Optical and structural properties of CuSbS2 thin films grown by thermal evaporation method

Structural, optical and electrical properties of CuSbS₂ thin films grown by thermal evaporation have been studied relating the effects of substrate heating conditions of these properties. The CuSbS₂ thin films were carried out at substrate temperatures in the temperature range 100-200 °C. The structure and composition were characterized by XRD, SEM and EDX. X-ray diffraction revealed that the films are (111) oriented upon substrate temperature 170 °C and amorphous for the substrate temperatures below 170 °C. No secondary phases are observed for all the films. The optical absorption coefficients and band gaps of the films were estimated by optical transmission and reflection measurements at room temperature. Strong absorption coefficients in the range 10⁵-10⁶ cm^− 1 at 500 nm were found. The direct gaps Eg lie between 0.91-1.89 eV range. It is observed that there is a decrease in optical band gap Eg with increasing the substrate temperature. Resistivity of 0.03-0.96 Ω cm, in dependence on substrate temperature was characterized. The all unheated films exhibit p-type conductivity. The characteristics reported here also offer perspective for CuSbS₂ as an absorber material in solar cells applications.     

Role of oxygen in enhancing N-type conductivity of CuInS2 thin films

Post-growth treatments in air atmosphere were performed on CuInS₂ films prepared by the single-source thermal evaporation method. Their effect on the structural, optical and electrical properties of the films was studied by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), optical reflection and transmission and resistance measurements. The films were annealed from 100 to 350 °C in air. The stability of the observed N-type conductivity after annealing depends strongly on the annealing temperature. Indeed it is shown that for annealing temperatures above 200 °C the N-type conductivity is stable. The resistance of the N-CuInS₂ thin films correlates well with the corresponding annealing temperature. The samples after annealing have direct bandgap energies of 1.45-1.50 eV.     

Effect of substrate temperature and annealing treatment on the electrical and optical properties of silver-based multilayer coating electrodes

Multilayer coatings consisting of thin silver layers sandwiched between layers of transparent conducting metal oxides are investigated from the view point of low-resistance electrodes for use in flat panel displays, solar cells, etc. ZnO/Ag/ZnO multilayer films were prepared on glass substrates by simultaneous RF magnetron sputtering of ZnO and dc magnetron sputtering of Ag. Optimization of the deposition conditions of both ZnO layers and metallic layers were performed for better electrical and optical properties. The structural, electrical and optical properties of the films (deposited at room temperature, different substrate temperature and annealed at different conditions) were characterized with various techniques. We could not produce high-quality transparent conductive electrodes simply by annealing at various temperatures. However, improved electrical properties and a considerable shift in the transmittance curves was observed after heat treatment. The experimental results show that the electrical resistivity of as-grown films can be decreased to 10^− 5 Ω cm level with post-annealing at 400 °C for 2 h in vacuum atmosphere. After heat treatment, the sheet resistance was reduced as much as 20% which was due to the increased grain size of Ag film. The samples heat treated at 200-400 °C under vacuum or nitrogen atmosphere showed the best electrical properties. The key to the superior electrical and optical properties of the multilayer is the optimization of growth conditions of the silver layer by careful control of the oxide properties and the use of appropriate annealing temperature and atmosphere.     

Structural and electrical properties of sputtered indium-zinc oxide thin films

In this study, indium-zinc oxide (IZO) thin films have been prepared at a room temperature, 200 and 300 °C by radio frequency magnetron sputtering from a In₂O₃-12 wt.% ZnO sintered ceramic target, and their dependence of electrical and structural properties on the oxygen content in sputter gas, the substrate temperature and the post-heat treatment was investigated. X-ray diffraction measurements showed that amorphous IZO films were formed at room temperature (RT) regardless of oxygen content in sputter gas, and micro-crystalline and In₂O₃-oriented crystalline films were obtained at 200 and 300 °C, respectively. From the analysis on the electrical and the structural properties of annealed IZO films under Ar atmosphere at 200, 300, 400 and 500 °C, it was shown that oxygen content in sputter gas is a critical parameter that determines the local structure of amorphous IZO film, stability of amorphous phase as well as its eventual crystalline structure, which again decide the electrical properties of the IZO films. As-prepared amorphous IZO film deposited at RT gave specific resistivity as low as 4.48 × 10^− 4 Ω cm, and the highest mobility value amounting to 47 cm²/V s was obtained from amorphous IZO film which was deposited in 0.5% oxygen content in sputter gas and subsequently annealed at 400 °C in Ar atmosphere.     

