Spectroscopic studies of sol–gel grown CdS nanocrystalline thin films for optoelectronic devices

CdS is one of the highly photosensitive candidate of II–VI group semiconductor material. Therefore CdS has variety of applications in optoelectronic devices. In this paper, we have fabricated CdS nanocrystalline thin film on ultrasonically cleaned glass substrates using the sol–gel spin coating method. The structural and surface morphologies of the CdS thin film were investigated by X-ray Diffraction (XRD) and Field Emission Scanning Electron Microscopy (FESEM) respectively. The surface morphology of thin films showed that the well covered substrate is without cracks, voids and hole. The round shape particle has been observed in SEM micrographs. The particles sizes of CdS nanocrystals from SEM were estimated to be～10–12 nm. Spectroscopic properties of thin films were investigated using the UV–vis spectroscopy, Photoluminescence and Raman spectroscopy. The optical band gap of the CdS thin film was estimated by UV–vis spectroscopy. The average transmittance of CdS thin film in the visible region of solar spectrum found to be～85%. Optical band gap of CdS thin film was calculated from transmittance spectrum ～2.71 eV which is higher than bulk CdS (2.40 eV) material. This confirms the blue shifting in band edge of CdS nanocrystalline thin films. PL spectrum of thin films showed that the fundamental band edge emission peak centred at 459 nm also recall as green band emission.     

Effect of 100 MeV O7+ ion beam irradiation on radio frequency reactive magnetron sputtered ZnO thin films

Zinc oxide (ZnO) thin films were deposited on sapphire substrates at room temperature by radio frequency (RF) magnetron sputtering. These films were irradiated with 100 MeV O⁷⁺ ions of the fluencies 5×10¹³ ions/cm² at room temperature (RT) and at liquid nitrogen temperature (LNT). Profilometer studies showed that the roughness of pristine and LNT irradiated ZnO thin films were higher than that of the RT irradiated ZnO thin film. The glancing angle X-ray diffraction analysis reveals a reduced intensity and increased full width at half maximum (FWHM) of the (002) diffraction peak in the case of LNT irradiated film indicating disorder. However, the intensity and FWHM of the (002) diffraction peak in the case of RT irradiated ZnO thin films are comparable to those of the pristine film. UV–visible transmission spectra show that the percentage of transmission and band gap energy are different for RT and LNT irradiated films. While the pristine ZnO thin film exhibits two emissions—a broad emission at 403 nm and a sharp emission at 472 nm in its photoluminescence spectrum; the emission at 472 nm was absent for the irradiated films. The atomic concentrations of zinc and oxygen during the irradiation process were obtained using auger electron spectroscopy.     

Role of thermal annealing on SiGe thin films fabricated by PECVD

Amorphous Silicon Germanium (a-SiGe) thin films of 500 nm thickness are deposited on silicon substrates using Plasma Enhanced Chemical Vapour Deposition (PECVD). To obtain polycrystalline nature of films, thermal annealing is done at various temperature (450–600 °C) and time (1–10 h). The surface morphology of the pre- and post-annealed films is investigated using scanning electron microscopy (SEM) and atomic force microscopy (AFM). The crystallographic structure of the film is obtained by X-ray diffraction method. Raman spectroscopy is carried out to quantify the Ge concentration and the degree of strain relaxation in the film. Nano-indentation is performed to obtain the mechanical properties of the film. It is found that annealing reduces the surface roughness of the film and increases the Ge concentration in the film. The grain size of the film increases with increase in annealing temperature. The grain size is found to decrease with increase in annealing time up to 5 h and then increased. The results show that 550 °C for 5 h is the critical annealing condition for variation of structural and mechanical properties of the film. Recrystallization starts at this condition and results in finer grains. An increase in hardness value of 7–8 GPa has been observed. Grain growth occurs above this critical annealing condition and degrades the mechanical properties of the film. The strain in the film is only relaxed to about 55% even for 10 h of annealing at 600 °C. Transmission Electron Microscopy (TEM) observations show that the strain relaxation occurs by forming misfit dislocations and these dislocations are confined to the SiGe/Si interface.     

Investigation of the blue–green emission and UV photosensitivity of Cu-doped ZnO films

Cu-doped zinc oxide (ZnO:Cu) films were deposited on p-Si (100) substrates using radio-frequency reactive magnetron sputtering. The structure and optical properties of the films were characterized by X-ray diffraction spectroscopy (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and fluorescence spectroscopy. XRD and SEM results revealed that ZnO:Cu film had a better preferential orientation along the c-axis compared with pure ZnO film. The chemical state of copper and oxygen in ZnO:Cu films was investigated by XPS. The results suggest that the Cu ion has a mixed univalent and bivalent state. The integrated Cu²⁺/Cu⁺ intensity ratio increased with the O₂ partial pressure. Photoluminescence measurements at room temperature revealed a double peak in the blue regions and a green emission peak. The close relationship between the valence state of Cu ions and the blue–green emission is discussed in detail. A higher photocurrent was observed for ZnO:Cu films under UV illumination. UV photodetectors based on ZnO:Cu films have high sensitivity and fast response and recovery times. Under periodic UV illumination at 380 nm the ZnO:Cu films showed stable photocurrent growth and decay, so the films are potential candidate materials for UV photodetectors.     

