Synthesis of nanostructured CuxS thin films by chemical route at room temperature and investigation of their size dependent physical properties

Nanostructured semiconductors show very interesting physical properties than bulk crystal due to size effects that arises because of quantum confinement of the electronic states. Using cupric acetate and sodium thiosulphate as cationic and anionic precursor, nanostructured Cu₂S thin films were successfully prepared at room temperature by chemical bath deposition technique. By varying the deposition time from 9 to 24 h, the Cu₂S films of thickness 70-233 nm were prepared. The different characterization methods such as X-ray diffraction (XRD), scanning electron microscopy (SEM), optical absorption and electrical resistivity measurement techniques were used to investigate size dependent properties of Cu₂S thin films. As thickness increases, the hexagonal covellite phase of CuS observed at thickness 70 nm gets converted to monoclinic chalcosite phase of Cu₂S. The resistivity and activation energy is found to be thickness dependent. The optical band-gap energy increases from 2.48 to 2.90 eV as thickness decreases from 233 to 70 nm. The influence of film thickness on carrier concentration, mobility and thermo-emf is reported.     

New process for synthesis of ZnO thin films: Microstructural, optical and electrical characterization

Nanocrystalline ZnO thin films were prepared on glass substrates by using spin coating technique. The effect of annealing temperature (400-700 °C) on structural, compositional, microstructural, morphological, electrical and optical properties of ZnO thin films were studied by X-ray diffraction (XRD), Energy dispersive Spectroscopy (EDS), Atomic Force Microscopy (AFM), High Resolution Transmission Microscopy (HRTEM), Scanning Electron Microscopy (SEM), Electrical conductivity and UV-visible Spectroscopy (UV-vis). XRD measurements show that all the films are nanocrystallized in the hexagonal wurtzite structure and present a random orientation. The crystallite size increases with increasing annealing temperature. These modifications influence the optical properties. The AFM analysis revealed that the surface morphology is smooth. The HRTEM analysis of ZnO thin film annealed at 700 °C confirms nanocrystalline nature of film. The SEM results shows that a uniform surface morphology and the nanoparticles are fine with an average grain size of about 40-60 nm. The dc room temperature electrical conductivity of ZnO thin films were increased from 10⁻⁶ to 10⁻⁵ (Ω cm)⁻¹ with increase in annealing temperature. The electron carrier concentration (n) and mobility (μ) of ZnO films annealed at 400-700 °C were estimated to be of the order of 4.75-7.10 × 10¹⁹ cm⁻³ and 2.98-5.20 × 10⁻⁵ cm² V⁻¹ S⁻¹.The optical band gap has been determined from the absorption coefficient. We found that the optical band gap energy decreases from 3.32 eV to 3.18 eV with increasing annealing temperature between 400 and 700 °C. This means that the optical quality of ZnO films is improved by annealing.It is observed that the ZnO thin film annealing at 700 °C has a smooth and flat texture suited for different optoelectronic applications.     

New process for synthesis of nickel oxide thin films and their characterization

Sol-gel spin coating method has been successfully employed for the deposition of nanocrystalline nickel oxide (NiO) thin films. The films were annealed at 400-700 °C for 1 h in an air and changes in the structural, morphological, electrical and optical properties were studied. The structural properties of nickel oxide films were studied by means of X-ray diffraction (XRD) and scanning electron microscopy (SEM). XRD analysis shows that all the films are crystallized in the cubic phase and present a random orientation. Surface morphology of the nickel oxide film consists of nanocrystalline grains with uniform coverage of the substrate surface with randomly oriented morphology. The electrical conductivity showed the semiconducting nature with room temperature electrical conductivity increased from 10⁻⁴ to 10⁻² (Ω cm)⁻¹ after annealing. The decrease in the band gap energy from 3.86 to 3.47 eV was observed after annealing NiO films from 400 to 700 °C. These mean that the optical quality of NiO films is improved by annealing.     

