Influence of thermoannealing on crystallinity and optical properties of Sb2S3 thin films

Sb₂S₃ thin films are obtained by evaporating of Sb₂S₃ powder onto glass substrates maintained at room temperature under pressure of 2×10^‐5 torr. The composition of the thin films was determined by energy dispersive analysis of X‐ray (EDAX). The effect of thermal annealing in vacuum on the structural properties was studied using X‐ray diffraction (XRD) technique and scanning electron microscopy (SEM). The as‐deposition films were amorphous, while the annealed films have an orthorhombic polycrystalline structure. The optical constants of as‐deposited and annealed Sb₂S₃ thin films were obtained from the analysis of the experimental recorded transmission spectral data over the wavelength range 400‐1400 nm. The transmittance analysis allowed the determination of refractive index as function of wavelength. It was found that the refractive dispersion data obeyed the single oscillator model, from which the dispersion parameters (oscillator energy, E₀, dispersion energy, E_d) were determined. The static refractive index n(0), static dielectric constant, ε_∞, and optical band gap energy, E_g, were also calculated using the values of dispersion parameters. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Substrate temperature effect on the optical properties of amorphous Sb2S3 thin films

Sb₂S₃ amorphous thin films were prepared by thermal evaporation of corresponding powder on thoroughly cleaned glass substrates held at temperature in the range 300‐473 K. X‐ray diffraction and atomic force microscopy have been used to order to identify the structure and morphology of surface thin films. The optical constants of the deposition films were obtained from the analysis of the experimental recorded transmission data over the wavelength range 400‐1400 nm. An analysis of the absorption coefficient values revealed an optical indirect transition with the estimation of the corresponding band gap values. It was found that the optical band gap energy decrease with substrate temperature from 1.67 eV at 300 K to 1.48 eV at 473K. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Influence of the substrate temperature on the structural,optical, and electrical properties of tin selenide thin films deposited by thermal evaporation method

Thin films of tin selenide (SnSe) were deposited on sodalime glass substrates, which were held at different temperatures in the range of 350‐550 K, from the pulverized compound material using thermal evaporation method. The effect of substrate temperature (T_s) on the structural, morphological, optical, and electrical properties of the films were investigated using x‐ray diffraction analysis (XRD), scanning electron microscopy (SEM), transmission measurements, and Hall‐effect characterization techniques. The temperature dependence of the resistance of the films was also studied in the temperature range of 80‐330 K. The XRD spectra and the SEM image analyses suggest that the polycrystalline thin films having uniform distribution of grains along the (111) diffraction plane was obtained at all T_s. With the increase of T_s the intensity of the diffraction peaks increased and well‐resolved peaks at 550 K, substrate temperature, were obtained. The analysis of the data of the optical transmission spectra suggests that the films had energy band gap in the range of 1.38‐1.18 eV. Hall‐effect measurements revealed the resistivity of films in the range 112‐20 Ω cm for films deposited at different T_s. The activation energy for films deposited at different T_s was in the range of 0.14 eV‐0.28 eV as derived from the analysis of the data of low‐temperature resistivity measurements. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of annealing temperature on the structural and optical properties of amorphous Sb2Te2Se thin films

Thin films of Sb₂Te₂Se were prepared by conventional thermal evaporation of the presynthesized material on Corning glass substrates. The chemical composition of the samples was determined by means of energy‐dispersive X‐ray spectrometry. X‐ray diffraction studies on the as‐deposited and annealed films revealed an amorphous‐to‐crystalline phase transition. The as‐deposited and annealed films at T _a = 323 and 373 K are amorphous, while those annealed at T _a= 423 and 473 K are crystalline with a single‐phase of a rhombohedral crystalline structure as that of the source material. The unit‐cell lattice parameters were determined and compared with the reported data. The optical constants (n , k ) of the investigated films were determined from the transmittance and reflectance data at normal incidence in the spectral range 400–2500 nm. The analysis of the absorption spectra revealed non‐direct energy gaps, characterizing the amorphous films, while the crystalline films exhibited direct energy gaps. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Compositional dependence of the optical properties of amorphous Sb2Se3−xSx thin films