Effect of annealing on the structural and optical properties of laser ablated nanostructured barium tungstate thin films

High quality BaWO₄ thin films are successfully deposited on quartz substrate for a duration of 30 min using pulsed laser ablation technique and using a laser radiation of wavelength 355 nm and the effect of thermal annealing on the structural and optical properties is studied by using techniques like X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy, micro-Raman, FTIR and UV–visible spectroscopy. All the films show monoclinic crystalline structure with (2 0 2) plane as the preferred orientation of crystal growth. From the XRD analysis it is found that the optimum annealing temperature for better crystallization of the BaWO₄ film is 700 °C and there is no phase change observed with annealing temperature. The presence of the characteristic bands for the BaWO₄ in the Raman spectra of the films suggests the formation of BaWO₄ crystalline phase in all the films. SEM and AFM analyses show that as the annealing temperature increases the connectivity between individual grains increases and shows an ordered packing. The geometrical optimization and energy calculation of the title compound were done using the Gaussian 09 software package and the calculations were carried out using the CAM-B3LYP functional combined with standard Lanl2Dz basis set. The thickness of the films was calculated using lateral SEM images and also from optical transmission spectral data using PUMA software.     

Effect of thermal annealing on physical properties of vacuum evaporated In2S3 buffer layer for eco-friendly photovoltaic applications

The present communication reports the effect of thermal annealing on the physical properties of In₂S₃ thin films for eco-friendly buffer layer photovoltaic applications. The thin films of thickness 150 nm were deposited on glass and indium tin oxide (ITO) coated glass substrates employing thermal vacuum evaporation technique followed by post-deposition thermal annealing in air atmosphere within a low temperature range 150–450 °C. These as-deposited and annealed films were subjected to the X-ray diffraction (XRD), UV–vis spectrophotometer, current–voltage tests and scanning electron microscopy (SEM) for structural, optical, electrical and surface morphological analysis respectively. The compositional analysis of as-deposited film is also carried out using energy dispersive spectroscopy (EDS). The XRD patterns reveal that the as-deposited and annealed films (≤300 °C) have amorphous nature while films annealed at 450 °C show tetragonal phase of β-In₂S₃ with preferred orientation (109) and polycrystalline in nature. The crystallographic parameters like lattice constant, inter-planner spacing, grain size, internal strain, dislocation density and number of crystallites per unit area are calculated for thermally annealed (450 °C) thin films. The optical band gap was found in the range 2.84–3.04 eV and observed to increase with annealing temperature. The current–voltage characteristics show that the as-deposited and annealed films exhibit linear ohmic behavior. The SEM studies show that the as-deposited and annealed films are uniform, homogeneous and free from crystal defects and voids. The grains in the thin films are similar in size and densely packed and observed to increase with thermal annealing. The experimental results reveal that the thermal annealing play significant role in the structural, optical, electrical and morphological properties of deposited In₂S₃ thin films and may be used as cadmium-free eco-friendly buffer layer for thin films solar cells applications.     

Improvement in crystal quality of ZnO film on Si substrate by using a homo-buffer layer

ZnO thin films without and with a homo-buffer layer have been prepared on Si(1 1 1) substrates by pulsed laser deposition (PLD) under various conditions. Photoluminescence (PL) measurement indicates that the optical quality of ZnO thin film is dramatically improved by introducing oxygen into the growth chamber. The sample deposited at 60 Pa possesses the best optical properties among the oxygen pressure range studied. X-ray diffraction (XRD) results show that the films directly deposited on Si are of polycrystalline ZnO structures. A low-temperature (500 °C) deposited ZnO buffer layer was used to enhance the crystal quality of the ZnO film. Compared to the film without the buffer layer, the film with the buffer layer exhibits aligned spotty reflection high-energy electron diffraction (RHEED) pattern and stronger near-band-edge emission (NBE) with a smaller full-width at half-maximum (FWHM) of 98 meV. The structural properties of ZnO buffer layers grown at different temperatures were investigated by RHEED patterns. It is suggested that the present characteristics of the ZnO epilayer may be raised further by elevating the growth temperature of buffer layer to 600 °C.     