Effect of thermal annealing time on optical and structural properties of TeO2 thin films

TeO₂ thin films were deposited on quartz substrates by rf reactive sputtering technique from a Te metal target. The obtained samples were annealed in an argon atmosphere at 450 °C for different annealing times up to 90 min. X-ray diffraction studies revealed that the as-grown samples were amorphous and there was no appreciable change in structure for a short annealing time. Thin films became polycrystalline with the tetragonal (α-phase) structure of tellurium dioxide crystal with the increase of the thermal annealing time. The refractive index and optical energy gap of the films were calculated by modelling transmittance spectra. The optical energy gap decreased continuously from 3.83 eV to 3.71 eV with increasing thermal annealing time.     

Annealing effect of ZnO/Au/ZnO transparent conductive films

Au intermediate ZnO (ZAZ) thin films were prepared by radio frequency and direct current magnetron sputtering on glass substrates and then vacuum annealed. The thickness of each layer of the ZAZ films was set at 50 nm, 3 nm, and 47 nm, respectively. The structural, electrical, and optical properties of ZAZ films were investigated with respect to the variation of annealing temperature.As-deposited AZO films showed X-ray diffraction peaks corresponding to ZnO (002) and Au (111) planes and those peak intensities increased with post-deposition vacuum annealing. The optical and electrical properties of the films were strongly influenced by post-deposition annealing. Although the optical transmittance of the films deteriorated with an Au interlayer, as-deposited ZAZ films showed a low resistivity of 2.0 × 10⁻⁴ Ω cm, and the films annealed at 300 °C had a lower resistivity of 9.8 × 10⁻⁵ Ω cm. The work function of the films increased with annealing temperature, and the films annealed at 300 °C had a higher work function of 4.1 eV than the films annealed at 150 °C. The experimental results indicate that vacuum-annealed ZAZ films are attractive candidates for use as transparent electrodes in large area electronic applications such as solar cells and large area displays.     

Opto-electronic properties of sputter-deposited Cu2O films treated with rapid thermal annealing

Cu₂O thin films were first deposited using magnetron sputtering at 200 °C. The samples produced were then annealed by a rapid thermal annealing (RTA) system at 550 °C in a protective atmosphere with or without the addition of oxygen. After annealing, various Cu₂O and CuO films were formed. These films were characterized, as a function of oxygen concentration in RTA, using UV-VIS photometer, four-point probe, and Hall measurement system. The results show that these Cu₂O thin films annealed at 550 °C with more than 1.2% oxygen added in the protective argon atmosphere would transform into the CuO phase. Apparently, the results of RTA are sensitive to the amount of oxygen added in the protective atmosphere. The resistivity of these Cu₂O thin films decreases with the increase in the oxygen amount in the annealing atmosphere, most likely due to the increase in carrier mobility. In addition, Cu₂O/ZnO (doped with AlSc) junctions were produced at 200 °C and annealed. The rectifying effect of P-N junction disappeared after annealing, probably due to the damage of p-n interface, which directly causes current leakage at the junction.     

Structural and optical characterization of CuInS2 thin films grown by vacuum evaporation method

Structural and optical properties of CuInS₂ thin films grown by the single-source thermal evaporation method have been studied. The films were annealed from 100 to 500 °C after an evaporation in air. The surface morphology was investigated by scanning electron microscopy. The maximum grain size of the samples after annealing at 400 °C was over 500 nm. The EPM analysis concluded that the polycrystalline CuInS₂ thin films after annealing below 100 °C were Cu-rich, and those annealed above 200 °C were In-rich. The bandgap energy of the CuInS₂ films after annealing above 300 °C was about 1.48 eV.     

Influence of deposition regime on physical properties of gallium doped zinc oxide films

Zinc oxide films doped by gallium were deposited using RF diode sputtering from a ceramic ZnO + 2% Ga₂O₃ target on Corning glass in argon atmosphere. Samples were supported in three different positions against a substrate holder - horizontal, and at 60 and 80° to the horizontal position. Two series of samples 700-1000 nm in thickness were prepared: one at room temperature (RT) and the second at 200 °C. XRD, optical and electrical experiments indicated that the films are polycrystalline having average crystallite sizes from 30 to 80 nm, integrated transmittances in the range of 400-1000 nm increased from 85 to 90 per cent and optical band-gap values increased from 3 to 3.2 eV with higher deposition temperature. The resistivity of the obliquely sputtered samples positioned at 80° to the substrate holder was one order lower than the horizontally positioned samples. No significant changes were observed in case of optical properties of the films in dependence on the tilt-angle.     