Thin films of Sb₂Se_3−xS_x solid solutions (x = 0, 1, 2, and 3) were deposited by thermal evaporation of presynthesized materials on glass substrates held at room temperature. The films compositions were confirmed by using energy dispersive analysis of X-rays (EDAX). X-ray diffraction studies revealed that all the as-deposited films as well as those annealed at T_a < 423 K have amorphous phase. The optical constants (n, k) and the thickness (t) of the films were determined from optical transmittance data, in the spectral range 500-2500 nm, using the Swanepoel method. The dispersion parameters were determined from the analysis of the refractive index. An analysis of the optical absorption spectra revealed an Urbach’s tail in the low absorption region, while in the high absorption region an indirect band gap characterizes the films with different compositions. It was found that the optical band gap energy increases quadratically as the S content increases.     

Effect of substrate temperature on the properties of vacuum evaporated indium selenide thin films

Thin films of InSe were obtained by thermal evaporation techniques on glass substrates maintained at various temperatures (T_sb = 30°, 400°C). X‐ray diffraction analysis showed the occurrence of amorphous to polycrystalline transformation in the films deposited at higher substrate temperature (400°C). The polycrystalline films were found to have a hexagonal lattice. Compositions of these films have been characterized by EDAX and the surface analysis by scanning electron microscopy. Optical properties of the films, investigated by using spectrophotometer transmittance spectra in the wavelength range (300 – 1100 nm), were explained in terms of substrate temperatures. Films formed at room temperature showed an optical band gap (E_g^opt) 1.56 eV; where as the films formed at 400°C were found to have a E_g^opt of 1.92 eV. The increase in the value of E_g^opt with T_sb treatment is interpreted in terms of the density of states model as proposed by Mott and Davis. The analysis of current ‐Voltage characteristics, based on space charge limited currents (SCLC) measurements, confirms the exponential decrease of density of states from the conduction band edge towards the Fermi level for both the amorphous and polycrystalline films. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Photo and thermal induced effects on (As2S3)0.85Sb0.15 amorphous thin films

Exposure with above band gap light and thermal annealing at a temperature near to glass transition temperature, of thermally evaporated amorphous (As₂S₃)_0.85Sb_0.15 thin films were found to be accompanied by structural effects, which in turn, lead to changes in the optical properties. The optical properties of thin films induced by illumination and annealing were studied by Fourier Transform Infrared spectrometry, X-ray Photoelectron Spectroscopy and Raman Spectroscopy. Photodarkening or photobleaching was observed in the film depending upon the conditions of the light exposure or annealing. These changes of the optical properties are assigned to the change of homopolar bond densities. The photodarkening in the as-prepared film was seen at low temperature (4.2 K).     

Growth and electrical properties of flash evaporated AgGaTe2 thin films

Thin films have been prepared by flash evaporation technique of a stoichiometric bulk of AgGaTe₂ compound in vacuum and analysed using X‐ray diffraction, transmission electron microscopy, selected area diffraction and energy dispersive analysis of X‐rays. The effect of substrate temperature on the structural properties – grain size, film orientation, composition, and stoichiometry of the films have been studied. It was found that the polycrystalline, stoichiometric films of AgGaTe₂ can be grown in the substrate temperature range of 473K < Ts < 573K. The influence of substrate temperature (Ts) on the electrical characteristics‐ Resistivity, Hall Mobility, Carrier concentration of AgGaTe₂ thin films were studied. The electrical resistivity was found to decrease with increase in substrate temperature up to 573K and then increases. The variation of activation energy of AgGaTe₂ thin films were also investigated. The implications are discussed. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Influence of density of states on optical properties of GaSe thin film

