Structural,photoelectrical and photoluminescence properties of Ta-doped SnO2 monocrystal films grown on MgF2 (110) substrates

Epitaxial Ta-doped SnO₂ films with Ta concentrations from 0 to 8?at.% have been deposited on MgF₂ (110) substrates by the metal-organic chemical vapor deposition (MOCVD) method. The effects of Ta doping on the structural, photoelectrical and photoluminescence (PL) properties of the obtained films were studied in detail. The results showed that the single crystal rutile SnO₂ films were obtained and the heteroepitaxial relationship was SnO₂ (110) || MgF₂ (110) with SnO₂ [001] || MgF₂ [001]. The highest Hall mobility of 74.2?cm²?V^?1?s^?1 was achieved for the 5?at.% Ta-doped SnO₂ film and the minimum resistivity as low as 2.5?×?10^?4?Ω?cm was obtained at 6?at.% of Ta-doping. In the visible region, all the obtained films had average transmittances exceeding 87%. As the Ta concentration increased from 0 to 8?at.%, the optical band gap of the films rose from 3.89 to 4.32?eV. The room temperature PL spectra of Ta-doped SnO₂ films showed intense green emission, weak violet and yellow emissions. The corresponding PL mechanisms were discussed.     

Effect of rapid thermal annealing on the properties of zinc tin oxide films prepared by plasma-enhanced atomic layer deposition

The effect of rapid thermal annealing treatments on the microstructure, surface morphology, and optical characteristics of zinc tin oxide (ZTO) films produced by plasma-enhanced atomic layer deposition was investigated. The ZTO films were annealed in oxygen atmosphere for 2 min at four selected temperatures from 500 to 800 °C. The X-ray diffraction showed that the annealing temperature has a great influence on the crystalline characteristics of ZTO films. The film shows complete amorphous structure for as-deposited ZTO film. Meanwhile, the spinel zinc stannate Zn₂SnO₄ was obtained for the samples annealed from 500 to 800 °C, which shows polycrystalline nature. The X-ray photoelectron spectroscopy proved that the annealing process in oxygen gas can effectively can reduce the oxygen vacancy defects in the films. In addition, the photoluminescence spectroscopy manifests an ultraviolet emission with a broad peak range from 345 to 385 nm. Moreover, the ultraviolet luminescence intensity increases continuously with the increase of annealing temperature. Spectroscopic ellipsometry analyses demonstrate that the refractive index of annealed films increases as the increase of annealing temperature, while the extinction coefficient decreases gradually with the increase of annealing temperature in the visible light range.     

Improved electrical and optical properties in epitaxial Cd2SnO4 films

Epitaxial Cd₂SnO₄ films were fabricated on MgO(00l) single crystalline substrates by pulsed laser deposition technique at various substrate temperatures and growth oxygen pressures. The microstructure, transport, and optical properties of the films were studied in detail. High-resolution X-ray diffraction and high-resolution transmission electron microscopy results demonstrate that all the Cd₂SnO₄ films are grown epitaxially on MgO(00l) substrates. Atomic force microscope images indicate that the films have smooth surface morphologies. Hall-effect measurements reveal that the epitaxial film grown at 680^°C and 40 Pa presents the minimum resistivity value of 0.61 mΩcm and maximal Hall mobility of 32.87 cm² V⁻¹ s⁻¹. The metal–semiconductor transitions of Cd₂SnO₄ films were observed and explained by competitive effects of two conductive mechanisms. The optical transmittance of the Cd₂SnO₄ films is higher than 75% in the visible and near-infrared range, and the optical bandgap was determined to be about 3.09 eV for the film grown at optimal condition. The band structure and density of states of the Cd₂SnO₄ were calculated by the density functional theory.     

