatedly used for the removal of dyes from aqueous solutions.     

A nontoxic and low-cost hydrothermal route for synthesis of hierarchical Cu2ZnSnS4 particles

We explore a facile and nontoxic hydrothermal route for synthesis of a Cu₂ZnSnS₄ nanocrystalline material by using l-cysteine as the sulfur source and ethylenediaminetetraacetic acid (EDTA) as the complexing agent. The effects of the amount of EDTA, the mole ratio of the three metal ions, and the hydrothermal temperature and time on the phase composition of the obtained product have been systematically investigated. The addition of EDTA and an excessive dose of ZnCl₂ in the hydrothermal reaction system favor the generation of kesterite Cu₂ZnSnS₄. Pure kesterite Cu₂ZnSnS₄ has been synthesized at 180°C for 12 h from the reaction system containing 2 mmol of EDTA at 2:2:1 of Cu/Zn/Sn. It is confirmed by Raman spectroscopy that those binary and ternary phases are absent in the kesterite Cu₂ZnSnS₄ product. The kesterite Cu₂ZnSnS₄ material synthesized by the hydrothermal process consists of flower-like particles with 250 to 400 nm in size. It is revealed that the flower-like particles are assembled from single-crystal Cu₂ZnSnS₄ nanoflakes with ca. 20 nm in size. The band gap of the Cu₂ZnSnS₄ nanocrystalline material is estimated to be 1.55 eV. The films fabricated from the hierarchical Cu₂ZnSnS₄ particles exhibit fast photocurrent responses under intermittent visible-light irradiation, implying that they show potentials for use in solar cells and photocatalysis.     

Influence of copper concentration on sprayed CZTS thin films deposited at high temperature

In this study, Cu₂ZnSnS₄ (CZTS) thin films were deposited by spray pyrolysis technique at constant substrate temperature. The effects of the copper concentration on the structural, morphological and optical properties of the films were investigated. The copper concentration was varied from 0.15 to 0.25 M in the steps of 0.05 M. The structural studies revealed that the Cu poor film shows low intense peaks, but as Cu concentration increases a relatively more intense and sharper diffraction peaks (112), (200), (220), and (312) of the kesterite crystal structure were observed. Raman spectroscopy analysis confirmed the formation of phase-pure CZTS films. From the morphological studies, it is found that the grain size increased as the Cu concentration increases from 0.15 to 0.25 M. The optical band-gap values were estimated to be 1.61, 1.52 and 1.45 eV for copper concentration 0.15, 0.20 and 0.25 M, respectively. Photoelectrochemical cells using films of different copper concentrations were fabricated and the best cell exhibited an efficiency of 1.09% for 0.25 M of copper concentration.     

A Promising Modified SILAR Sequence for the Synthesis of Photoelectrochemically Active Cu2ZnSnS4 (CZTS) Thin Films

A promising modified SILAR sequence approach has been employed for the synthesis of photoelectrochemically active Cu₂ZnSnS₄ (CZTS) thin films. To study the influence of sulfurization temperatures on the CZTS thin films, the CZTS precursor thin films were annealed at temperatures of 520, 540, 560, and 580 °C for 1 h in an H₂S (5 %)+Ar (95 %) atmosphere. These films were characterized for their structural, morphological, and optical properties using X-ray diffraction, Raman spectroscopy, field emission scanning electron microscopy, and UV-vis spectrophotometer techniques. The film sulfurized at an optimized temperature of 580 °C shows the formation of a prominent CZTS phase with a dense microstructure and optical band gap energy of 1.38 eV. The photoelectrochemical (PEC) device fabricated using optimized CZTS thin films sulfurized at 580 °C exhibits an open circuit voltage (V_oc) of 0.38 V and a short circuit current density (J_sc) of 6.49 mA cm⁻², with a power conversion efficiency (η) of 0.96 %.     

