Preparation of Cu2ZnSnS4 thin films by sulfurization of stacked metallic layers

Stacked precursors of Cu, Sn, and Zn were fabricated on glass/Mo substrates by electron beam evaporation. Six kinds of precursors with different stacking sequences were prepared by sequential evaporation of Cu, Sn, and Zn with substrate heating. The precursors were sulfurized at temperatures of 560 °C for 2 h in an atmosphere of N₂ + sulfur vapor to fabricate Cu₂ZnSnS₄ (CZTS) thin films for solar cells. The sulfurized films exhibited X-ray diffraction peaks attributable to CZTS. Solar cells using CZTS thin films prepared from six kinds of precursors were fabricated. As a result, the solar cell using a CZTS thin film produced by sulfurization of the Mo/Zn/Cu/Sn precursor exhibited an open-circuit voltage of 478 mV, a short-circuit current of 9.78 mA/cm², a fill factor of 0.38, and a conversion efficiency of 1.79%.     

Air-Stable Low-Symmetry Narrow-Bandgap 2D Sulfide Niobium for Polarization Photodetection

Low-symmetry 2D materials with unique anisotropic optical and optoelectronic characteristics have attracted a lot of interest in fundamental research and manufacturing of novel optoelectronic devices. Exploring new and low-symmetry narrow-bandgap 2D materials will be rewarding for the development of nanoelectronics and nano-optoelectronics. Herein, sulfide niobium (NbS₃), a novel transition metal trichalcogenide semiconductor with low-symmetry structure, is introduced into a narrowband 2D material with strong anisotropic physical properties both experimentally and theoretically. The indirect bandgap of NbS₃ with highly anisotropic band structures slowly decreases from 0.42 eV (monolayer) to 0.26 eV (bulk). Moreover, NbS₃ Schottky photodetectors have excellent photoelectric performance, which enables fast photoresponse (11.6 µs), low specific noise current (4.6 × 10⁻²⁵ A² Hz⁻¹), photoelectrical dichroic ratio (1.84) and high-quality reflective polarization imaging (637 nm and 830 nm). A room-temperature specific detectivity exceeding 10⁷ Jones can be obtained at the wavelength of 3 µm. These excellent unique characteristics will make low-symmetry narrow-bandgap 2D materials become highly competitive candidates for future anisotropic optical investigations and mid-infrared optoelectronic applications.     

Characterization of vertical Bridgman grown Cd0.9Zn0.1Te0.97Se0.03 single crystal for room-temperature radiation detection

We report a modified vertical Bridgman method to grow Cd_0.9Zn_0.1Te_0.97Se_0.03 (CZTS) single crystals using in-house zone-refined 7 N (99.99999%) purity elemental precursors for room-temperature radiation detection. CZTS is an economic yet high performance alternative to expensive CdZnTe (CZT) detectors for room-temperature gamma-ray detection. Radiation detector in planar geometry has been fabricated on an 11.0?×?11.0?×?3.0 mm³ CZTS single crystal. A bulk resistivity of 10¹⁰ Ω.cm has been achieved without using any compensating dopant. The elemental composition of the grown crystal has been examined using energy-dispersive X-ray (EDX) analysis. Powder X-ray diffraction (XRD) showed formation of zincblende phase with a lattice constant of 6.447 Å, and sharp peaks confirmed the formation of highly crystalline single-phase CZTS crystals. A modified Vegard’s law has been applied to calculate the atomic percentage of Se in the grown crystals from the XRD patterns and compared with the intended and the measured stoichiometry. The electron mobility-lifetime (μτ) product and the drift mobility have been calculated to be 1.5?×?10^–3 cm²/V and 710 cm²/V.s, respectively, using alpha spectroscopy. The presented vertical Bridgman growth method uses a single pass through the controlled heating zone in contrast to the previously reported multiple pass growth techniques, thus, reducing the growth duration by two third which would help to further reduce the cost of production of CZTS-based room-temperature detectors.