Degradation of thin films of YBa2Cu3O7 by annealing in air and in vacuum

The degradation of epitaxial thin films of YBa₂Cu₃O₇ has been studied as a function of annealing temperature in air and in vacuum; some samples had an evaporated overlayer of CaF₂. Degradation was monitored by the measurement of electrical properties after consecutive 30-min annealing treatments. The room-temperature resistance registered significant increases for all samples after annealing at temperatures above about 200°C; the critical current density at 77 K was degraded for annealing temperatures 400°C in air, and 200–250°C in vacuum. By annealing in oxygen at 550°C, electrical properties were restored in degraded bare YBCO samples annealed in vacuum, but not for those annealed in air.     

Structures and properties of titania thin films annealed under different atmosphere

The effects of crystallinity, phase and oxygen vacancies on optical and photocatalytic properties of titania (TiO₂) thin films were systematically studied. The as-deposited amorphous titania films were prepared by reactive sputtering titanium metal targets in argon–oxygen plasma at 100 °C and subsequently annealed at various temperatures of 400–800 °C in air, vacuum and H₂ atmosphere. The results indicate that in general the crystallinity of the annealed films is enhanced with the increasing annealing temperature. At the same temperature, the H₂ annealed films achieve better crystallinity but containing more oxygen vacancies than the films annealed in air and in vacuum. In H₂ or in vacuum, the concentration of oxygen vacancies in the annealed films increases with increasing temperature, while in air it remains constant. Oxygen vacancies in titania film not only facilitate phase transformation but also lower the band gap of titania, and make the film visible-light responsive. Photocatalytic properties of the TiO₂ films were characterized in UV and visible light irradiation by following the Ag reduction and degradation of methylene blue. The films annealed at 600–700 °C in H₂ possess the best film crystallinity and the proper concentration of oxygen vacancies and exhibit the best photocatalytic performance under both UV and visible light.     

Composition, structural and electrical properties of thin films prepared by laser ablation of neodymium-doped potassium gadolinium tungstate

Thin films were grown on (001) SiO₂, SiO₂/(100) Si or (100) MgO substrates by laser ablation of neodymium-doped potassium gadolinium tungstate (Nd:KGW) single crystal target. The films were deposited at temperatures between room temperature and 750 °C and pressures between 1 × 10^− 4 Pa and 50 Pa of oxygen ambient. The influence of the deposition conditions on the composition, structure, morphology and electrical properties of the films was investigated. Special attention was paid to the films deposited in vacuum (1 × 10^− 4 Pa) or at very low oxygen pressures. Under such conditions, the potassium (K), gadolinium (Gd) and oxygen (O) content decreased strongly as the temperature was increased. At room temperature, the films were K and O stoichiometric, in contrast with Gd, which showed a concentration twice higher. The films were polycrystalline, with the exception of those deposited at temperatures below 500 °C, which were amorphous. However, all were smooth and dense. The films grown in vacuum and at temperatures between 500 and 700 °C consist mainly of “â-tungsten” - tungsten oxide (W₃O) phase. The films grown on SiO₂/Si possessed the best surface quality with nano-size relief. The resistivity measurements as a function of the temperature showed that the films produced in vacuum and at temperatures below 500 °C were highly insulating, whereas at 600 °C they exhibited semiconducting behavior or a metallic one at 700 °C. This behavior can be attributed to the existence of various valence states for tungsten below W⁶⁺ in the films and to their crystal structure.     