Tuned interactions of silver nanoparticles with ZSM-5 zeolite by adhesion-promoting poly(acrylic acid) deposited by electrospray ionization (ESI)

The electrospray ionization (ESI) method was used for deposition of thin films of poly(acrylic acid) (PAA) on Cu/ZSM-5 (5 wt.% Cu) and Ag–Cu/ZSM-5 (1 wt.% Ag and 4 wt.% Cu) composites. For comparative purposes, the ZSM-5 zeolite was synthesized under hydrothermal conditions and loaded with PAA under the same treating conditions as the composites. This method allowed the formation of uniform polymer films of controlled thickness on conductive substrates. The structural characteristics were characterized by X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy, atomic force microscopy and X-ray diffraction (XRD). The deposited PAA layer over ZSM-5 acts as a common dispersing and stabilizing agent through coordination-driven guest-templated polymer via interaction of Ag⁺ and Cu²⁺ with carboxylic acid groups, thus increasing and controlling the adhesion and the release of metallic species. A short exposure to light and temperature has reduced the metal ions to Cu⁰ and Ag⁰ metallic nanoparticles. The results of XRD analysis let suggest that the interaction of Cu and Ag with carboxylic groups of PAA inhibits the formation of large metallic silver particles. These samples were being studied for their potential as antibacterial agents toward the bacterial strains such as Staphylococcus pneumonia, Bacillus subtilis, Escherichia coli and Pseudomonas aeruginosa as Gram positive and Gram negative bacteria, respectively. Aspergillus fumigatus and Candida albicans as Fungi were also evaluated. The Cu/ZSM-5 and Ag–Cu/ZSM-5 nanocomposites coated with a 10 nm thick PAA layer exhibit significant antibacterial activity.     

Spray-deposited kesterite Cu2ZnSnS4 (CZTS): Optical,structural, and electrical investigations for solar cell applications

Kesterite Cu₂ZnSnS₄ (CZTS)-based solar devices have become a popular alternative to copper indium gallium selenide (CIGS) due to its outstanding properties such as high efficiency, non-toxicity, cost-effectiveness, suitable optoelectrical properties, and earth-abundancy. In this study, we directly fabricated CZTS films via a single-step spray pyrolysis technique, in contrast to conventional techniques where post sulfurization is required. The spray deposited CZTS films are investigated for their optical, structural, and electrical properties. The X-ray diffraction (XRD) and Raman analysis study revealed the synthesis of the phase-pure kesterite CZTS films without impurity phases. Large crystallites of CZTS are obtained at a deposition temperature of 400 °C, exhibiting a porous granular morphology with different grain sizes upon temperature variation. The size-dependent optical properties revealed that the CZTS films exhibited admirable visible light absorption of 10⁵ cm^?1 and an electronic bandgap ranging between 1.42 and 1.58 eV. The minimum dielectric loss obtained for optimized CZTS due to fewer intrinsic defects confirmed the materials’ applicability. Thus, the study provides a simple, viable route to fabricate CZTS without post-treatment to build affordable solar cells.     

Single step electrosynthesis of Cu2ZnSnS4 (CZTS) thin films for solar cell application

The Cu₂ZnSnS₄ (CZTS) thin films have been electrodeposited onto the Mo coated and ITO glass substrates, in potentiostatic mode at room temperature. The deposition mechanism of the CZTS thin film has been studied using electrochemical techniques like cyclic voltammetery. For the synthesis of these CZTS films, tri-sodium citrate and tartaric acid were used as complexing agents in precursor solution. The structural, morphological, compositional, and optical properties of the CZTS thin films have been studied using X-ray diffraction (XRD), scanning electron microscopy (SEM), EDAX and optical absorption techniques respectively. These properties are found to be strongly dependent on the post-annealing treatment. The polycrystalline CZTS thin films with kieserite crystal structure have been obtained after annealing as-deposited thin films at 550 in Ar atmosphere for 1 h. The electrosynthesized CZTS film exhibits a quite smooth, uniform and dense topography. EDAX study reveals that the deposited thin films are nearly stoichiometric. The direct band gap energy for the CZTS thin films is found to be about 1.50 eV. The photoelectrochemical (PEC) characterization showed that the annealed CZTS thin films are photoactive.     