     

Cu2ZnSnS4 thin film solar cells from electroplated precursors: Novel low-cost perspective

Thin-film solar cells based on Cu₂ZnSnS₄ (CZTS) absorbers were fabricated successfully by solid-state reaction in H₂S atmosphere of electrodeposited Cu-Zn-Sn precursors. These ternary alloys were deposited in one step from a cyanide-free alkaline electrolyte containing Cu(II), Zn(II) and Sn(IV) metal salts on Mo-coated glass substrates. The solar cell was completed by a chemical bath-deposited CdS buffer layer and a sputtered i-ZnO/ZnO:Al bilayer. The best solar cell performance was obtained with Cu-poor samples. A total area (0.5 cm²) efficiency of 3.4% is achieved (V_oc = 563 mV, j_sc = 14.8 mA/cm², FF = 41%) with a maximum external quantum efficiency (EQE) of 80%. The estimated band-gap energy from the external quantum efficiency (EQE) measurements is about 1.54 eV. Electron backscatter-diffraction maps of cross-section samples revealed CZTS grain sizes of up to 10 µm. Elemental distribution maps of the CZTS absorber show Zn-rich precipitates, probably ZnS, and a Zn-poor region, presumably Cu₂SnS₃, close to the interface Mo/CZTS.     

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.     

Sulfurization free spray deposited kesterite Cu2ZnSnS4 absorber layer for photovoltaic applications

The growth of Cu₂ZnSnS₄ thin films was optimized via sulfurization free chemical spray pyrolysis technique. The sulfate based precursors were used to prepare the CZTS films with varying sulfur contents ranging from 0.08 to 0.12 M to maintain the stoichiometric and avoid sulfurization or H₂S gas. The formation of secondary phases on the CZTS films was minimized by controlling the sulfur concentrations with the 2- methoxyethanol solvent. The CZTS kesterite structure with preferential orientation along (112) plane was confirmed by X-Ray diffraction at the sulfur content of 0.12 M. From the Raman analysis, we observed that the addition of the higher sulfur concentration to the precursor solution resulted in a pure phase CZTS peak at 336 cm^?1 and reduces the secondary phase segregation. Scanning electron microscopy confirms that higher sulfur concentrations facilitate the growth of CZTS films with larger grain size and achieved Cu-poor and Zn-rich compositions for 0.12 M sulfur concentration from energy dispersive spectra. The UV analysis revealed the maximum absorption peak in the visible region with increasing sulfur concentration and the measurement of the Hall effect affirmed p-type conductivity with carrier concentrations ranging from 10¹⁴ to 10¹⁶ cm^?3 as sulfur concentration increased. The charge transport property of the deposited films was characterized by electrochemical impedance spectroscopy where higher sulfur concentrations resulted in lower internal charge transfer resistance, which is the ideal absorber layer in thin film photovoltaic cells.

     

Synthesis and Broadband Photodetection of a P-Type 1D Van der Waals Semiconductor HfSnS3

1D van der Waals (vdW) materials have attracted significant interest in recent years due to their giant anisotropic and weak interlayer-coupled characters. More 1D vdW materials are urgently to be exploited for satisfying the practice requirement. Herein, the study of 1D vdW ternary HfSnS₃ high-quality single crystals grown via the chemical vapor transport technique is reported. The Raman vibration modes and band structure of HfSnS₃ are analyzed via DFT calculations. Its strong in-plane anisotropic is verified by the polarized Raman spectroscopy. The field-effect transistors (FETs) based on the HfSnS₃ nanowires demonstrate p-type semiconducting behavior as well as outstanding photoresponse in a broadband range from UV to near-infrared (NIR) with short response times of ≈0.355 ms, high responsivity of ≈11.5 A W⁻¹, detectivity of ≈8.2 × 10¹¹, external quantum efficiency of 2739%, excellent environmental stability, and repeatability. Furthermore, a typical photoconductivity effect of the photodetector is illustrated. These comprehensive characteristics can promote the application of the p-type 1D vdW material HfSnS₃ in optoelectronics.     