Amorphous hafnium oxide thin films for antireflection optical coatings

Hafnium oxide (HfO₂) thin films were grown on silicon and quartz substrates by radio frequency reactive magnetron sputtering at temperature < 52 °C. X-ray diffraction of the films showed no structure, suggesting that the films grown on the substrates are amorphous. The optical properties of these films have been investigated using spectroscopic ellipsometry with wavelength range 200-1400 nm and ultraviolet-visible spectrophotometer techniques. Also, the effects of annealing temperatures on the structure and optical properties of the amorphous HfO₂ (a-HfO₂) have been investigated. The films appeared to be monoclinic structure upon high temperature (1000 °C) annealing as confirmed by X-ray diffraction. The results show that the annealing temperature has a strong effect on the optical properties of a-HfO₂ films. The optical bandgap energy of the as-deposited films is found to be about 5.8 eV and it increases to 5.99 eV after the annealing in Ar gas at 1000 °C. The further study shows that the measurement of the optical properties of the amorphous films reveals a high transmissivity (82%-99%) and very low reflectivity (< 8%) in the visible and near-infrared regions at any angle of incidence. Thus, the amorphous structure yields HfO₂ film of significantly higher transparency than the polycrystalline (68%-83%) and monoclinic (78%-89%) structures. This means that the a-HfO₂ films could be a good candidate for antireflection (AR) optical coatings.     

Nickel-lithium oxide alloy transparent conducting films deposited by spray pyrolysis technique

In this research, nickel oxide (NiO) transparent semiconducting films are prepared by spray pyrolysis technique on glass substrates. The effect of Ni concentration in initial solution and substrate temperature on the structural, electrical, thermoelectrical, optical and photoconductivity properties of NiO thin films are studied. The results of investigations show that optimum Ni concentration and suitable substrate temperature for preparation of basic undoped NiO thin films with p-type conductivity and high optical transparency is 0.1 M and 450 °C, respectively. Then, by using these optimized deposition parameters, nickel-lithium oxide ((Li:Ni)O_x) alloy films are prepared. The XRD structural analysis indicate the formation of the cubic structure of NiO and (Li:Ni)O_x alloy films. Also, in high Li doping levels, Ni₂O₃ and NiCl₂ phases are observed. The electrical measurements show that the resistance of the films decreases with increasing Li level up to 50 at%. For these films, the optical band gap and carrier concentration are obtained to be 3.6 eV and 10¹⁵-10¹⁸ cm⁻³, respectively.     

Optical properties of Se or S-doped hydrogenated amorphous silicon thin films with annealing temperature and dopant concentration

We report the effects of the thermal annealing and dopant concentration on the optical properties of Se or S-doped hydrogenated amorphous silicon thin films. The Se and S-doped a-Si:H (a-Si,Se:H and a-Si,S:H) thin films were prepared by glow discharge plasma enhanced chemical vapor deposition (GD-PECVD) on 7059 corning glass. The films were subsequently annealed in vacuum in the temperature range from 100 to 500 °C. Influence of doping and annealing was examined by means of optical transmission spectroscopy of the films in the wavelength range of 300-1100 nm taken at room temperature. The absorption coefficients and refractive indices decreased as the annealing temperature increased from 100 to 300 °C and then increased again as the annealing temperature further increased to 500 °C, while the highest bandgap was observed at 300 °C for all of the samples. For a given dopant concentration bandgap was observed to be higher in a-Si,S:H than a-Si,Se:H thin films.     