Molecular-solution printing of Cu2ZnSnS4 (CZTS) thin film

In this work, a novel molecular-solution printing approach combined with a rapid thermal annealing process for the facile fabrication of Cu₂ZnSnS₄ (CZTS) thin film is reported. The intrinsic relationship between annealing parameters (temperature and time) and the properties of the fabricated samples was investigated systematically. Furthermore, the mechanism behind this CZTS formation approach was studied in detail. The results show that the best properties were obtained for the sample annealed at 600 °C for 45 min, which displayed a pure kesterite CZTS phase, acceptable morphology consisting of 1.0–1.5 μm size nanoparticles, a satisfactory Cu-poor and Zn-rich composition, and an ideal bandgap of ~1.42 eV. Thus, the prepared sample is a promising candidate for the fabrication of high-performance photovoltaic devices.     

Visible light photocatalytic H2-production activity of epitaxial Cu2ZnSnS4/ZnS heterojunction

Novel visible light driven photocatalyst Cu₂ZnSnS₄/ZnS composites were prepared by two-step hydrothermal method. The two semiconductors in the composites are lattice-matched and form close contact between them. With 0.1% Cu₂ZnSnS₄ grew on ZnS surface, the composite exhibits a high and stable visible light photocatalytic H₂ generation of 432 μmolg^− 1 h^− 1. This excellent visible light activity could be attributed to the enhancement of visible light absorption by surfacial modification of ZnS with CZTS and the photoinduced interfacial charge transfer from the valence band of ZnS to Cu₂ZnSnS₄ in the close contact interface.     

Effects of ethyl acetate additive on Cu2ZnSnS4 solar cells fabricated with a facile dimethylformamide-based solution coating process

The solution based on dimethylformamide (DMF) has shown promising application prospects in the fabrication of high-efficiency Cu₂ZnSnS₄ solar cells. However, due to the high boiling temperature of the solvent, it is difficult to completely volatilize DMF during the evaporation process after spin coating, leading to remains of C and O atoms at grain boundaries, which severely restricts the photoelectric performance of solar cells. In this study, ethyl acetate (EA) with green character was used as an additive to optimize the film formation process of DMF-based CZTS precursor. The experimental results showed that using a small amount of EA additives could effectively improve morphology, crystallinity, composition distribution and electrical properties of the CZTS absorber. In addition, the CZTS and CdS heterojunctions exhibited a cliff-like energy band structure, and the optimized conduction band offset increased the activation energy required for the carrier recombination path, consequently reducing the carrier recombination. Compared with the pure DMF precursor solution, the photoelectric conversion efficiency of CZTS solar cells with an EA addition ratio of 10% was improved by 42%, and the open circuit voltage of the device reached 601 mV.     

Cu2ZnSnS4 nanoparticles synthesized via reaction media with glycine

Single-phase kesterite Cu₂ZnSnS₄ (CZTS) nanoparticles, with spherical-like shape and average sizes of 3 nm, were synthesized by a novel aqueous route in which glycine molecules had two crucial roles. The first one was to promote the gradual release of Cu⁺ and Zn²⁺ ions from their respective complexes. The other role is to act as a capping agent to control the growth of the nanoparticles and aggregation. The reaction and growth mechanisms were discussed in relation to the reactants' nature, studies of the crystalline structure and morphology of the CZTS nanoparticles. Inks were prepared with the precipitated nanoparticles to fabricate films on fused-silica substrates by the combining the doctor Blade technique and axial compression. Analysis of CZTS film, annealed at the temperature of 500 °C in Ar-atmosphere, proved micron-sized particles’ formation with improved crystallinity. Optical studies revealed that both nanoparticles and films exhibit broad absorption edges extending to the near-infrared. The bandgap energy values of the developed materials are in the range of 1.41–1.45 eV.     