Cu2ZnSnS4 solar cells prepared with sulphurized dc-sputtered stacked metallic precursors

In the present work we report the details of the preparation and characterization results of Cu₂ZnSnS₄ (CZTS) based solar cells. The CZTS absorber was obtained by sulphurization of dc magnetron sputtered Zn/Sn/Cu precursor layers. The morphology, composition and structure of the absorber layer were studied by scanning electron microscopy, energy dispersive spectroscopy, X-ray diffraction and Raman scattering. The majority carrier type was identified via a hot point probe analysis. The hole density, space charge region width and band gap energy were estimated from the external quantum efficiency measurements. A MoS₂ layer that formed during the sulphurization process was also identified and analyzed in this work. The solar cells had the following structure: soda lime glass/Mo/CZTS/CdS/i-ZnO/ZnO:Al/Al grid. The best solar cell showed an open-circuit voltage of 345 mV, a short-circuit current density of 4.42 mA/cm², a fill factor of 44.29% and an efficiency of 0.68% under illumination in simulated standard test conditions: AM 1.5 and 100 mW/cm².     

Cu2ZnSnS4 solar cell prepared entirely by non-vacuum processes

Cu₂ZnSnS₄ (CZTS) solar cell with superstrate structure of fluorine-doped tin oxide glass/TiO₂/In₂S₃/CZTS/Carbon was prepared entirely by non-vacuum processes. The compact TiO₂ window and In₂S₃ buffer layers, CZTS absorber layer and Carbon electrode layer were prepared by spray pyrolysis method, ball milling and screen printing combination processes and screen printing process, respectively. The short-circuit current density, open-circuit voltage, fill factor and conversion efficiency of the best fabricated solar cell are 8.76 mA/cm², 250 mV, 0.27 and 0.6%, respectively. The fabrication process for the CZTS solar cell did not employ any vacuum conditions or high-toxic materials (such as CdS, H₂Se, H₂S or Se).     

Development of CZTS-based thin film solar cells

The low cost, environmental harmless Cu₂ZnSnS₄ (CZTS)-based thin film solar cells are fabricated by using abundant materials. The CZTS film possesses promising characteristic optical properties; band-gap energy of about 1.5 eV and large absorption coefficient in the order of 10⁴ cm^− 1. All constituents of this CZTS film, which are abundant in the crust of the earth, are non-toxic. Therefore, if we can use CZTS film practically as the absorber of solar cells, we will be free from both of the resource saving problem and the environmental pollution.In our CZTS project, CZTS absorber films were prepared by two independent techniques. One is three rf sources co-sputtering followed by annealing in sulfurized atmosphere. The latest conversion efficiency of over 6.7% was achieved by this technique. The other is co-evaporation technique. CZTS films were grown on Si (100) by vacuum co-evaporation using elemental Cu, Sn, S and binary ZnS as sources. XRD patterns indicated that the polycrystalline growth was suppressed and the orientational growth was relatively induced in a film grown at higher temperatures.In this presentation, the development of CZTS-based thin film solar cells will be surveyed.     

Light Confinement Effect Induced Highly Sensitive,Self‐Driven Near‐Infrared Photodetector and Image Sensor Based on Multilayer PdSe2/Pyramid Si Heterojunction

In this study, a highly sensitive and self‐driven near‐infrared (NIR) light photodetector based on PdSe₂/pyramid Si heterojunction arrays, which are fabricated through simple selenization of predeposited Pd nanofilm on black Si, is demonstrated. The as‐fabricated hybrid device exhibits excellent photoresponse performance in terms of a large on/off ratio of 1.6 × 10⁵, a responsivity of 456 mA W^?1, and a high specific detectivity of up to 9.97 × 10¹³ Jones under 980 nm illumination at zero bias. Such a relatively high sensitivity can be ascribed to the light trapping effect of the pyramid microstructure, which is confirmed by numerical modeling based on finite‐difference time domain. On the other hand, thanks to the broad optical absorption properties of PdSe₂, the as‐fabricated device also exhibits obvious sensitivity to other NIR illuminations with wavelengths of 1300, 1550, and 1650 nm, which is beyond the photoresponse range of Si‐based devices. It is also found that the PdSe₂/pyramid Si heterojunction device can also function as an NIR light sensor, which can readily record both “tree” and “house” images produced by 980 and 1300 nm illumination, respectively.     