Effect of annealing temperature on the structure and optical properties of sputtered TiO2 films

TiO₂ thin films were deposited by DC reactive magnetron sputtering. Some TiO₂ thin films samples were annealed for 5 min at different temperatures from 300 to 900 °C. The structure and optical properties of the films were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (SEM) and ultraviolet-visible (UV-vis) spectrophotometry, respectively. The influence of the annealing temperature on the structure and optical properties of the films was investigated. The results show that the as-deposited TiO₂ thin films are mixtures of anatase and rutile phases, and possess the column-like crystallite texture. With the annealing temperature increasing, the refractive index and extinction coefficient increase. When the annealing temperature is lower than 900 °C, the anatase phase is the dominant crystalline phase; the weight fraction of the rutile phase does not increase significantly during annealing process. As the annealing temperature rises to 900 °C, the rutile phase with the large extinction coefficient becomes the dominant crystalline phase, and the columnar structure disappears. The films annealed at 300 °C have the best optical properties for the antireflection coatings, whose refractive index and extinction coefficient are 2.42 and 8 × 10⁻⁴ (at 550 nm), respectively.     

Structural, optical and electrical properties of CuIn5S8 thin films grown by thermal evaporation method

Stoichiometric compound of copper indium sulfur (CuIn₅S₈) was synthesized by direct reaction of high purity elemental copper, indium and sulfur in an evacuated quartz tube. The phase structure of the synthesized material revealed the cubic spinel structure. The lattice parameter (a) of single crystals was calculated to be 10.667 Å. Thin films of CuIn₅S₈ were deposited onto glass substrates under the pressure of 10⁻⁶ Torr using thermal evaporation technique. CuIn₅S₈ thin films were then thermally annealed in air from 100 to 300 °C for 2 h. The effects of thermal annealing on their physico-chemical properties were investigated using X-ray diffraction (XRD), Energy-dispersive X-ray spectroscopy (EDX), scanning electron microscope (SEM), optical transmission and hot probe method. XRD studies of CuIn₅S₈ thin films showed that as-deposited films were amorphous in nature and transformed into polycrystalline spinel structure with strong preferred orientation along the (3 1 1) plane after the annealing at 200 °C. The composition is greatly affected by thermal treatment. From the optical transmission and reflection, an important absorption coefficient exceeds 10⁴ cm⁻¹ was found. As increasing the annealing temperature, the optical energy band gap decreases from 1.83 eV for the as-deposited films to 1.43 eV for the annealed films at 300 °C. It was found that CuIn₅S₈ thin film is an n-type semiconductor at 300 °C.     

Preparation and optical characteristics of ZnO films by chelating sol-gel method

The effect of different annealing temperatures on the structure, morphology, and optical properties of ZnO thinf ilms prepared by the chelating sol-gel method was investigated. Zinc-oxide thin films were coated on quartz glass substrates by dip coating. Zinc nitrate, absolute ethanol, and citric acid were used as precursor, solvem, and chelating agent, respectively. The results show that ZnO films derived flom zinc-citrate have lower crystallization temperature (below 400℃),and that the crystal structure is wurtzite. The films, treated over 500℃, consist of nano-pardcles and show to be porous at 600℃. The particle size of the film increases with the increase of the annealing temperature. The largest particle size is 60 nm at 600℃. The optical transmittances related to the annealing temperatures become 90% higher in the visible range. The film shows a stalting absorption at 380 ran, and the optical band-gap of the thin film (fired at 500℃) is 3.25 eV and close to the intrinsic band-gap of ZnO (3.2 eV).     

Synthesis and characterization of Cu2ZnSnS4 thin films grown by PLD: Solar cells

As-deposited and annealed Cu₂ZnSnS₄ (CZTS) thin films have been synthesized onto Mo coated glass substrates at different deposition times using pulsed laser deposition (PLD) technique. The effect of deposition time (film thickness) and annealing onto the structural, morphological, compositional and optical properties of CZTS thin films have been investigated. The polycrystalline CZTS thin films with tetragonal crystal structure have been observed from structural analysis. FESEM and AFM images show the smooth, uniform, homogeneous and densely packed grains and increase in the grain size after annealing. The internal quantitative analysis has been carried out by XPS study which confirms the stoichiometry of the films. The optical band gap of CZTS films grown by PLD is about 1.54 eV, which suggests that CZTS films can be useful as an absorber layer in thin film solar cells. Device performance for deposited CZTS films has been studied.     

