Effect of periodic precursor on sulfurization process of Cu2ZnSnS4 thin film

In this study, Cu₂ZnSnS₄ (CZTS) thin films were fabricated by periodically sequential depositions of metallic precursors by magnetron sputtering followed by sulfurization. The element compositions, crystal structures, and surface morphologies of the single-period precursor (Zn/Sn/Cu) and four-period precursor (Zn/Sn/Cu/Zn/Sn/Cu/Zn/Sn/Cu/Zn/Sn/Cu) during the sulfurization process were investigated. The experimental results showed that in the initial stage of sulfurization, the single-period precursor had a more efficient reaction with sulfur vapor below 300?°C because of its thicker metal layers. During the process of sulfurization, the CZTS phase first formed in the four-period film at 400?°C, owing to the wide distribution of the internal layer in the periodic thin film. With a further increase in temperature, the crystallinity of CZTS was enhanced and the secondary phases were reduced. A CZTS phase with Cu-poor and Zn-rich composition was confirmed in both thin films after complete sulfurization. The CZTS thin film with a four-period precursor showed a better degree of crystallization, and a single phase of CZTS was obtained more easily than in the single-period thin film. Therefore, using a periodic structure can promote the sulfurization reaction of Cu-Zn-Sn precursors and enhance the properties of CZTS thin films.     

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 %.     

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.     

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.     

Impact of SnS Buffer Layer at Mo/Cu2ZnSnS4 Interface

Cu₂ZnSnS₄ (CZTS) compound is a promising candidate for thin‐film solar cells since its constituents are earth abundant and nontoxic. One of the major challenges to obtain a high‐quality CZTS absorber is to overcome the interfacial mismatch and formation of secondary phases between the CZTS and Mo substrate during the sulfurization process. Generally, the CZTS decomposed into Cu₂S, ZnS, and SnS phases during sulfurization, and high‐density voids and cracks were observed. These micro‐ or macroreactions changed the stoichiometry of CZTS. In this paper, we present the insertion of a SnS buffer layer at Mo/CZTS interface to inhibit the undesired reaction and improve the thin‐film quality. The insertion of the thin SnS buffer layer prevented the CZTS absorber to contact directly with Mo and suppressed the present of secondary phases, pores and cracks. Crack‐free and smooth morphology was obtained. The cell efficiency was significantly improved.     

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.     

Study of interface properties between Cu2ZnSnS4 thin films and metal substrates

In this study, the effects of various metal substrates on the interface properties of Cu₂ZnSnS₄ (CZTS)/metal structures were investigated. The crystal phases, morphologies, and element distributions at the interfaces between CZTS thin films and various metal substrates (Mo, W, Ti, and Al foils) were characterized by X-ray diffraction, Raman spectroscopy, scanning electron microscopy, and secondary ion mass spectroscopy. MoS₂ and WS₂ phases were formed at the CZTS/Mo and CZTS/W interfaces, respectively. No Ti-S and Al-S compounds were formed at the CZTS/Ti and CZTS/Al interfaces. The formation of these phases was dependent on the lowest reaction temperature between the metal foil and S vapor. The size of particles at the back surface of the CZTS thin film on the Ti substrate was larger than that on the other substrates, because the Ti element improved the crystallinity of CZTS. The presence of a thick WS₂ layer at the CZTS/W interface was attributed to the fact that the (211) plane of the W foil caused exposure of a greater number of W atoms in the sulfurization process because of the body-centered cubic crystal structure of W. The diffusion of Ti atoms into the CZTS thin film was due to the large average hop distance of defects in the CZTS thin film and the relatively low activation energy of Ti atoms. Current–voltage curves and energy band diagrams revealed that the ohmic contacts formed at the CZTS/Mo and CZTS/Ti interfaces were better than those formed at the CZTS/W interface and that a Schottky contact was formed at the CZTS/Al interface.     