Enhancement in photovoltaic performance of CZTS Thin-film solar cells through varying stacking order and sulfurization time

The CZTS samples were produced by a two-stage method, which includes deposition of Cu, Sn, Zn, and ZnS layers using magnetron sputtering to obtain CuSn/Zn/Cu and CuSn/ZnS/Cu stacks. The latter stage involves the sulfurization process of stacked films at 550 °C for varied sulfurization time (60, 90, 120, and 150 s) employing Rapid Thermal Processing (RTP) method to attain CZTS structure. The prepared CZTS thin films were analyzed utilizing several characterization methods. The energy-dispersive X-ray spectroscopy (EDX) measurements revealed that all sulfurized samples had Cu-poor and Zn-rich chemical composition. All samples showed that diffraction peaks belonged to pure kesterite CZTS phase subject to their XRD patterns. Besides, it was observed that the sulfurization time had a crucial effect on the crystal size of the samples. The Raman spectra of the samples verified the constitution of kesterite CZTS phase and it provides detection of some CTS-based secondary phases. The scanning electron microscopy (SEM) image of the films revealed that polycrystalline surface structures were observable in all the samples. However, plate-like surface features were observed in some samples that may refer to CTS-based secondary phases depending on chemical composition. From 1.40 to 1.48 eV optical band gap values were obtained from (αhν)² vs. photon energy (hν) plots. The Van der Pauw measurements exhibited that the CZTS samples produced employing CuSn/ZnS/Cu stack had lower resistivity (~?10^–3 Ω cm), higher carrier concentration values (~?10²¹ cm^?3), and higher charge mobility. The solar cells prepared using the most promising CZTS samples employing CuSn/Zn/Cu and CuSn/ZnS/Cu precursor films revealed 1.95% and 3.10% conversion efficiencies, respectively.

     

Electrical and photoelectric properties of GeS layered crystals grown by different techniques

Thermally stimulated currents and anisotropic electrical conductivity are studied in GeS layered crystals prepared by the Bridgman-Stockbarger, Pizzarello, and sublimation techniques. All the crystals arep-type, regardless of the growth technique, owing to the presence of Ge vacancies. The conductivity anisotropy in the melt-grown crystals is high compared to the vapor-grown GeS. The anisotropy rises exponentially with temperature. The concentrations and ionization energies of traps in GeS crystals are determined from thermally stimulated current curves. The spectral response of the photocurrent through the crystals prepared by sublimation, whose structural perfection is higher than that of the melt-grown crystals, is governed by the spectral dependence of the absorption coefficient forad ≪ 1 (near-edge region) and by the spectral dependence of reflectivity for αd > 1 (high-α region). Regardless of the growth technique, the 293-K photocurrent spectra of GeS crystals show strongly polarized peaks at 1.65 (E ∥a) and 1.78 eV (E ∥b), which are due to the Λ ₁ ^v → Λ ₁ ^c and Δ ₂ ^v → Δ ₂ ^c optical transitions. The low-temperature photoresponse athv < 1.7 eV is due to absorption by Si impurity.     

Synthesis and optical characterization of n-ZnO and p-Cu2ZnSnS4 nanocrystalline thin films for low cost solar cells

High quality ZnO/Cu₂ZnSnS₄ thin films as a window/absorber layers were successfully synthesized via spin coating the sol-gel precursor of each composition without using any vacuum facilities. In this study, the impact of annealing temperature (400 °C, 3 h) on the ZnO window layer and different thickness (3 and 5 layers) of the Cu₂ZnSnS₄ (CZTS) absorber layer were investigated. X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDX), scanning electron microscope (SEM) and UV–vis–NIR spectroscopy were used for the structural, compositional, morphological and optical absorption analysis of each layer. ZnO exhibits wurtzite hexagonal crystal structure with particle size equals to 8.60 and 28.59 nm for fresh and annealed films, respectively. Micro-strain and dislocations density decreased with the annealing temperature. X-ray diffraction patterns for CZTS films show small peak at (112) according to the kesterite structure with particle size in nano-scale for the two thicknesses. ZnO films demonstrated direct optical band gap of 3.23 and 3.21 eV for fresh and annealed films, respectively. CZTS films (3 and 5 layers) also have direct optical band with optimum value (1.51 eV) for thickness of 5 layers. The J-V characteristics of the CZTS-based thin film solar cells (CZTS/ZnO/ZnO:Ag) were measured under air mass AM 1.5 and 100 mW/cm² illumination. The values of the short circuit current (J_sc), open circuit voltage (V_oc) and fill factor (FF) also have been obtained.     