Influence of indium doping on the properties of spray deposited CdS0.2Se0.8 thin films

Polycrystalline indium doped CdS_0.2Se_0.8 thin films with varying concentrations of indium have been prepared by spray pyrolysis at 300 °C. The as deposited films have been characterized by XRD, AFM, EDAX, optical and electrical resistivity measurement techniques. The XRD patterns show that the films are polycrystalline with hexagonal crystal structure irrespective of indium doping concentration. AFM studies reveal that the RMS surface roughness of film decreases from 34.68 to 17.76 with increase in indium doping concentration up to 0.15 mol% in CdS_0.2Se_0.8 thin films and further it increases for higher indium doping concentrations. Traces of indium in CdS_0.2Se_0.8 thin films have been observed from EDAX studies. The optical band gap energy of CdS_0.2Se_0.8 thin film is found to decrease from 1.91 eV to 1.67 eV with indium doping up to 0.15 mol% and increase after 0.15 mol%. The electrical resistivity measurement shows that the films are semiconducting with minimum resistivity of 3.71 × 10⁴ Ω cm observed at 0.15 mol% indium doping. Thermoelectric power measurements show that films exhibit n-type conductivity.     

Low temperature processed highly conducting, transparent, and wide bandgap Gd doped CdO thin films for transparent electronics

Gadolinium (Gd) doped cadmium oxide (CdO) thin films are grown at low temperature (100 °C) using pulsed laser deposition technique. The effect of oxygen partial pressures on structural, optical, and electrical properties is studied. X-ray diffraction studies reveal that these films are polycrystalline in nature with preferred orientation along (1 1 1) direction. Atomic force microscopy studies show that these films are very smooth with maximum root mean square roughness of 0.77 nm. These films are highly transparent and transparency of the films increases with increase in oxygen partial pressure. We observe an increase in optical bandgap of CdO films by Gd doping. The maximum optical band gap of 3.4 eV is observed for films grown at 1 × 10⁻⁵ mbar. The electrical resistivity of the films first decreases and then increases with increase in oxygen partial pressure. The lowest electrical resistivity of 2.71 × 10⁻⁵ Ω cm and highest mobility of 258 cm²/Vs is observed. These low temperature processed highly conducting, transparent, and wide bandgap semiconducting films could be used for flexible optoelectronic applications.     

Synthesis and characterization of sol-gel derived gallium-doped zinc oxide thin films

Gallium-doped ZnO (GZO) semiconductor thin films were prepared by a sol-gel spin coating process. The effects of Ga dopant concentrations on the microstructure, electrical resistivity, optical properties, and photoluminescence (PL) were studied. XRD results showed that all the as-prepared GZO films had a wurtzite phase and a preferred orientation along the [0 0 2] direction. ZnO thin films doped with Ga had lower electrical resistivity, lower RMS roughness, and improved optical transmittance in the visible region. The lowest average electrical resistivity value, 2.8 × 10² Ω cm, was achieved in the ZnO thin films doped with 2% Ga, which exhibited an average transmittance of 91.5%. This study also found that the optical band gap of Ga-doped films was 3.25 eV, slightly higher than that of undoped samples (3.23 eV), and the PL spectra of GZO films showed strong violet-light emission centers at about 2.86 eV (the corresponding wavelength of which is about 434 nm).     

