Properties of Cu2ZnSn(SxSe1−x)4 thin films prepared by one-step sulfo-selenization of alloyed metal precursors

The pentenary system, Cu₂ZnSn(S_xSe_1−x)₄ (CZTSSe), is a promising alternative for thin film solar cells. In this study, CZTSSe thin films were prepared using a two-stage process involving the thermal diffusion of sulfur (S) and selenium (Se) vapors into sputtered metallic precursors at approximately 450 °C. The effects of the sulfur content on the composition, structure, optical and electrical characteristics of the CZTSSe thin films were investigated. The films showed a kesterite structure with a predominant (112) orientation. X-ray diffraction and Raman spectroscopy confirmed the formation of a single phase CZTSSe compound. The band gap was dependent on the sulfur content and was calculated to be 1.25 eV, 1.33 eV and 1.40 eV for CZTSSe films with a S/(S + Se) ratio of 0.3, 0.5 and 0.7, respectively. All films exhibited p-type semiconductor properties.     

Optical properties of ternary ZnS x Se1−x polycrystalline thin films

Ternary ZnS_xSe_1–x polycrystalline thin films were prepared by evaporation in vacuum of 10^–5 Torr. The molecular fractionx varied in the region ox1. The optical constants (the refractive indexn, the absorption indexk, and the absorption coefficient) were determined in the wavelength range 300–1600nm. A plot representing ₂=f(hv) shows that the ZnS_xSe_1–x polycrystalline thin films of different compositions have two direct transitions corresponding to the energy gapsE andE+. The variation in eitherE orE+ withx indicates that this system belongs to the amalgamation type. Such variation follows a quadratic equation. The bowing parameter was found to be 0.456 eV, roughly equal to the calculated value 0.60 eV using the empirical pseudopotential method based on the virtual-crystal approximation, in which the disorder effect has not been taken into account.     

Band gap control and photoluminescence properties of Ba(Co2x Ti1−x )O3 thin films prepared by Sol–gel method

This paper reports on the preparation, characterization and optical properties of transparent Ba(Co_2x Ti_1?x )O₃ (0 ≤ x ≤ 0.06) thin films prepared by sol–gel method and deposited on fused quartz substrate by spin-coating technique. Their formation is confirmed by X-ray diffraction patterns, energy dispersive X-ray spectrometry and Fourier transformed infrared measurements. Hitherto unreported near-band-gap photoluminescence in ultraviolet, at 378 nm (3.28 eV), of exciton origin is observed which remains unaffected with change in excitation wavelength from 320 to 350 nm. A weak defect emission appears in green region. For larger excitation wavelength, i.e., 488 nm, emission arising from localized states again occurs in green region but with lower energy. The occurrence of efficient violet–blue PL emission is related to ‘direct’ band gap and shallow levels with high optical band gap values. Analysis of band gap variation with dopant concentration, determined using Tauc’s plot assuming them both of ‘direct’ and ‘indirect’ nature, also indicates the ‘direct’ nature. Co⁺² ions as dopants promote a decrease of band gap of films linearly. Scanning electron micrographs show the granular and flakes-like surface growth. Atomic force microscopy images show the presence of ribbon-like nanostructured grains throughout the surface of the films which is smooth with small values of surface roughness.     

Photovoltaic structures using AgSb(S x Se1−x )2 thin films as absorber

Photovoltaic structures were prepared using AgSb(S _x Se_1?x )₂ as absorber and CdS as window layer at various conditions via a hybrid technique of chemical bath deposition and thermal evaporation followed by heat treatments. Silver antimony sulfo selenide thin films [AgSb(S _x Se_1?x )₂] were prepared by heating multilayers of sequentially deposited Sb₂S₃/Ag dipped in Na₂SeSO₃ solution, glass/Sb₂S₃/Ag/Se. For this, Sb₂S₃ thin films were deposited from a chemical bath containing SbCl₃ and Na₂S₂O₃. Then, Ag thin films were thermally evaporated on glass/Sb₂S₃, followed by selenization by dipping in an acidic solution of Na₂SeSO₃. The duration of dipping was varied as 3, 4 and 5 h. Two different heat treatments, one at 350 °C for 20 min in vacuum followed by a post-heat treatment at 325 °C for 2 h in Ar, and the other at 350 °C for 1 h in Ar, were applied to the multilayers of different configurations. X-ray diffraction results showed the formation of AgSb(S _x Se_1?x )₂ thin films as the primary phase and AgSb(S,Se)₂ and Sb₂S₃ as secondary phases. Morphology and elemental detection were done by scanning electron microscopy and energy dispersive X-ray analysis. X-ray photoelectron spectroscopic studies showed the depthwise composition of the films. Optical properties were determined by UV–vis–IR transmittance and reflection spectral analysis. AgSb(S _x Se_1?x )₂ formed at different conditions was incorporated in PV structures glass/FTO/CdS/AgSb(S _x Se_1?x )₂/C/Ag. Chemically deposited post-annealed CdS thin films of various thicknesses were used as window layer. J–V characteristics of the cells were measured under dark and AM1.5 illumination. Analysis of the J–V characteristics resulted in the best solar cell parameters of V _oc = 520 mV, J _sc = 9.70 mA cm^?2, FF = 0.50 and η = 2.7 %.     