A systematic investigation on the effect of substrate temperature on the structure, optical absorption and density of states of vacuum evaporated gallium monoselenide (GaSe) thin films is reported. The X‐ray diffraction analysis shows an occurrence of amorphous to polycrystalline transformation in the films deposited at higher‐temperature substrates (573K). The compositional analysis is made with Auger Electron Spectroscopy (AES). The thickness of the film (175nm) is measured by a multiple beam interferometery. Optical characteristics of the GaSe sample have been analyzed using spectrophotometer in the photon energy range of 1.0 ‐ 4 eV. The absorption mechanism has been recognized and the allowed indirect as well as forbidden direct transitions have been found. As‐deposited films show two indirect and allowed transitions due to spin‐orbit splitting of the valence band, as reported here for the first time. Low field conduction have enabled us to determine the density of states in amorphous and poly‐GaSe films. The amorphous and polycrystalline GaSe thin films have localized states density values of N (E_F) = 1.686 × 10¹⁷ cm^‐3 eV^‐1 and 1.257 × 10¹⁵ cm^‐3 eV^‐1 respectively. The experimental results are interpreted in terms of variations in the density of localized states due to progressive decrease of the unsaturated bonds during deposition. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Properties of Sm‐doped CaNb2O6 thin films deposited by radio‐frequency magnetron sputtering

Sm‐doped CaNb₂O₆ (CaNb₂O₆:Sm) phosphor thin films were prepared by radio‐frequency magnetron sputtering on sapphire substrates. The thin films were grown at several growth temperatures and subsequently annealed at 800 °C in air. The crystallinity, surface morphology, optical transmittance, and photoluminescence of the thin films were investigated by X‐ray diffraction, scanning electron microscopy, ultraviolet‐visible spectrophotometry, and fluorescence spectrophotometry, respectively. All of the thin films showed a main red emission radiated by the transition from the ⁴G_5/2 excited state to the ⁶H_9/2 ground state of the Sm³⁺ ions and several weak bands under ultraviolet excitation with a 279 nm wavelength. The optimum growth temperature for depositing the high‐quality CaNb₂O₆:Sm thin films, which was determined from the luminescence intensity, was found to be 400 °C, where the thin film exhibited an orthorhombic structure with a thickness of 370 nm, an average grain size of 220 nm, a band gap energy of 3.99 eV, and an average optical transmittance of 85.9%. These results indicate that the growth temperature plays an important role in controlling the emission intensity and optical band gap energy of CaNb₂O₆:Sm thin films.     

Structure and electrical conduction of Sb2O3 thin films

Antimony trioxide (Sb₂O₃) thin films have been deposited onto glass substrates using thermal evaporation technique at room temperature. The structural feature and surface morphology were characterized by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). Sandwich‐type structures were deposited with films thickness d = 0.55 μm using evaporated electrodes of silver. Current‐voltage (J‐U) characteristics have been measured at various fixed temperatures in the range 293‐473 K. In all cases, at low electric field (E <10⁴ V/cm), ohmic behavior is observed. However, at high electric field (E >10⁴ V/cm), non‐ohmic behavior is observed. An analysis of the experimental data indicates that in the range of high‐applied electric field, the dominant conduction mechanism is space charge limited currents (SCLC). Using the relevant SCLC theory, the carrier concentration, total trap concentration and the ratio of free charge to trapped charge have been calculated and correlated with changes in the structures of antimony trioxide thin films. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Influence of silver concentration in Agx(Sb0.33S0.67)100−x thin amorphous films on photoinduced crystallization

One of the recent applications of thin chalcogenide films is in rewritable optical data recording. This technology is based on reversible phase transition between crystalline and amorphous state. Currently, the primary materials for rewritable optical are Ge–Sb–Te and Ag–In–Sb–Te alloys, but materials research still continues due to the need for increased storage capacity and data recording rates. (Ag)–Sb–S thin films were prepared by thermal evaporation of Sb₃₃S₆₇ bulk and optically induced diffusion and dissolution of thermally evaporated Ag films. Prepared samples were characterized by electron microprobe (SEM-EDX), differential scanning calorimetry (DSC) and by UV–Vis–NIR and Raman spectroscopy. The phase-change recording processes in (Ag)–Sb–S films were carried out by photocrystallization experiments done by Ar⁺ ion laser. The laser exposed dots were studied by scanning electron microscopy (SEM) and transmission optical microscopy. Micro X-ray diffraction (μ-XRD) was used for the exposed dots crystallinity study. Photocrystallization kinetic curves (showing the dependence of optical transmission on laser exposure time) were also established. Crystallization mechanism of Ag_x(Sb_0.33S_0.67)_100−x samples was discussed.     