A new synergistic effect in one step sputtered ZnO/Zn2SnO4 heterojunction films for H2 sensing related to crystal structure and film compactness

In this paper, ZnO/Zn₂SnO₄ heterojunction films were one step fabricated by magnetron sputtering and the dependence of crystal structures, film compactness and H₂ sensing properties on annealing process were investigated and discussed. The results showed that three typical surface morphologies can be controlled by adjusting annealing temperatures and periods. The films annealed at the temperature of 550 °C for 6 h showed the best H₂ sensing properties. It exhibited a response (R_a/R_g) of 28.3–100 ppm H₂ at the temperature of 230 °C and the detection limit is 30.2 ppb. Meanwhile, it also showed a good selectivity and long-term stability to H₂. The H₂ sensing mechanism is attributed to the synergistic effect between ZnO (0001) signal crystal facets and ZnO/Zn₂SnO₄ heterojunction structures which enhanced the gas reactivity and resistance modulation range. On the contrary, insufficient annealing restricts the film crystallinity and the growth of hexagonal ZnO while undue annealing destroys the compactness of the films, leading to poor H₂ sensing properties.     

Growth of Zn2GeO4 thin film by thermal evaporation on ITO substrate for thermoelectric power generation applications

In this paper, we have reported the growth of Zn₂GeO₄ thin film and investigated its potential for thermoelectric power generation applications. Zn₂GeO₄ alloy thin film was grown on Indium coated glass substrate by the evaporation of Zn and Ge metals with constant oxygen gas flow rate of 100 sccm in tube furnace. The grown film was cut into pieces and annealed at various temperatures from 500° to 700°C with a step of 100?°C in a programmable furnace for one hour. The structure of as grown and annealed thin films was verified by XRD and Raman spectroscopy measurements. The XRD data evident that Zn₂GeO₄ alloy hexagonal structure along with GeO₂ and ZnO phases were observed at annealing temperatures 600 and 700?°C but below this temperature no alloy phase was detected by XRD and Raman Spectroscopy. To calculate the thermoelectric properties, temperature dependent Seebeck measurements were performed in the temperature range of 25–100?°C. It was observed that the value of Seebeck coefficient was increased from 91 to 847?μV/K as the annealing temperature increases from 500° to 700°C. This behavior was explained as; high temperature causes stress and cracks in the grown films which may induce electric and thermal discontinues at tips of cracks which cause high thermoelectric concentration. Scanning electron microscope images verified the development of cracks in the samples as annealing temperature increases. The behavior of Seebeck coefficient with the measurement temperature was also observed and explained in detail. The high value of Seebeck coefficient suggested that this material can be a potential candidate for thermoelectric power generation applications in near future.     

Fabrication and thermo stability of the SnO2/Ag/SnO2 tri-layer transparent conductor deposited by magnetic sputtering

Using the magnetic sputtering technique, the SnO₂/Ag/SnO₂ tri-layer transparent films were fabricated on float glasses successfully. Compared with the commercial FTO (F-doped SnO₂) film, the SnO₂/Ag/SnO₂ tri-layer films have higher visible-light transmittance and better conductivity. The total thickness of the SnO₂/Ag/SnO₂ films is one third of the commercial FTO film leading to the high visible-light transmittance. The high carrier concentration of the SnO₂/Ag/SnO₂ films contributes to the tri-layer films’ low resistivity. In addition, to further improve the performance of the SnO₂/Ag/SnO₂ tri-layer films, samples were annealed under different temperatures. The results illustrate that the lowest sheet resistance (5.92 Ω/sq) and the highest visible-light transmittance (87.0%) were obtained after annealing at 200 °C. Furthermore, the thermal stability of the films could be enhanced by a multi-step annealing process due to the recrystallization effect.     