Optimization of Cu<Subscript>2</Subscript>ZnSnS<Subscript>4</Subscript> thin film absorber layer growth without sulphurization using triethanolamine as complexing agent for thin film solar cells applications

Quaternary kesterite Cu₂ZnSnS₄ (CZTS) thin films have been prepared via a simple spin-coating technique based on a sol–gel precursor of 2-methoxyethanol solution with metal salts and thiourea. Solution processed CZTS thin film growth parameters using complexing agent triethanolamine (TEA) have been investigated. Effects of complexing agent TEA on structural, morphological, optical, electrical and photovoltaic properties of CZTS thin films were systematically investigated. X-ray diffraction and Raman spectroscopy studies reveal that amorphous nature of CZTS thin film changes into polycrystalline with kesterite crystal structure with optimized TEA concentartion. Surface morphology of CZTS films were analyzed by field emission scanning electron microscope and atomic force microscope, which revealed the smooth, uniform, homogeneous and densely packed grains and systematic grain growth formation with varying TEA concentrations. UV–Vis spectra revealed a direct energy band gap ranging from 1.78 to 1.50 eV, which was found to depend upon the TEA concentration. X-ray photoelectron spectroscopy demonstrated stoichiometric atomic ratios of multicationic quaternary CZTS thin film grown without sulphurization. p-type conductivity was confirmed using Hall measurements and the effect of varying concentartion of TEA on electrical and photovoltaic properties are studied. The SLG/FTO/ZnO/CZTS/Al thin film solar cell is fabricated with the CZTS absorber layer grown at optimized TAE concentration of 0.06 M. It shows a power conversion efficiency of 0.87% for a 0.16 cm² area with V_oc = 0.257 mV, J_sc = 8.95 mA/cm² and FF?=?38%.     

Doughnut-shaped hierarchical Cu2ZnSnS4 microparticles synthesized by cyclic microwave irradiation

For the first time, hierarchical doughnut-shaped Cu₂ZnSnS₄ (CZTS) microparticles were synthesized by microwave-assisted solution method. N,N-dimethylformamide and polyvinylpyrrolidone (PVP) were used as solvent and stabilizing agent respectively, and the results showed that PVP played an important role in the formation of hierarchical nanostructures. Structural analysis by X-ray diffraction and Raman studies confirmed the formation of single phase kesterite CZTS. Morphological analysis by scanning electron microscope showed doughnut-shaped CZTS microparticles composed of large number of interpenetrating nanoplates. Optical analysis by UV–Vis diffused reflectance spectra showed strong absorption in the visible region with an optical band gap of 1.54 eV. Asymmetric broad emission bands around 1.55 eV and 1.30 eV were observed in the photoluminescence spectrum. A possible formation mechanism for doughnut-shaped CZTS microparticles was put forward and discussed briefly.     

Phase-Modulated Multidimensional Perovskites for High-Sensitivity Self-Powered UV Photodetectors