Electrical properties of PbxSn1‐xS thin films prepared by hot wall deposition method

The Pb_xSn_1‐xS (x = 0 – 0.25) thin films were prepared on glass substrates by hot wall vacuum deposition. The films were polycrystalline monophase in nature and had orthorhombic crystal structure. The thickness of the films was about 2‐3 μm. The temperature dependences of the conductivity were measured in the temperature range from 150 to 420 K. The films revealed p‐type of conductivity. The Seebeck coefficient and conductivity values of the films was in the range of α = 6 – 360 μV/K and σ = 4.8×10^‐5 – 1.5×10^‐2 Ω^‐1·cm^‐1, respectively, at room temperature depending on concentration of the lead in the films. The lead atoms created the substitution defects Pb_Sn in the crystal lattice of the Pb_xSn_1‐xS. These defects formed the donor energy levels in the band gap. The activation energy of the films increased in the range ΔE_a = 0.121 – 0.283 eV with increasing of the lead concentration. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effects of Ge addition on the optical and electrical properties of eutectic Sb70Te30 films

The aim of this work is to study the influence of Ge addition on the optical and electrical properties in eutectic SbTe thin films (with the compositions: Sb₇₀Te₃₀, Ge₂Sb₇₀Te₂₈, Ge₅Sb₇₀Te₂₅ and Ge₁₀Sb₆₅Te₂₅) using visible optical reflectance, ellipsometry measurements, near infrared transmittance spectra, and four probe electrical resistivity measurements. From near infrared transmittance measurements the optical band gap was determined using Tauc’s expression for amorphous materials, a value of about 0.47 eV was obtained without any clear dependence on the Ge content. All amorphous films have approximately the same reflectance value, however the contrast ratio between the crystalline and amorphous phases decrease with increase of Ge. Using in situ four probe measurements versus temperature the dependence of the activation energy of conductance and the onset of the crystallization temperature have been determined for different materials. Four probe measurements have shown that the resistivity of amorphous films increases with increase of Ge. The results obtained have shown that optical and electrical properties of SbTe films with near eutectic composition change with the Ge content and depending on the application, in either optical or electrical memory devices, the most suitable composition needs to be determined.     

Well‐defined Sb2S3 nanostructures: citric acid‐assisted synthesis,electrochemical hydrogen storage properties

Well‐defined (three‐dimensional) 3‐D dandelion‐like Sb₂S₃ nanostructures consisted of numerous nanorods have been achieved via a facile citric acid‐assisted solvothermal process. The as‐prepared products were characterized by X‐ray diffraction (XRD), field‐emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and high‐resolution TEM (HRTEM), respectively. The influence factors of the formation of the hierarchical Sb₂S₃ nanostructures are discussed in details based on FESEM characterizations. By simply controlling the quantity of citric acid, the nucleation and growth process can be readily tuned, which brings the different morphologies and nanostructures of the final products. On the basis of a series of contrastive experiments, the aggregation‐based process and anisotropic growth mechanism are reasonably proposed to understand the formation mechanism of Sb₂S₃ hierarchical architectures with distinctive morphologies including nanorods, and dandelion‐like nanostructures. Charge‐discharge curves of the obtained Sb₂S₃ nanostructures were measured to investigate their electrochemical hydrogen storage behaviors. It revealed that the morphology played a key role on the hydrogen storage capacity of Sb₂S₃ nanostructure. The dandelion‐like Sb₂S₃ nanostructures exhibited higher hydrogen storage capacity (108 mAh g⁻¹) than that of Sb₂S₃ nanorods (95 mAh g⁻¹) at room temperature.     