Improved formaldehyde sensor of Zn2SnO4/SnO2 microcubes by compositional evolution and Y2O3 decoration

Zn₂SnO₄/SnO₂(ZTO/SnO₂) and Y doped Zn₂SnO₄/SnO₂(ZTO/SnO₂) microcubes were synthesized by a hydrothermal route at 130?°C and subsequently used for obtaining gas sensors. To evaluate the structure, morphology, chemical state and optical bandgap, our sensors were characterized by XRD, SEM, XPS and UV–vis analysis. Compared with sensors based on ZTO/SnO₂ microcubes, the Y doped ZTO/SnO₂ microcubes had an optimum sensing performance to 100?ppm formaldehyde (HCHO), for instance lower working temperature (210?°C) and better response (46.07). In addition, the enhanced sensing mechanism of Y doped ZTO/SnO₂ microcubes was discussed in detail.     

Controlled synthesis of Mg(OH)2 thin films by chemical solution deposition and their thermal transformation to MgO thin films

The chemical solution deposition of Mg(OH)₂ thin films on glass substrates and their transformation to MgO by annealing in air is presented. The chemical solution deposition consists of a chemical reaction employing an aqueous solution composed of magnesium sulfate, triethanolamine, ammonium hydroxide, and ammonium chloride. The as-deposited films were annealed at different temperatures ranging from 325 to 500?°C to identify the Mg(OH)₂-to-MgO transition temperature, which resulted to be around 375?°C. Annealing the as-deposited Mg(OH)₂ films at 500?°C results in homogeneous MgO thin films. The properties of the Mg(OH)₂ and MgO thin films were analyzed by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, UV–Vis spectroscopy, and by circular transmission line model. Results by X-ray diffraction show that the as-deposited thin films have a brucite structure (Mg(OH)₂), that transforms into the periclase phase (MgO) after annealing at 500?°C. For the as-deposited Mg(OH)₂ thin film, a nanowall surface morphology is found; this morphology is maintained after the annealing to obtain MgO, which occurred with the evident formation of pores on the nanowall surface. The assessed chemical composition from X-ray photoelectron spectroscopy yields Mg_0.36O_0.64 (O/Mg ratio of 1.8) for the as-deposited Mg(OH)₂ film, where the expected stoichiometric composition is Mg_0.33O_0.67 (O/Mg ratio of 2.0); the same assessment yields Mg_0.60O_0.40 (O/Mg ratio of 0.7) for the annealed thin film, which indicates the obtainment of a MgO material with oxygen vacancies, given the deviation from the stoichiometric composition of Mg_0.50O_0.50 (O/Mg ratio of 1.0). These results confirm the deposition of Mg(OH)₂ films and the obtainment of MgO after the heat-treatment. The energy band gap of the films is found to be 4.64 and 5.10?eV for the as-deposited and the film annealed at 500?°C, respectively. The resistivity of both Mg(OH)₂ and MgO thin films lies around 10⁸?Ω·cm.     

Influence of Heat Treatment on the Optical Properties of Thermal Evaporated SnO<Subscript>2</Subscript> Thin Films

In this investigation, the optical properties of the thermally evaporated SnO₂ films and their dependence on the heat treatment were studied. The transmittance, T (λ), spectra were measured over the spectral range of 0.2 to 0.8 μm for SnO₂ films that were annealed at different temperatures (300, 350, 400, 450, 500, 550 and 600 K) in vacuum for 1h. All films showed high transparency in the visible range and increased with increasing the wavelength. These films have become more transparent after annealing at different temperatures. The optical constants of annealed SnO₂ films were obtained by modeling the measured transmission spectra. The best fit modeling of transmission spectra was obtained by applying Drude and OJL models combined with the effective medium approximation Bruggeman model. Increasing the annealing temperatures decreased both the refractive index and the extinction coefficient of the films. While the optical band gap energy increased from 3.05 to 4.11 eV by increasing the annealing temperature from 300 to 600 K, respectively. Analyzing the refractive index dispersion by using the Wemple-DiDomenico model revealed that the oscillator resonance energy E_o decreased whereas the oscillator dispersion energy E_d increased with increasing the annealing temperature.     