Fabrication of Cu2ZnSn(SxSe1−x)4 thin film solar cell by single step sulfo-selenization of stacked metallic precursors

We have synthesized an efficient Cu₂ZnSn(S_xSe_1−x)₄ (CZTSSe) absorbers by using single-step rapid thermal sulfo-selenization process of sputtered stack metallic precursor (Zn/Sn/Cu) films. The structural and morphological studies confirm that the suitability of the rapid thermal sulfo-selenization process for the synthesis of a CZTSSe absorber without any secondary phases with large grains. The annealing atmosphere with a mixed-chalcogen source enhances the grain growth of the CZTSSe absorber as compared with pure Cu₂ZnSnS₄ (CZTS) and Cu₂ZnSnSe₄ (CZTSe) absorbers. The CZTSSe thin film solar cell shows the best conversion efficiency of ∼7%.     

Growth mechanism, microstructure and transport properties of Sr1−x La x CuO2 (x=0.10−0.15) thin films

Sr_1−x La _x CuO₂ (x=0.10−0.15) thin films with an infinite-layer type structure were grown on BaTiO₃ buffered (001) SrTiO₃ substrates by pulsed laser deposition (PLD). The evolution of the growth front was monitored, in-situ, by high-pressure reflection high-energy electron diffraction (RHEED), while the surface morphology was analyzed by means of atomic force microscopy (AFM), ex-situ. X-ray diffraction (XRD) was used to determine the evolution of the film structure with deposition and cooling parameters, as well as to study the type and level of epitaxial strain in the Sr_1−x La _x CuO₂ films. The RHEED data showed that the Sr_1−x La _x CuO₂ films grow on BaTiO₃/SrTiO₃ following a 2D or Stranski-Krastanov mechanism, depending on the La doping level. The transition point (critical thickness d _c) from layer-by-layer like (2D) to island (3D) growth depends on the film stoichiometry: decreasing the La doping concentration x from 0.15 to 0.10, the critical thickness d _c increases from ∼45 nm to ∼75 nm. In order to induce superconductivity, the Sr_1−x La _x CuO₂ films were cooled down under reduction conditions. The as-deposited films showed semiconducting or metallic behavior, the resistivity decreasing with increasing La concentration. Post-deposition vacuum annealing resulted in a superconducting transition onset (but no zero resistance down to 4.2 K) only for some of the x=0.15 Sr_1−x La _x CuO₂ films.     

Preparation and properties of Y1−xHoxBa2Cu3O7−δ thin films by TFA-MOD method

Y_1?xHo_xBa₂Cu₃O_7?δ (x = 0, 0.1, 0.2, 0.3, 0.4, 0.5) thin films were prepared on LaAlO₃ (0 0 1) substrates by trifluoroacetate metal organic deposition (TFA-MOD) without change of the processing parameters. The highest J_c was attributed to the sample of Y_0.6Ho_0.4Ba₂Cu₃O_7?δ thin film, whose critical current density is about 1.6 times as compared to that of YBa₂Cu₃O_7?δ thin film at 77 K and self field. The flux pinning type was not varied with Ho substitution and can be attributed to δl pinning model, which is attributed to the close ionic radius between the Y³⁺ and Ho³⁺ ions. The improvement of J_c by Ho substitution without change of the processing parameters will provide an effective route to enhance the J_c of YBCO-based thin films using TFA-MOD method.     

Effect of air humidity on the microstructure and properties of large-area YBa2Cu3O7−x films by TFA-MOD process

Large-area YBa₂Cu₃O_7?x (YBCO) films had been successfully fabricated on LaAlO₃ (LAO) substrate by metalorganic deposition using trifluoroacetates (TFA-MOD) and the effect of air humidity on the structure and properties of YBCO films was systematically investigated. The precursor coating process was performed in the air humidity range of 70–40%. According to the X-ray diffraction (XRD) and scanning electron microscopy (SEM) images, the films prepared at high air humidity showed poor electrical performance due to large pores and impurity phases. In contrast, dense, homogeneous and epitaxially grown YBCO films prepared at low air humidity with the critical current densities of 3.8–5.0 MA cm^?2 at 77 K had been obtained.     