Chemical solution deposition of epitaxial indium- and aluminum-doped Ga2O3 thin films on sapphire with tunable bandgaps

Compared to the vacuum-required deposition techniques, the chemical solution deposition (CSD) technique is superior in terms of low cost and ease of cation adjustment and upscaling. In this work, highly epitaxial indium- and aluminum-doped Ga₂O₃ thin films are deposited using a novel CSD technique. The 2θ, rocking curve, and φ-scan modes of x-ray diffraction (XRD) measurements and high-resolution transmission electron microscopy suggest that these thin films have a pure beta phase with good in- and out-of-plane crystallization qualities. The effect of incorporating indium and aluminum into the crystallization process is studied using high-temperature in situ XRD measurements. The results indicate that indium and aluminum doping can shift the crystallization of the thin films to lower and higher temperatures, respectively. Additionally, ultraviolet-visible spectroscopy measurements indicate that the bandgap of the sintered thin films can be tuned from 4.05 to 5.03 eV using a mixed precursor solution of In:Ga = 3:7 and Al:Ga = 3:7. The photodetectors based on the (InGa)₂O₃, pure Ga₂O₃, and (AlGa)₂O₃ samples exhibit the maximum photocurrents at 280, 255, and 230 nm, respectively. The results suggest that the described CSD technique is promising for producing high-quality bandgap tunable deep-ultraviolet photoelectrical and high-power devices.     

A systematic study on the growth of molybdenum disulfide with the carbon disulfide as the sulfurizing source

In this work, the growth of molybdenum disulfide (MoS₂) was systematically investigated. Firstly, the stepwise investigation of dual source precursor approach was determined by energy dispersive X-ray, non-resonant Raman spectroscopy and Fourier transform Infrared. The spin-coated MoS-based films were transformed into MoS₂ thin films via thermal vapour sulfurization with carbon disulfide as the sulfurizing source. The extension of sulfurization duration provides the better homogeneity and compactness of MoS₂ thin films. However, the deformation of MoS₂ nanostructure was observed beyond 40 min of sulfurization duration. X-ray photoelectron spectroscopy detects the present of Mo⁴⁺ 3d and S²⁻ 2p chemical states, which proves the highly formation of 2H-MoS₂. Next, absorption features of MoS₂ were discovered at ∼668 nm, ∼617 nm, and ∼447 nm. Resonant Raman (RR) spectroscopy shows multilayers of MoS₂ are grown. However, multilayers wall of MoS₂ nanoparticles was observed by the high-resolution transmission electron spectroscopy (HRTEM). The deviation of these observations (RR and HRTEM) is due to the rotational stacking fault of MoS₂ layers.     

Structural and Optical Properties of Nanoscale Galinobisuitite Thin Films

Galinobisuitite thin films of (Bi₂S₃)(PbS) were prepared using the chemical bath deposition technique (CBD). Thin films were prepared by a modified chemical deposition process by allowing the triethanolamine (TEA) complex of Bi³⁺ and Pb²⁺ to react with S²⁻ ions, which are released slowly by the dissociation of the thiourea (TU) solution. The films are polycrystalline and the average crystallite size is 35 nm. The composition of the films was measured using the atomic absorption spectroscopy (AAS) technique. The films are very adherent to the substrates. The crystal structure of Galinobisuitite thin films was calculated by using the X-ray diffraction (XRD) technique. The surface morphology and roughness of the films were studied using scanning electron microscopes (SEM), transmission electron microscopes (TEM) and stylus profilers respectively. The optical band gaps of the films were estimated from optical measurements.     

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.     

Tuning oxygen impurities and microstructure of nanocrystalline silicon photovoltaic materials through hydrogen dilution

As a great promising material for third-generation thin-film photovoltaic cells, hydrogenated nanocrystalline silicon (nc-Si:H) thin films have a complex mixed-phase structure, which determines its defectful nature and easy residing of oxygen impurities. We have performed a detailed investigation on the microstructure properties and oxygen impurities in the nc-Si:H thin films prepared under different hydrogen dilution ratio treatment by the plasma-enhanced chemical vapor deposition (PECVD) process. X-ray diffraction, transmission electron microscopy, Raman spectroscopy, and optical transmission spectroscopy have been utilized to fully characterize the microstructure properties of the nc-Si:H films. The oxygen and hydrogen contents have been obtained from infrared absorption spectroscopy. And the configuration state of oxygen impurities on the surface of the films has been confirmed by X-ray photoelectron spectroscopy, indicating that the films were well oxidized in the form of SiO₂. The correlation between the hydrogen content and the volume fraction of grain boundaries derived from the Raman measurements shows that the majority of the incorporated hydrogen is localized inside the grain boundaries. Furthermore, with the detailed information on the bonding configurations acquired from the infrared absorption spectroscopy, a full explanation has been provided for the mechanism of the varying microstructure evolution and oxygen impurities based on the two models of ion bombardment effect and hydrogen-induced annealing effect.     