Phase transformation and dielectric properties of sputtering-prepared Zn–Ti–O thin films

Zn–Ti–O films were co-sputtered from Zn and Ti targets and then annealed at temperatures ranging from 600 °C to 900 °C for 2 h under an air atmosphere. The [Ti]/([Ti]+[Zn]) ratio decreased from 75.52 to 28.26 as the Zn-target power increased from 25 W to 75 W. The phase transition of the films strongly depended on the [Ti]/([Ti]+[Zn]) ratio. High [Ti]/([Ti]+[Zn]) ratios led to the coexistence of ZnTiO₃, Zn₂Ti₃O₈, and rutile TiO₂ phases. Zn₂Ti₃O₈ gradually became the major crystalline phase as the [Ti]/([Ti]+[Zn]) ratio and rutile TiO₂ and ZnTiO₃ phases decreased. The aforementioned phases disappeared when the [Ti]/([Ti]+[Zn]) ratio was especially low. In their place, Zn₂TiO₄ and even ZnO phases developed. The dielectric constant of the films increased with increasing [Ti]/([Ti]+[Zn]) ratio. However, extremely high [Ti]/([Ti]+[Zn]) ratios increased the dielectric loss of the films. The film mainly composed of the Zn₂Ti₃O₈ phase exhibited optimal dielectric properties, including a dielectric constant and loss equal to 40.1 and 0.0304, respectively, at 1 MHz.     

Annealing impact on the structural and optical properties of electrospun SnO2 nanofibers for TCOs

Tin oxide (SnO₂) nanofibers were fabricated by electrospinning technique and subsequent annealed at different temperatures. The structure, morphology and optical properties of the annealed samples were characterized by X-ray diffraction (XRD), Raman, scanning electron microscopy/energy dispersive spectroscopy (SEM/EDS), transmission electron microscopy (TEM), Fourier transformed infrared (FTIR),and optical absorption techniques. The phase of SnO₂ of all samples is rutile (tetragonal), and at higher annealing temperatures, good crystallinity and lower absorption were obtained. Annealing of the samples at 600 °C caused the lower absorption and higher optical band gap, and the decrease of the absorption was probably because the fiber structure changed from solid to hollow structure. From PL spectra, it was observed that the SnO₂ hollow nanofibers annealed at 600 °C revealed green emission at 530 nm.     

Epitaxial growth of LaMnO3 thin films on different single crystal substrates by polymer assisted deposition

Structure of epitaxial LaMnO₃ thin films grown on different single crystal substrates by unconventional polymer assisted deposition (PAD) method was investigated. Epitaxial films were prepared from lanthanum manganite water based solutions deposited by spin coating on single crystal MgO (001), SrTiO₃ (001) and SrTiO₃ (110) substrates, and the influence of substrate type on the film structure was analysed. Better uniformity of the epitaxial LaMnO₃ films on SrTiO₃ substrates was obtained, but a non-stoichiometric La_1-xMnO₃ phase was formed after the heat treatment at 750 °C. In addition, the prepared thin films were multiple annealed at different temperatures up to 900 °C, in order to investigate importance of post-annealing treatment. Epitaxial nature of the prepared films was preserved after annealing at up to 900 °C and the structure rearrangement through formation of cell closer to bulk stochiometric LaMnO₃ phase was observed.     

Effects of thermal annealing on the optical properties of Ar ion irradiated ZnS films

Ar-ion-implantation to a dose of 1×10¹⁷ ions/cm² was performed on cubic ZnS thin films with (111) preferred orientation deposited on fused silica glass substrates by vacuum evaporation. After ion implantation, ZnS films were annealed in flowing argon at different temperatures from 400 to 800 °C. The effects of ion implantation and post-thermal annealing on the structural and optical properties of ZnS films were investigated by X-ray diffraction (XRD), photoluminescence (PL) and optical transmittance measurements. XRD reveals that the diffraction peaks recover at ∼500 °C. The optical transmittances show that the bandgap of ZnS films blueshifts when annealed below 500 °C, and redshifts when annealed above 500 °C. PL results show that the intrinsic defect related emissions decrease with increasing annealing temperature from 400 to 500 °C, and increase with increasing annealing temperature from 500 to 800 °C. The observed PL emissions at 414 and 439 nm are attributed to the transitions of Zn_i→V_Zn and V_S→VBM, respectively.     