A comparative study of the properties of thermally evaporated CuIn2n + 1S3n + 2 (n = 0, 1, 2 and 3) thin films

CuInS₂, CuIn₃S₅, CuIn₅S₈ and CuIn₇S₁₁ compounds were synthesized by the horizontal Bridgman method using high-purity copper, indium and sulphur elements. Crushed powders of these ingots were used as raw materials for the vacuum thermal evaporation. So, CuIn_2n + 1S_3n + 2 (n = 0, 1, 2, and 3) thin films were deposited by single source vacuum thermal evaporation onto glass substrates heated at 150 °C. The structural, compositional, morphological, electrical and optical properties of the deposited films were studied using X-ray diffraction (XRD), energy dispersive X-ray, atomic force microscopy and optical measurement techniques. XRD results revealed that all the films are polycrystalline. However, CuInS₂ and CuIn₃S₅ films had a chalcopyrite structure with preferred orientation along 112 while CuIn₅S₈ and CuIn₇S₁₁ films exhibit a spinel structure with preferred orientation along 311. The absorption coefficients of the all CuIn_2n + 1S_3n + 2 films are in the range of 10⁻⁴ and 10⁻⁵ cm⁻¹. The direct optical band gaps of CuIn_2n + 1S_3n + 2 layers are found to be 1.56, 1.78, 1.75 and 1.30 eV for n = 0, 1, 2, and 3, respectively. CuIn₃S₅ and CuIn₅S₈ films are p type with electrical resistivities of 4 and 12 Ω cm whereas CuInS₂ and CuIn₇S₁₁ are highly compensated with resistivities of 1470 and 1176 Ω cm, respectively.     

Thermal treatment effect on the optical properties of ZrO2 thin films deposited by thermionic vacuum arc

This paper shows the ex situ thermal treatment effects of the ZrO₂ thin films obtained by TVA (thermionic vacuum arc) technique on the optical properties (e.g., transmittance, refractive index and band-gap energy) of ZrO₂ thin films. The crystal structure, surface and optical properties were investigated for ZrO₂ thin films deposited on glass substrates by thermionic vacuum arc (TVA) method. The thermal treatment effect on the optical properties of the thin films was determined. The XRD analysis showed that the deposited ZrO₂ thin films have baddeleyite (monoclinic) and zirconium (hexagonal) structures. The thicknesses and refractive index were determined by interferometric measurements. The thin films were thermal treated at different temperatures (350 °C, 450 °C and 550 °C), and the analysis showed that the optical properties of ZrO₂ deposited thin films were improved by thermal treatment at 450 °C.     

Fabrication of transparent conducting amorphous Zn-Sn-In-O thin films by direct current magnetron sputtering

Amorphous ZnO-SnO₂-In₂O₃ films were grown by direct current magnetron sputtering from vacuum hot pressed ceramic oxide targets of Zn:In:Sn cation ratios 1:2:1 and 1:2:1.5 onto glass substrates. X-ray diffraction analysis showed that the microstructure remained amorphous during annealing at 200 °C for up to 5 hours. By monitoring the electrical resistivity, oxygen content and substrate temperature were optimized during deposition. The optimal films were characterized by Hall Effect, work function and optical spectroscopy measurements. Films of 1:2:1 composition showed the lowest resistivity (7.6 × 10^− 4 Ω-cm), when deposited onto substrates preheated to 300 °C. Transmissivity of all films exceeded 80% in the visible spectral region. The energy gap was 3.52-3.74 eV, and the work function ranged 5.08-5.22 eV, suitable for cathode applications in organic light emitting diodes. Overall, the film characteristics were comparable or superior to those of amorphous tin-doped indium oxide and zinc-doped indium oxide films and may serve as viable, lower-cost alternatives.     

Effect of thermal annealing treatment on structural, electrical and optical properties of transparent sol-gel ZnO thin films

Effect of thermal annealing in different ambients on the structural, electrical and optical properties of the sol-gel derived ZnO thin films are studied. XRD results show that the annealed ZnO films with wurtzite structure are randomly oriented. Crystallite size, carrier concentration, resistivity and mobility are found to be dependent on the annealing temperature. The change in carrier concentration is discussed with respect to the removal of adsorbed oxygen from the grain boundaries. The highest carrier concentration and lowest resistivity are 8 × 10¹⁸ cm⁻³ and 2.25 × 10⁻¹ Ω cm, respectively, for the film annealed at 500 °C in vacuum. The annealed films are highly transparent with average transmission exceeding 80% in the wavelength region of 400-800 nm. In all three ambients, the optical band gap value does not change much below 500 °C temperature while above this temperature band gap value decreases for nitrogen and air and increases for vacuum.     