Effects of the sulfurization temperature on sol gel-processed Cu2ZnSnS4 thin films

As a promising and alternative solar absorber material, the copper–zinc–tin–sulfide compound (Cu₂ZnSnS₄) has been drawing attention in recent years for the production of cheap thin-film solar cells owing to the high natural abundance and non-toxicity of all the constituents, a tunable direct-band-gap energy and a large optical absorption coefficient. In addition, to overcome the problem of expensive vacuum-based methods, solution-based approaches are being developed for Cu₂ZnSnS₄ deposition. In this study, we have produced Cu₂ZnSnS₄ thin films via the sol–gel technique and subsequent sulfurization. The effects of the sulfurization temperature on the structural, morphological, compositional and optical properties of the films were investigated. X-ray diffraction and Raman spectroscopy analyses confirmed the formation of phase-pure CZTS films. The crystallinity of the films increased with an increasing sulfurization temperature. From the surface images and the results of the composition analysis, it was found that the films are uniform, composed of homogenously distributed grains and have compositions with Cu deficit. The values of the optical absorption coefficients for the films were found to be 10⁴ cm^?1 based on absorbance spectroscopy. The optical band-gap values were estimated to be between 1.32 and 2.27 eV depending on the sulfurization temperature.     

Synthesis and characterization of sol gel derived nontoxic CZTS thin films without sulfurization

Recently, great attention has been paid to the development of earth rich and nonhazardous Copper Zinc Tin Sulfide (CZTS–Cu₂ZnSnS₄) thin films for application in photovoltaic devices owing to its high absorption coefficient over the visible and infrared region. However, sulfurization process is an indispensable step in growing stoichiometric thin film using conventional physical vapor deposition. Hence, it is imperative to devise a liquid based technique without intentional sulfurization for the optimum quality growth of CZTS thin films. In the current work, layer-by-layer sol-gel deposition technique was utilized to grow high quality CZTS thin films without sulfurization and their structural and optical characteristics were investigated using XRD studies and UV-visible spectroscopy respectively. The morphology and chemical composition of the prepared CZTS films are estimated by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) analysis respectively. Highly absorbing and crystalline CZTS films have been successfully grown in the present work which could be further utilized as an absorber layer in photovoltaic applications.     

Nanocomposite synthesis and characterization of Kesterite,Cu2ZnSnS4 (CZTS) for photovoltaic applications

Nanocomposite processing of binary metal chalcogenide solids has led to the synthesis of Kesterite, Cu₂ZnSnS₄ (CZTS), which is an important emerging material for thin film photovoltaic devices. Nanophase precursors are combined in stoichiometric ratios and annealed in a 350–500 °C sulfur-rich nitrogen atmosphere to form CZTS. Processing methods for CZTS in the literature are either energy-intensive, requiring the sequential sputtering of metal layers at 700 °C, followed by an annealing step in a sulfur-containing atmosphere at 500 °C, or the use of chemicals and solvents that are detrimental to the environment. The presence of CZTS is clear in the resulting powders as confirmed by both XRD and UV–Vis analysis. Our results show that increasing the annealing temperature of the nanophase precursor mixture led to a higher level of CZTS purity and that a copper-poor and zinc-rich environment produced the purest CZTS. Tin disulfide, SnS₂, precursors produced a purer CZTS than when tin monosulfide, SnS, was used, because the latter is more volatile and decomposes at lower temperatures than the former. This synthetic route is more cost effective and environmentally friendly, avoiding the use of long processing times and harsh solvents.     

Cu2ZnSnS4 as a hole-transport layer in triple-cation perovskite solar cells: Current density versus layer thickness

Cu₂ZnSnS₄ (CZTS) is a good candidate for cost-effective perovskite solar cells (PSCs) due to its direct bandgap with a value of 1.4–1.5 eV. In this study, we investigate CZTS ink as an inorganic hole-transport-layer (HTL) in CsMAFAPbIBr mixed halide PSCs. We study the cell efficiency and hole extraction from the perovskite layer for different thicknesses of HTL. The optimized device exhibits better hole selectivity, and the best efficiency of the device (12.84%) is achieved for the CZTS layer with a thickness of 159 nm. The prepared samples were also tested by open-circuit voltage decay analysis and electrochemical impedance spectroscopies. Results show that the optimized device effectively prohibits the electrons-holes recombination with a charge transfer resistance of 9.38 Ω cm². This work suggests that the optimal thickness of CZTS as an HTL in triple-cation PSC is about 159 nm by giving short-circuit current density of 23.69 mA cm^?2.     