Influence of post-annealing atmosphere on microstructure,optical and electrical properties of zinc cadmium oxide films deposited by DC and RF magnetron co-sputtering

Zinc cadmium oxide (Zn_1−xCd_xO) films were deposited on quartz substrates by direct current (DC) and radio frequency (RF) reactive magnetron co-sputtering and the influence of post-annealing atmosphere on their microstructure, optical and electrical properties were investigated by X-ray diffraction (XRD), optical absorbance, photoluminescence (PL) and Hall measurements. Results indicate that the band gap (E_g) of all Zn_1−xCd_xO films annealed in different atmospheres are smaller than that of the undoped ZnO, the observed shifts in E_g being 0.43, 0.37 and 0.32 eV for the Zn_1−xCd_xO films annealed in argon, oxygen and vacuum, respectively. Hall measurement results indicate that all Zn_1−xCd_xO films annealed in different atmospheres show the n-type conduction, but the Zn_1−xCd_xO film annealed in vacuum has low resistivity and high concentration, which has room-temperature resistivity of 1.59 Ω cm and carrier concentration of 2.07×10¹⁷ cm⁻³. Compared with Zn_1−xCd_xO films annealed in oxygen and argon, Zn_1−xCd_xO film annealed in vacuum has the best crystal quality, luminescence and electrical properties. The influencing mechanism of the post-annealing atmosphere on the electrical and optical properties of the Zn_1−xCd_xO film is discussed.     

Impact on nonlinear/linear optical and structural parameters in quaternary In15Ag10S15Se60 thin films upon annealing at different temperatures

In the present study, the effect of thermal annealing on structural, linear, and nonlinear optical properties of quaternary chalcogenide In₁₅Ag₁₀S₁₅Se₆₀ thin film has been reported. The bulk sample synthesized by the melt quenching technique was used for the thin film preparation by the thermal evaporation method. Post deposition, the thin films were annealed at different temperatures like 100 °C, 150 °C, 200 °C, and 250 °C for 2 hs. X-ray diffraction (XRD) and Raman spectroscopy were used for structural studies, which showed the increase in crystalline phases with the increase of annealing temperature. The morphological images taken by field emission scanning electron microscope (FESEM) showed the densification and enlargement of scattered grains for annealed films. Furthermore, the constituent elements and their percentage in the sample were confirmed by Energy dispersive X-ray analysis (EDX). The linear and nonlinear optical parameters were calculated from the transmittance data obtained from UV–Vis spectroscopy in the wavelength range of 600–1100 nm. There is a large reduction in third-order nonlinear susceptibility at the higher annealing temperature. Subsequently, the transmission increased, whereas the absorption decreased with the annealing temperature. The extinction coefficient decreased while there was an increase in optical bandgap for the annealed films due to the decrease in surface defects and disorder, which forms the localized states in the bandgap. The oscillator energy, dispersion energy, dielectric constant, optical conductivity were calculated and discussed in detail. The change in both linear and nonlinear parameters by thermal annealing could be useful for controlling the optical properties of In₁₅Ag₁₀S₁₅Se₆₀ thin film, which could be the preferable candidate for numerous photonic applications.     