Role of annealing duration on the microstructure and electrochemical performance of β-V2O5 thin films

Vanadium pentoxide thin films have been prepared by sol–gel spin coating method. The eight-layered films coated on fluorine-doped tin oxide substrate and glass substrate were subjected to different durations of annealing under a constant annealing temperature of 300?°C from 30 to 120?min. The X-ray diffraction spectrum reveals crystallinity along (2?0?0) direction. The SEM images of these films show the variation in the surface morphology with increase in annealing duration. The supercapacitor behaviour has been studied using cyclic voltammetry technique and electrochemical impedance spectroscopy. The film annealed for 60?min exhibits a maximum specific capacitance of 346?F/g at a scan rate of 5?mV/s with a charge transfer resistance of 172 Ω.     

Effect of annealing temperature on the microstructure and optical–electrical properties of Cu–Al–O thin films

We have successfully prepared Cu–Al–O thin films on silicon (100) and quartz substrates by radio frequency (RF) magnetron sputtering method. The as-deposited Cu–Al–O film is amorphous in nature and post-annealing treatment in argon ambience results in crystallization of the films and the formation of CuAlO₂. The annealing temperature plays an important role in the surface morphology, phase constitution and preferred growth orientation of CuAlO₂ phase, thus affecting the properties of the film. The film annealed at 900 °C is mainly composed of CuAlO₂ phase and shows smooth surface morphology with well-defined grain boundaries, thus exhibiting the optimum optical–electrical properties with electrical resistivity being 79.7 Ω·cm at room temperature and optical transmittance being 80% in visible region. The direct optical band gaps of the films are found in the range of 3.3–3.8 eV depending on the annealing temperature.     

Production of YBa2Cu3O7−x superconducting thin films by pulsed pseudospark electron beam evaporation

Thin-film superconducting YBa₂Cu₃O_7–x layers have been produced in a single-step process by pulsed electron beam evaporation from a stoichiometric 1-2-3 target. The films were produced at the 100 surface of SrTiO₃ substrates heated to a temperature of approximately 1000 K in a pure oxygen atmosphere of about 10 Pa total pressure. After deposition the films were cooled in situ within 20 minutes to ambient temperature. At present, the films are polycrystalline and show a T_c,zero of 83 K with a transition width of 3–5 K. Critical current densities of 7·10⁴ A/cm² at 4.2 K and zero magnetic field have been achieved. The pulsed electron beams used in these experiments are produced by a pseudospark discharge; the estimated energy density deposited at the target surface by the electron beam is of the order of 4 J/cm².     

Thermoelectric properties of n-Bi2Te3 − x − y Se x S y solid solutions under high pressure

The thermoelectric properties of n-Bi₂Te_{3 ? x ? y} Se _x S _y solid solutions with atomic substitutions in the tellurium sublattice (x = 0.27, 0.3, y = 0, and x = y = 0.09) have been studied under a pressure to 8 GPa. It has been found that the Seebeck coefficient and the resistance decrease with increasing P, and power factor χ increases in all compositions and becomes maximal at pressures of 2–4 GPa. It has been shown that the power factor χ, which is proportional to the product of the effective mass of the density of states m/m m/m ₀ and the charge carrier mobility μ₀ in the form (m/m ₀)^3/2μ₀, increases with increasing pressure mainly due to the increase in the mobility and also depends on the solid solution composition. In the composition with substitution Te → Se + S (x = y = 0.09), the peculiarity of the dependence of m/m ₀ on P in the pressure range corresponding to maximal values of the power factor can be explained by the existence of an electronic topological transition. The increase in the power factor under pressure in n-type Bi₂Te_{3 ? x ? y} Se _x S _y solid solutions combined with similar data for p-type Bi_{2 ? x} Sb _x Te₃ solid solutions obtained earlier, including the estimations of possible changes in the thermal conductivity with increasing pressure, give grounds to design thermoelements with improved value of the thermoelectric figure-of-merit, which can be 50–70% at pressures of 2–4 GPa.     

Birefringence of CuGa(S1−x Sex)2 single crystals

The magnitude and dispersion of birefringence of single crystals of CuGa(S_1?x Se_x)₂ solid solutions is studied in the spectral region of 0.5–2.5 μ at T=300 K. The effect of the substitution of selenium for sulfur on special features of birefringence dispersion is analyzed within the framework of the single-oscillator model.     