Cu2ZnSnS4 ceramic target: Determination of sintering temperature by TG–DSC

In this work, mixed powders of Cu₂S, ZnS and SnS₂ were used to sinter CZTS ceramic target. Thermal properties of Cu-poor and Zn-rich mixed powders were investigated by thermogravimetry and differential scanning calorimetry (TG–DSC). It has been found that the formation temperature of CZTS was not obvious in DSC curve. Obvious weight loss begun from 800 °C and a strong endothermic peak of melting appeared at around 880 °C depending on the relative tin content in mixed powders. For different compositions in Cu-poor and Zn-rich region, all TG and DSC curves showed similar profile as a function of temperature. To reduce volatilization and low melting point compound of SnS and Cu–Sn–S when sintering, a sintering temperature of 750 °C was adopted. CZTS targets (360 mm×80 mm) have been successfully fabricated with Cu-poor and Zn-rich composition, kesterite phase and high compactness of above 93%.     

Structural,optical and electrical properties of indium doped Cu2ZnSn(S,Se)4 thin films synthesized by the DC and RF reactive magnetron cosputtering

Element doping into the Cu₂ZnSn(S,Se)₄ (CZTSSe) absorber is an effective method to optimize the performance of thin film solar cells. In this study, the Cu₂In_xZn_1-xSn(S,Se)₄ (CIZTSSe) precursor film was deposited by magnetron cosputtering technique using indium (In) and quaternary Cu₂ZnSnS₄ (CZTS) as targets. Meanwhile, the In content was controlled using the direct current (DC) power on In target (P_In). A single kesterite CIZTSSe alloy was formed by successfully doping a small number of In³⁺ into the main lattice of CZTSSe. The partial Zn²⁺ cations were substituted by In³⁺ ions, resulting in improving properties of CZTSSe films. Morphological analysis showed that large grain CIZTSSe films could be obtained by doping In. The well-distributed, smooth, and dense film was obtained when the P_In was 30 W. The band gap of CIZTSSe could be continuously adjusted from 1.27 to 1.05 eV as P_In increased from 0 to 40 W. In addition, the CIZTSSe alloy thin film at P_In = 30 W exhibited the best p-type conductivity with Hall mobility of 6.87 cm²V^?1s^?1, which is a potential material as the absorption layer of high-performance solar cells.     

The role of sulphur in the sulfurization of CZTS layer prepared by DC magnetron sputtering from a single quaternary ceramic target

The influence of sulphur vapour pressure, controlled by its mass, on the grain growth and optoelectronic properties of Cu₂ZnSnS₄ (CZTS) films prepared by a two-step procedure based on sputtering was studied. It was found that both the crystallinity and grain size of the films were promoted with the increase of the sulphur vapour pressure, indicating that the crystal growth was controlled by the sulphur vapour pressure. In addition, the crystal growth process of CZTS was investigated by analysing the microstructure and elemental composition of the sulfurized films with different masses of sulphur. It was also found that the content of Sn in the sulfurized films decreased after high-temperature annealing. However, the second phase SnS₂ was observed on the sample surface, which led to the increase of the optical band gap of the film. Moreover, we proposed the regulatory mechanism of sulphur vapour pressure in the grain growth of CZTS film. Finally, a highly crystalline p-type kieserite Cu₂ZnSnS₄ film with carrier concentration of 8.16?×?10¹⁷ cm^?3, mobility of 1.24?cm²/V?s and optical bandgap of 1.54?eV was obtained. This CZTS layers are expected to fabricate high efficiency thin film solar cells.