Low temperature processed SnO2 films using aqueous precursor solutions

We present a comparison study of the microstructure developments during aqueous solution deposition of SnO₂, particularly, through chemical bath deposition (CBD) and liquid phase deposition (LPD) at very low temperatures (40–75 °C). The effects of solution chemistry on the microstructural details and electrical properties of SnO₂ thin films are presented and discussed. Smooth, nanoparticulate SnO₂ films were obtained from supersaturated precursor solutions with lower precursor concentrations while more aggregated SnO₂ films were generated from higher precursor concentrations. Loosely-packed and porous structures were obtained from low supersaturation solutions with very low pHs. The deposition rates were also evaluated under various deposition conditions. XRD result shows that annealing process helps improve the degree of crystallinity of the as-deposited films that are composed of 3–10 nm nanocrystalline particles. One advantage of LPD of SnO₂ films is in-situ fluorine doping during deposition. The resulting electrical resistivity of F-doped SnO₂ films was about 18.7 Ω cm after the films were annealed at 450 °C.     

Microstructure effect on field emission from tetrahedral amorphous carbon films annealed in nitrogen and acetylene ambient

Tetrahedral amorphous carbon (ta-C) films have been deposited by filtered cathodic vacuum arc technique. The samples were then annealed at various temperatures in nitrogen and acetylene ambient. The surface morphologies and microstructure of the films were characterized using atomic force microscopy, scanning electron microscopy, visible and ultraviolet Raman spectroscopy. A thin layer of amorphous carbon was deposited on the surface of the ta-C films after annealed at 700 and 800 °C while submicro crystalline pyrolytic graphite was formed on the surface of the ta-C film annealed at 900 °C. The surface layer was found to enhance the sp² clustering of the underlying ta-C layer. Field emission results reveal that the sp² cluster size plays an important role in electron field emission properties. The threshold field decreases as the sp² cluster size increases. For the film annealed at 800 °C, the lowest threshold field and the largest cluster size concurred.     

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 %.     

Sintering densification behavior of ZnO–SnO2 binary ceramic targets

In this work, high-performance ZnO–SnO₂ binary ceramic targets for magnetron sputtering of transparent conductive oxide (TCO) films were prepared by pressureless oxygen atmosphere sintering. The sintering behavior and densification mechanism of the ZnO–SnO₂ binary targets were analyzed by systematically studying the oxide powder state, formation process of the solid reaction phase, and evolution of the target microstructure. The data revealed that the ZnO–SnO₂ powder treatment improved the sintering activity and the powder dispersion; furthermore, it promoted a mutual reaction between the different components during sintering and the homogeneity of the target composition. The densification of the pure SnO₂ ceramic target was difficult to achieve, and the addition of ZnO led to a continuous interaction between the ZnO and SnO₂ components. The Zn₂SnO₄ phase started to form, and a temporary shrinkage of the target occurred above 800°C. After formation of the stable Zn₂SnO₄ and SnO₂ phases, the target shrunk rapidly with increasing temperature, densification occurred during growth, and the two phases started to interact. The sintering temperature provided the driving force for the target densification, with the densification activation energy of the ZnO–SnO₂ binary ceramic target estimated to be 580 kJ/mol based on the master sintering curve. A binary ceramic target with a high density (99.78% relative density), a fine grain size, and a homogeneous phase structure was achieved at a temperature of 1600°C. These findings are promising for the further improvement and performance enhancement of SnO₂-based materials.     

Characterization of polycrystalline SnO2 films deposited by DC sputtering technique with potential for technological applications

Polycrystalline SnO₂ films with different thicknesses were successfully deposited on glass substrate at room temperature using a DC sputtering technique. As-grown films showed the formation of an amorphous SnO₂ phase, whereas the thermal annealed samples showed the formation of a SnO₂ rutile-type structure. The structural study showed that the crystallinity of the annealed films was improved as a function of film thickness. Scanning electron microscopy images of the annealed films unveiled the formation of cracked surfaces along with columnar growth, irrespective of the depositon time. Raman spectroscopy measurements evidenced the presence of modes related to a surface disorder,a progressive strain reduction and a crystallinity improvement. UV–vis data analysis indicates a reduction in the band gap energy with films thickness due to presence of strain states as confirmed by theoretical calcuations. It was observed that the strained states in the films affected the sensing response to a methane gas flow with a better sensitivity for the thinner film.