铜锌锡硫半导体薄膜材料的制备与表征

采用水热法成功制备了Cu2ZnSnS4(CZTS)半导体材料,通过浸涂法制备了相应的薄膜,并在N2气氛中于400℃对薄膜进行了退火处理.用X射线荧光光谱分析了所得CZTS粉末中各组成元素的含量,并分别用X射线衍射、扫描电子显微镜和紫外-可见-近红外光谱对CZTS薄膜样品的晶体结构、表面形貌和带隙进行了表征.结果表明:所...     

Distribution of relaxation time in solution-processed polycrystalline CZTS thin films: Study of impedance spectroscopy

Here we report the complex impedance spectroscopic analysis of polycrystalline CZTS thin films synthesized by sol-gel spin coating technique without any post deposition sulphurization. The films are characterized by microstructural, compositional, optical and electrical studies to confirm the formation of kesterite phase of CZTS comprises of well distributed compact grains with the optical band gap 1.44?eV. Room temperature electrical characterizations of the CZTS thin films by four-probe and Hall effect technique revealed the p-type conductivity of the films with resistivity ~ 1.45?×?10^?2 Ω?cm, mobility ~ 3.7?×?10³ cm² V^?1 s^?1 and carrier concentration ~ 1.82?×?10¹⁷ cm^?3. The distribution of relaxation time (DRT) function with improved frequency resolution is reconstructed from the impedance spectra of CZTS film recorded in the frequency range 50?Hz to 5?MHz at room temperature to identify the number of electrical processes in the polycrystalline film. The Nyquist plot is fitted into electrical model consist of three parallel combinations of resistor (R) and capacitor (C) in series as three major peaks in DRT function indicates the presence of different relaxation processes with major contributions from core grains along with smaller contributions from grain boundary and interfaces. The room temperature frequency dependence of dielectric constant, loss tangent and ac conductivity is also studied for the CZTS films.     

Heteroepitaxial growth of Cu2O films on Nb-SrTiO3 substrates and their photovoltaic properties

In this paper, p-type Cu₂O thin films have been epitaxially grown on n-type semiconducting (001) oriented Nb-SrTiO₃ (NSTO) substrates with different Nb doping concentration by pulsed laser deposition technique. X-ray diffraction and high resolution transmission electron microscopy reveal a cube-on-cube epitaxial relationship between Cu₂O and NSTO. It is found that the deposition temperature, the thickness of Cu₂O films and the Nb doping concentration of NSTO substrates have critical impact on the photovoltaic (PV) properties of the Cu₂O/NSTO heterojunction devices. A maximum PV performance is observed in ITO/Cu₂O/NSTO device when the deposition temperature, film thickness and Nb doping concentration of NSTO are 550 °C, 76 nm, and 0.7 wt% NSTO, respectively. The optimized PV output corresponds to the open circuit voltage, short-circuit current density, fill factor and photovoltaic conversion efficiency about 0.45 V, 1.1 mA/cm², 46% and 0.23%,respectively. This work offers an insight into the strategy for developing and designing novel optoelectronics of NSTO-based oxide heterostructures.     

Diamond-like carbon thin films by microwave surface-wave plasma CVD aimed for the application of photovoltaic solar cells