Electric and dielectric behavior of CaCu3Ti4O12-based thin films obtained by soft chemical method

CaCu₃Ti₄O₁₂ (stoichiometric) and Ca_1.1Cu_2.9Ti₄O₁₂ (non-stoichiometric) thin films have been prepared by the soft chemical method on Pt/Ti/SiO₂/Si substrates, and their electrical and dielectric properties have been compared as a function of the annealing temperature. The crystalline structure and the surface morphology of the films were markedly affected by the annealing temperature and excess calcium. The films show frequency-independent dielectric properties at room temperature which is similar to those properties obtained in single-crystal or epitaxial thin films. The room temperature dielectric constant of the 570-nm-thick CCTO thin films annealed at 600 °C at 10 kHz was found to be 124. The best non-ohmic behavior (α = 12.6) presented by the film with excess calcium annealed at 500 °C. Resistive hysteresis on the I-V curves was observed which indicates these films can be used in resistance random access memory (ReRAM).     

Annealing driven performance and optical effects in nanocrystalline SnO2 thin films induced by pulsed delivery

Tin dioxide thin films were prepared successfully by pulsed laser deposition techniques on glass substrates. The thin films were then annealed for 30 min from 50 °C to 550 °C at 50 °C intervals. The influence of the annealing temperature on the microstructure and optical properties of SnO₂ thin films was investigated using X-ray diffraction, optical transmittance and reflectance measurements. Various optical parameters, such as optical band gas energy, refractive index and optical conductivity were calculated from the optical transmittance and reflectance data recorded in the wavelength range 300-2500 nm. We found that the SnO₂ thin film annealed at temperatures up to 400 °C is a good window material for solar cell application. Our experimental results indicated that SnO₂ thin films with the high optical quality could be synthesized by pulsed laser deposition techniques.     

Temperature impact on morphological evolution of ZnO and its consequent effect on physico-chemical properties

The temperature influenced morphology evolution and its effect on physico-chemical properties of ZnO thin films deposited onto glass substrates from alkaline environment, complexed via EDTA chelant are systematically studied. Temperature dependent growth mechanism model for change in microstructure is proposed. The physico-chemical properties of deposited films are studied by the analysis of structural, morphological, surface wettabillity, optical and electrical properties. Nanocrystalline ZnO thin films with hexagonal structure having mari-gold flowers and tetra pods like morphologies with optical band gaps 3.1 and 2.96 eV showed drastic surface wettabillity transformation from highly hydrophobic (142°) to superhydrophilic (<5°) behavior for bath placed at room temperature (300 K) and 333 K, respectively. The room temperature photoluminescence spectrum in the visible light region showed decreasing in intensity and electric resistivity measurement showed reduction in electrical resistivity from 10⁶ to 10⁴ Ω cm as consequence of increment in deposition temperature. The morphology evolution as impact of bath temperature can provide wide scope with significant change in physico-chemical properties of smart ZnO, which can be potentially tuned in many functional applications with feasibility.     

Structural, optical and electrical properties of In-doped Cd2SnO4 thin films by spray pyrolysis method

Preparation of highly conducting and transparent In-doped Cd₂SnO₄ thin film by spray pyrolysis method at a substrate temperature of 525 °C is reported. In-doping concentration is varied between 1 and 5 wt.%. The effect of In-doping on structural, optical and electrical properties was investigated using different techniques such as X-ray diffraction, atomic force microscopy, optical transmittance and Hall measurement. X-ray diffraction studies revealed that the films are polycrystalline with cubic crystal structure. The undoped and In-doped Cd₂SnO₄ films exhibit excellent optical transparency. The average optical transmittance is ∼87% in the visible range for 3 wt.% In-doping. Further In-doping widens the optical band gap from 2.98 ± 0.1 eV to 3.04 ± 0.1 eV. A minimum resistivity of 1.76 ± 0.2 × 10⁻³ Ω cm and maximum carrier concentration of 9.812 ± 0.4 × 10¹⁹ cm⁻³ have been achieved for 1 wt.% In-doping in Cd₂SnO₄ thin films.     