The influence of annealing temperature on the structural, electrical and optical properties of ion beam sputtered CuInSe2 thin films

CuInSe₂ (CIS) thin films were prepared by ion beam sputtering deposition of copper layer, indium layer and selenium layer on BK7 glass substrates followed by annealing at different temperatures for 1 h in the same vacuum chamber. The influence of annealing temperature (100-400 °C) on the structural, optical and electrical properties of CIS thin films was investigated. X-ray diffraction (XRD) analysis revealed that CIS thin films exhibit chalcopyrite phase and preferential (112) orientation when the annealing temperature is over 300 °C. Both XRD and Raman show that the crystalline quality of CIS thin film and the grain size increase with increasing annealing temperature. The reduction of the stoichiometry deviation during the deposition of CIS thin films is achieved and the elemental composition of Cu, In and Se in the sample annealed at 400 °C is very near to the stoichiometric ratio of 1:1:2. This sample also has an optical energy band gap of about 1.05 eV, a high absorption coefficient of 10⁵ cm⁻¹ and a resistivity of about 0.01 Ω cm.     

Physical properties of electrically conductive Sb-doped SnO2 transparent electrodes by thermal annealing dependent structural changes for photovoltaic applications

We have investigated the optical and electrical characteristics of antimony (Sb)-doped tin oxide (SnO₂) films with modified structures by thermal annealing as a transparent conductive electrode. The structural properties were analyzed from the relative void % by spectroscopic ellipsometry as well as the scanning electron microscopy images and X-ray diffraction patterns. As the annealing temperature was raised, Sb-doped SnO₂ films exhibited a slightly enhanced crystallinity with the increase of the grain size from 17.1 nm at 500 °C to 34.3 nm at 700 °C. Furthermore, the refractive index and extinction coefficient gradually decreased due to the increase in the relative void % within the film during the annealing. The resistivity decreased to 8.2 × 10⁻³ Ω cm at 500 °C, but it increased rapidly at 700 °C. After thermal annealing, the optical transmittance was significantly increased. For photovoltaic applications, the photonic flux density and the figure of merit over the entire solar spectrum were obtained, indicating the highest values of 5.4 × 10¹⁴ cm⁻² s⁻¹ nm⁻¹ at 1.85 eV after annealing at 700 °C and 340.1 μA cm⁻² Ω⁻¹ at 500 °C, respectively.     

Effects of deposition temperature on structure and properties of mo-doped indium oxide by radio frequency magnetron sputtering

Transparent conductive oxide (TCO) thin films of Mo-doped In₂O₃ (IMO) were prepared on glass substrates by radio frequency magnetron sputtering from the 2 wt% Mo-doped In₂O₃ ceramic target. The depositions were carried out under an oxygen-argon atmosphere by varying the deposition temperature from 200 °C to 350 °C. The crystal structure and thickness of IMO thin films were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The effects of deposition temperature on the electrical and optical transmittance properties of IMO thin films were investigated by four-point probe Hall system and UV-VIS-NIR spectrophotometer separately. The optimum deposited IMO thin films were obtained with resistivity of 6.9 × 10⁻⁴ Ω cm and carrier mobility 45 cm²v⁻¹s⁻¹ at 350 °C. The average optical transmittance of IMO films on glass substrates are over 80% in the near-infrared region.     

Effects of the annealing treatment on electrical and optical properties of ZnO transparent conduction films by ultrasonic spraying pyrolysis

Effects of the annealing treatment on properties of ZnO thin films prepared on silica glass substrates by the ultrasonic spraying pyrolysis process were studied. Zinc acetate dihydrate and methanol were used as a starting material and a solvent, respectively. For ZnO thin films untreated with annealing, the preferred grain growth along the (0 0 2) plane was observed. The electrical resistivity and the direct band gap values of these films decreased with increasing the deposit temperature. By applying the annealing treatment in a reducing atmosphere, while the degree of the preferred (0 0 2) orientation of films decreased, the electrical conductivity of films was improved. When compared with the resistivity values of films without the annealing treatment, the values of films annealed in the reducing atmosphere were decreased by about two orders of magnitude. The lowest resistivity value was 1.62×10⁻¹ Ω cm, which was obtained in the film annealed at 500 °C in nitrogen with 5% hydrogen. The optical transmittances of the films were higher than 80% regardless of the application of the annealing treatment in a reducing atmosphere. The direct band gap values of films annealed in a reducing atmosphere were approximately 3.27 eV.