2D Ruddlesden-Popper perovskites (PVKs) have recently shown overwhelming potential in various optoelectronic devices on account of enhanced stability to their 3D counterparts. So far, regulating the phase distribution and orientation of 2D perovskite thin films remains challenging to achieve efficient charge transport. This work elucidates the balance struck between sufficient gradient sedimentation of perovskite colloids and less formation of small-n phases, which results in the layered alignment of phase compositions and thus in enhanced photoresponse. The solvent engineering strategy, together with the introduction of poly(3,4-ethylene-dioxythiophene):polystyrene sulfonate (PEDOT:PSS) and PC₇₁BM layer jointly contribute to outstanding self-powered performance of indium tin oxide/PEDOT:PSS/PVK/PC₇₁BM/Ag device, with a photocurrent of 18.4 µA and an on/off ratio up to 2800. The as-fabricated photodetector exhibits high sensitivity characteristics with the peak responsivity of 0.22 A W⁻¹ and the detectivity up to 1.3 × 10¹² Jones detected at UV-A region, outperforming most reported perovskite-based UV photodetectors and maintaining high stability over a wide spectrum ranging from UV to visible region. This discovery supplies deep insights into the control of ordered phases and crystallinity in quasi-2D perovskite films for high-performance optoelectronic devices.     

Synthesis of Na0.5Bi0.5TiO3 anisotropic particles with grain orientation by conversion of Na0.5Bi4.5Ti4O15 crystals

A novel method for synthesizing Na_0.5Bi_0.5TiO₃ (BNT) anisotropic particles with grain orientation is reported. Anisotropically shaped particles of BNT were prepared by conversion of Na_0.5Bi_4.5Ti₄O₁₅ (NBT15) single crystals. Platelet NBT15 was produced by molten-salt synthesis. They were converted to BNT by second molten-salt synthesis at 800–1200 °C. NBT15 single-crystal platelets were transformed into platelet particles of polycrystalline BNT. The reaction is topotaxial, those recrystallized BNT were oriented with (h 0 0) plane parallel to the platelet. The use of converted BNT particles as seed was confirmed by performing templated grain growth (TGG) of BNT with 5% grain-oriented, anisotropic particles of BNT.     

Anisotropic Broadband Photoresponse of Layered Type‐II Weyl Semimetal MoTe2

Photodetectors based on Weyl semimetal promise extreme performance in terms of highly sensitive, broadband and self‐powered operation owing to its extraordinary material properties. Layered Type‐II Weyl semimetal that break Lorentz invariance can be further integrated with other two‐dimensional materials to form van der Waals heterostructures and realize multiple functionalities inheriting the advantages of other two‐dimensional materials. Herein, we report the realization of a broadband self‐powered photodetector based on Type‐II Weyl semimetal T_d‐MoTe₂. The prototype metal–MoTe₂–metal photodetector exhibits a responsivity of 0.40 mA W^?1 and specific directivity of 1.07 × 10⁸ Jones with 43 μs response time at 532 nm. Broadband responses from 532 nm to 10.6 μm are experimentally tested with a potential detection range extendable to far‐infrared and terahertz. Furthermore, we identify the response of the detector is polarization angle sensitive due to the anisotropic response of MoTe₂. The anisotropy is found to be wavelength dependent, and the degree of anisotropy increases as the excitation wavelength gets closer to the Weyl nodes. In addition, with power and temperature dependent photoresponse measurements, the photocurrent generation mechanisms are investigated. Our results suggest this emerging class of materials can be harnessed for broadband angle sensitive, self‐powered photodetection with decent responsivities.     

The effect of ZnO coating on LiMn2O4 cycle life in high temperature for lithium secondary batteries

The surface of the spinel LiMn₂O₄ was modified with zinc oxide by a chemical process to improve its electrochemical performance at high temperatures. The physical properties of the prepared products have been investigated by thermogravimetry (TG), X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive X-rays analysis (EDAX). The charge/discharge of the materials was carried at 1 mA/cm² in the range of 3.0 and 4.4 V at 55 °C. The discharge capacity of ZnO-coated LiMn₂O₄ (117 mAh/g) showed only 3% loss of the initial capacity (121 mAh/g) over 60 cycles. The cycle ability improvement of the spinel LiMn₂O₄ coated with ZnO is demonstrated at high temperatures. From the analysis of electrochemical impedance spectroscopy (EIS), the improvement of cycle ability may be attributed to the suppression on the formation of the passivation film and the reduction of Mn dissolution, which result from the modifying the surface of the spinel LiMn₂O₄ with zinc oxide.