Effects of thermal treatment on the characteristics of boron and tantalum-doped ZnO thin films deposited by the electrospraying method at atmospheric pressure

Metal-doped (B and Ta) ZnO thin films were deposited by the electrospraying method onto a heated glass substrate. The structural, electrical and optical properties of the films were investigated as a function of dopant concentration in the solution and also as a function of annealing temperature. The results show that all the prepared metal-doped ZnO films were polycrystalline in nature with a (0 0 2) preferred orientation. As the amounts of dopant were increased in the starting solution, the crystallinity and transmittance decreased. On the other hand, heat treatment of the films enhanced the transmittance, Hall mobility, carrier concentration and crystallinity. It was also observed that 2 at.% is the optimal doping amount in order to achieve the minimum resistivity and maximum optical transmittance. As-deposited films have high resistivity and low optical transmittance. The annealing of the as-deposited thin films in air resulted in the reduction of resistivity. Depending on the characteristics of dopant, mainly ionic radius, the effects of dopant were studied on the properties of ZnO thin films. Boron and tantalum have been considered as dopants, tantalum being the superior of the two, since it showed the lower resistivity and higher carrier concentration as well as higher mobility. The minimum value of resistivity was 1.95 × 10^− 4 Ω cm (15 Ω/□) with an optical transmittance more than 93% in the visible region and minimum resistivity of 2.16 × 10^− 4 Ω cm (18 Ω/□) with an optical transmittance greater than 96% for 2 at. % tantalum- and boron-doped ZnO films respectively. The present values of resistivities were closer to the indium tin oxide (ITO) resistivity and also closest to the lowest resistivity values among the ZnO films that were previously reported. The prepared films exhibit the good crystalline structure, homogenous surface, high optical transmittance and low resistivity that are preferable for optical devices.     

P-type transparent conducting SnO2:Zn film derived from thermal diffusion of Zn/SnO2/Zn multilayer thin films

Highly transparent, p-type conducting SnO₂:Zn thin films are prepared from the thermal diffusion of a sandwich structure of Zn/SnO₂/Zn multilayer thin films deposited on quartz glass substrate by direct current (DC) and radio frequency (RF) magnetron sputtering using Zn and SnO₂ targets. The deposited films were annealed at various temperatures for thermal diffusion. The effect of annealing temperature and time on the structural, electrical and optical performances of SnO₂:Zn films was studied. XRD results show that all p-type conducting films possessed polycrystalline SnO₂ with tetragonal rutile structure. Hall effect results indicate that the treatment at 400 °C for 6 h was the optimum annealing parameters for p-type SnO₂:Zn films which have relatively high hole concentration and low resistivity of 2.389 × 10¹⁷ cm^− 3 and 7.436 Ω cm, respectively. The average transmission of the p-type SnO₂:Zn films was above 80% in the visible light range.     

Annealing temperature dependence of the optical and structural properties of selenium-rich CdSe thin films

Structural and optical properties of selenium-rich CdSe (SR-CdSe) thin films prepared by thermal evaporation are studied as a function of annealing temperature. X-ray diffraction (XRD) patterns show that the as-prepared films were amorphous, whereas the annealed films are polycrystalline. Analyzing XRD patterns of the annealed films reveal the coexistence of both (hexagonal) Se and (hexagonal) CdSe crystalline phases. Surface roughness of SR-CdSe films is measured using atomic force microscope (AFM). Analyses of the absorption spectra in the wavelength range (200-2500 nm) of SR-CdSe thin films indicates the existence of direct and indirect optical transition mechanisms. The optical band gap (E_g) of as-prepared film is 1.92 and 2.14 eV for the indirect allowed and direct allowed transitions respectively. After annealing, the absorption coefficient and optical band gap were found to decrease, while the values of refractive index (n) and the extinction coefficient (k_ex) increase. The dispersion of the refractive index is described using the Wimple-Di Domenico (WDD) single oscillator model and the dispersion parameters are calculated as a function of annealing temperature. Besides, the high frequency dielectric constant (?_∞) and the ratios of the free carrier concentration to its effective mass (N/m*) are studied as a function of annealing temperature. The results are discussed and correlated in terms of amorphous-crystalline transformations.