Microstructure and optical properties of (Pb,Ca)TiO3 films grown on Si(1 0 0) substrates by a simple sol-gel process

Amorphous and polycrystalline (Pb_0.76Ca_0.24)TiO₃ (PCT) thin films deposited on an Si(1 0 0) substrate have been prepared by a simple sol-gel process. The microstructure and surface morphologies of the thin films have been studied by X-ray diffraction (XRD) and atomic force microscopy (AFM). The polycrystalline PCT film on the Si(1 0 0) substrate has a tetragonal perovskite structure with grain size from 60 to 110 nm. AFM reveals smooth surfaces and root mean square (rms) roughness of 0.17 and 4.4 nm for amorphous and polycrystalline films, respectively. The refractive index n and extinction coefficient k of the amorphous and polycrystalline thin films was obtained by spectroscopic ellipsometry as a function of the photon energy in the range from 2.0 to 5.4 eV. The maximum n and direct bandgap energies of amorphous and polycrystalline thin films were 2.66 and 4.11 eV, 2.64 and 3.84 eV, respectively.     

Preparation of shuttle‐like Sb2S3 nanorod‐bundles via a solvothermal approach under alkaline condition

Uniform shuttle‐like Sb₂S₃ nanorod‐bundles were synthesized via a polyvinylpyrrolidone (PVP) assisted solvothermal approach under alkaline condition, using antimony chloride (SbCl₃) and thiourea (CH₄N₂S, Tu) as the starting materials in ethanol. The phase structure, composition and morphology of the product were characterized by means of X‐ray diffraction (XRD), energy dispersive X‐ray spectrometry (EDS), transmission electron microscopy (TEM), and high‐resolution transmission electron microscopy (HRTEM). XRD and EDS results confirm that the synthesized Sb₂S₃ nanorod‐bundles have an orthorhombic structure and an atomic ratio of 3:2 for S:Sb. TEM and HRTEM results show that the shuttle‐like Sb₂S₃ bundles are composed of nanorods with a size distribution of 20‐40 nm and growing along c‐axis. Furthermore, experiments under different reaction conditions were carried out and the mechanism for the growth of nanorod‐bundles was discussed (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Characterization of Vacuum Evaporated Polycrystalline Cd0.96Zn0.04Te Thin Films by XRD,Raman Scattering and Spectroscopic Ellipsometry

Cd_0.96Zn_0.04Te thin films are deposited onto well cleaned glass substrates (Corning 7059) kept at room temperature by vacuum evaporation and the films are annealed at 423 K. Rutherford Backscattering Spectrometry and X‐ray diffraction techniques are used to determine the thickness, composition and crystalline structure and grain size of the films respectively. The films exhibited zinc blende structure with predominant (111) orientation. The surface morphology of the films is studied by Atomic Force Microscopy. The rms roughness of the as‐deposited films is 3.7 nm and on annealing the films at 423K, the rms roughness value decreases to 3.4 nm. The Raman spectra of the Cd_0.96Zn_0.04Te films are recorded at room temperature to study lattice vibrations and their interactions with other excitations. The intensity of the peak increases and the FWHM decreases on annealing the films. The pseudodielectric‐function spectra, ε(E) = ε₁(E) + i ε₂(E), of polycrystalline Cd_0.96Zn_0.04Te thin films in the 1.3 ‐ 5.5eV photon energy range at room temperature are measured by spectroscopic ellipsometry. The measured dielectric function spectra reveal distinct structures at energies of the E₁, E₁+Δ₁ and E₂ critical points are due to interband transitions.     

Preparation of Sb2S3 nanomaterials with different morphologies via a refluxing approach

Single-crystalline antimony trisulfide (Sb₂S₃) nanomaterials with flower-like and rod-like morphologies were successfully synthesized under refluxing conditions by the reaction of antimony trichloride (SbCl₃) and thiourea with PEG400 and OP-10 as the surfactants. X-ray diffraction (XRD) indicates that the obtained sample is orthorhombic-phase Sb₂S₃ with calculated lattice parameters a=1.124 nm, b=1.134 nm and c=0.382 nm. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images show that the flower-like Sb₂S₃ is 9–10 μm in size, which is composed of thin leaves with thickness of 0.05–0.2 μm, width of 0.8–2.2 μm and length of 2.5–3 μm, and the rod-like Sb₂S₃ is 45–360 nm in diameter and 0.7–4 μm in length, respectively. UV–Vis analysis indicates that the band gap of Sb₂S₃ nanorods is 1.52 eV, suitable for photovoltaic conversion. A possible mechanism of formation was proposed. The effects of reaction time and surfactants on the growth of nanomaterials with different morphologies were also investigated.