Synthesis and characterization of nanostructured (Pb1− x Sr x )TiO3 thin films by a modified chemical route

The coating solutions of nanostructured (Pb_{1– x} Sr _x )TiO₃ (PST) thin films have been prepared by the sol–gel combined metallo-organic decomposition method. The coating solutions were deposited on Pt/Ti/SiO₂/Si substrates using a spin-coating technique with spinning speed of 4300 rpm and annealed at 650°C. The effect of Sr content in reducing the grain size and tetragonal distortion of PST films has been studied. The optimum conditions for crystalline phase formation in the films have been analyzed by thermogravimetric, differential thermal analysis and Fourier transform infrared spectroscopy. The phase and microstructure of the films were studied by X-ray diffraction (XRD) and atomic force microscopy (AFM). The XRD pattern shows that the PST thin films are crystallized into tetragonal structures without any impurity phase and the distortion ratio reduces with increasing Sr concentration. The AFM results indicate an increase in grain size with increasing annealing temperature of the film and reduction in grain size with increasing Sr concentration.     

Effect of in situ post-deposition annealing on the formation of α-In2Se3 thin films grown by elemental evaporation

Stoichiometric polycrystalline In₂Se₃ thin films have been grown by elemental evaporation on both glass and quartz substrates. The compositions are examined by DAN fluorimetry and X-ray photoelectron spectroscopy (XPS). Structure of the films are characterized by X-ray diffraction. The structure of this -form of thin films have been determined to be hexagonal. Optimization of the preparative conditions employed for elemental evaporation, helped in preparing monophasic films by the suppression of other phases to a very minor extent. Influence of annealing conditions on the stoichiometry of the films are investigated in detail.     

Influence of the composition of TlGa1 − x Er x Se2 crystals on their dielectric characteristics and parameters of localized states

Frequency dependences of the real (?′) and imaginary (?″) parts of the complex permittivity, the dielectric loss tangent (tanδ), and the ac conductivity (σ_ac) in frequency range f = 5 × 10⁴?3.5 × 10⁷ Hz have been investigated for TlGa_{1 ? x} Er _x Se₂ crystals of various compositions. It has been established that the relaxation dispersion of ?′ and ?″ takes place for the studied crystals. The influence of the erbium content in the crystals on their dielectric coefficients has been studied. The ac conductivity of the TlGa_{1 ? x} Er _x Se₂ single crystals in the high-frequency range obeys the law σ_ac ～ f ^0.8, which is characteristic of the hopping mechanism of charge transfer over the states localized in the vicinity of the Fermi level. Parameters of the states localized in the band gap of TlGa_{1 ? x} Er _x Se₂ and the influence of the composition of the crystals on these parameters have been evaluated.     

Growth stages of YSZ-buffer layers and YBa2Cu3O7−x thin films on silicon substrates studied by scanning probe microscopy

Scanning probe microscopy has been applied to study various growth stages of YSZ (yttria-stabilized zirconia) buffer layers on silicon and of YBa₂Cu₃O_7–x thin films on YSZ/Si. YSZ buffer layers of 75 nm thickness exhibit a remarkable smooth surface with a rms roughness of about 0.5 nm for a surface area of 5 m×5 m. The subsequent growth of YBa₂Cu₃O_7–x thin films was investigated from nucleation to the formation of growth hills. Screw dislocations were found only in very rare cases.     

Growth of YBa2Cu3O7−x thin films on sapphire with a cerium-oxide sublayer

The possibility is demonstrated of preparing high-quality films of the high-temperature superconductor YBa₂Cu₃C_7-δ with thicknesses up to 2.6 μm by dc magnetron sputtering. It is found that inclusions consisting of CuO and YBa₂Cu₃O₈ coexist with the growing film and are “sinks” for defects, nonstoichiometric atoms, and mechanical stresses. Using x-ray diffraction and Rutherford backscattering, we find that the structural perfection of the films is improved by increasing the thickness when using the proposed fabrication technique. Zh. Tekh. Fiz. 69, 94–98 (January 1999)     

Temperature and composition dependence of the energy band gap of Pb1−x Mn x S solid solution

Photovoltaicp-n junctions inn-type Pb_1–xMn _x Sx0.04, have been made by sulphur diffusion. Current-voltage and resistance-voltage characteristics have been examined at various temperatures. The spectral responses of the diodes have been measured within the temperature range from 5 to 300 K at a zero bias. From these measurements the energy band gap of Pb_1–x Mn _x S solid solution has been determined as a function of temperature and manganese content. A phenomenological expression describing the variation of the energy gap of Pb_1–x Mn _x S with temperature and alloy composition has been proposed.