The nitrogen doped diamond-like carbon (DLC) thin films were deposited on quartz and silicon substrates by a newly developed microwave surface-wave plasma chemical vapor deposition, aiming the application of the films for photovoltaic solar cells. For film deposition, we used argon as carrier gas, nitrogen as dopant and hydrocarbon source gases, such as camphor (C₁₀H₁₆O) dissolved with ethyl alcohol (C₂H₅OH), methane (CH₄), ethylene (C₂H₄) and acetylene (C₂H₂). The optical and electrical properties of the films were studied using X-ray photoelectron spectroscopy, Nanopics 2100/NPX200 surface profiler, UV/VIS/NIR spectroscopy, atomic force microscope, electrical conductivity and solar simulator measurements. The optical band gap of the films has been lowered from 3.1 to 2.4 eV by nitrogen doping, and from 2.65 to 1.9 eV by experimenting with different hydrocarbon source gases. The nitrogen doped (flow rate: 5 sccm; atomic fraction: 5.16%) film shows semiconducting properties in dark (i.e. 8.1 × 10^{− 4} Ω^{− 1} cm^{− 1}) and under the light illumination (i.e. 9.9 × 10^{− 4} Ω^{− 1} cm^{− 1}). The surface morphology of the both undoped and nitrogen doped films are found to be very smooth (RMS roughness ≤ 0.5 nm). The preliminary investigation on photovoltaic properties of DLC (nitrogen doped)/p-Si structure show that open-circuit voltage of 223 mV and short-circuit current density of 8.3 × 10^{− 3} mA/cm². The power conversion efficiency and fill factor of this structure were found to be 3.6 × 10^{− 4}% and 17.9%, respectively. The use of DLC in photovoltaic solar cells is still in its infancy due to the complicated microstructure of carbon bondings, high defect density, low photoconductivity and difficulties in controlling conduction type. Our research work is in progress to realize cheap, reasonably high efficiency and environmental friendly DLC-based photovoltaic solar cells in the future.     

Chemical Vapor Deposition of Polymer Thin Films Using Cationic Initiation

Chemical vapor deposition (CVD) is an attractive technique for the fabrication of high‐quality polymer thin films. The scheme used to initiate polymer chain growth is fundamental to controlling polymer thin film chemistry. A new initiation scheme for polymer CVD utilizing cationic initiation with a strong Lewis acid, TiCl₄, in combination with a hydrogen donor, H₂O, is presented. This coinitiation scheme results in polystyrene deposition rates of 139 nm min^?1, relative to just 34 nm min^?1 when TiCl₄ is used alone. Characterization by Fourier transform infrared spectroscopy shows that the polymer structures of polystyrene films prepared by conventional solution‐based techniques and cationic CVD are similar. Synthesis of cross‐linked polymer thin films is also demonstrated by depositing poly(divinylbenzene) and showing its insolubility in a range of solvents. The practical utility of these poly(divinylbenzene) films as corrosion resistant coatings is demonstrated. In 1 n HCl, 200 nm thick films on stainless steel increase the polarization resistance by a factor of 44 relative to bare, untreated stainless steel.     

Novel approach to synthesize morphology variant tungsten oxide thin films for efficient chemical sensing

A new approach has been designed to synthesize and modify the morphology of high quality nanocrystalline tungsten oxide (WO₃) thin films using hot filament chemical vapor deposition (HFCVD) technique. The thin films were successfully synthesized having completely distinct morphologies using different processing conditions in very short duration of time 4–6 min. Two types of morphologies resembling a broccoli decorated with WO₃ nanograins (BWN) and another having faceted, pyramidal growth of WO₃ nanograins (PWN) were obtained. Both as-prepared films displayed excellent uniformity and exhibited the formation of standard monoclinic structure without undergoing any additional calcination/sintering. The morphology variant WO₃ thin films were applied as sensing electrodes to detect toxic chemical such as diethylamine (DEA) chemical. Due to smaller particle size, higher surface area and higher oxygen contents, the BWN thin film offered promising performance in DEA sensing with good sensitivity of ～3.5 μAμM^?1cm^?2 and fast response ～10 s.     

Annealing Effect on the Properties of Cu(In0.7Ga0.3)Se2 Thin Films Grown by Femtosecond Pulsed Laser Deposition

This work reports the crystallization, microstructure, and surface composition of CuIn_0.7Ga_0.3Se₂ (CIGS) thin films grown by femtosecond pulsed laser deposition at different annealing temperatures. The structural and optical properties of the CIGS films were characterized by X‐ray diffraction, Raman scattering, UV‐visible spectroscopy, and Hall effect measurement. The results indicate that binary crystals of CuSe initially formed on the as‐deposited film, but then completely turned into a quaternary chalcopyrite structure after annealing at 400°C. Phase transformation significantly affects the surface morphology, Hall properties, and band gap. Transmission electron microscopy further revealed that an interface between the Mo substrate and CIGS crystallites contains an amorphous layer even at the high temperature of 500°C. For the application of photovoltaic devices, we also report on the photoresponse of both as‐deposited and annealed films as demonstrated by preliminary tests.