Composition,structure and electrical properties of DC reactive magnetron sputtered Al2O3 thin films

Thin films of alumina (Al₂O₃) were deposited over Si 〈1 0 0〉 substrates at room temperature at an oxygen gas pressure of 0.03 Pa and sputtering power of 60 W using DC reactive magnetron sputtering. The composition of the as-deposited film was analyzed by X-ray photoelectron spectroscopy and the O/Al atomic ratio was found to be 1.72. The films were then annealed in vacuum to 350, 550 and 750 °C and X-ray diffraction results revealed that both as-deposited and post deposition annealed films were amorphous. The surface morphology and topography of the films was studied using scanning electron microscopy and atomic force microscopy, respectively. A progressive decrease in the root mean square (RMS) roughness of the films from 1.53 nm to 0.7 nm was observed with increase in the annealing temperature. Al–Al₂O₃–Al thin film capacitors were then fabricated on p-type Si 〈1 0 0〉 substrate to study the effect of temperature and frequency on the dielectric property of the films and the results are discussed.     

The effect of potential on electrodeposited CdSe thin films

Cadmium selenide (CdSe) thin films have been successfully prepared by the electrodeposition technique on indium doped tin oxide (ITO) substrates with aqueous solutions of cadmium sulphate and selenium dioxide. The deposited films were characterized with X-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersive analysis by X-rays (EDAX), photoluminescence (PL), UV spectrometry and electrical resistivity measurements. XRD analysis shows that the films are polycrystalline in nature with hexagonal crystalline structure. The various parameters such as crystallite size, micro strain, dislocation density and texture coefficients were evaluated. SEM study shows that the total substrate surface is well covered with uniformly distributed spherical shaped grains. Photoluminescence spectra of films were recorded to understand the emission properties of the films. The presence of direct transition with band gap energy 1.75 eV is established from optical studies. The electrical resistivity of the thin films is found to be 10⁶ Ω cm and the results are discussed.     

Effects of the Cd:Zn:S molar ratio and heat treatment on the optical and photoluminescence properties of nanocrystalline CdZnS thin films

Nanocrystalline cadmium zinc sulfide thin films with different molar ratios were prepared by sol–gel dip-coating in a polyethyleneglycol matrix. After heat treatment in air at 250, 350 and 450 °C, the thin films were characterized by studying their structural, morphological, compositional, optical (linear and nonlinear) and photoluminescence (PL) properties. According to X-ray diffraction (XRD) results, the samples are polycrystalline with a hexagonal crystal structure and an average grain size of 12–18 nm. The surface morphology of the films was examined by scanning electron microscopy (SEM). The results show that the films consist of nanocrystalline grains included in clusters with uniform coverage over the substrate surface. To determine their chemical composition, X-ray photoelectron spectra (XPS) of composite films were measured. The transmittance and bandgap of the films increased with the Zn concentration and decreased with increasing annealing temperature. The refractive index of the films was measured and the related dispersion is discussed in terms of the Wemple–DiDomenico single oscillator model. The third-order nonlinear polarizability of the films was estimated using a semi-empirical relation based on the single oscillator model. The results show that the films are suitable as optical switches. PL spectra were recorded for an excitation wavelength of 210 nm. The emission intensity for the films varied with the Zn ratio and the annealing temperature and the behavior of different peaks is discussed.     

Effects of the substrate temperature and solution molarity on the structural opto-electric properties of ZnO thin films deposited by spray pyrolysis

Zinc oxide (ZnO) was largely studied in various applications such as photovoltaic conversion, optoelectronics and piezoelectric, because of its interesting physical properties (morphological, structural, optical and electrical). The present work deals with the preparation of zinc oxide thin films (ZnO) deposited by the spray pyrolysis method. The starting solution was zinc chloride (ZnCl₂). Effects of solution molarity and substrate temperature on films properties were investigated. All films deposited were characterized by various techniques such as X-ray diffraction for structural characterizations, profilometry for thickness measurements, UV–vis transmission spectrophotometry for optical properties and the four probes conductivity measurements for electrical characterization. The X-ray diffraction (XRD) patterns show that the films deposited are polycrystalline with (0 0 2) plan as preferential orientation. The UV–vis spectroscopy confirms the possibility of good transparent ZnO thin films deposition with an average transmission of about ∼85% in the visible region. However, the measured electrical resistivities of the deposited films were in the order of 10⁴ Ω cm     

Annealing temperature dependent structural and optical properties of electrodeposited CdSe thin films

Cadmium selenide films were synthesized using simple electrodeposition method on indium tin oxide coated glass substrates. The synthesized films were post annealed at 200 °C, 300 °C and 400 °C. X-ray diffraction of the films showed the hexagonal structure with crystallite size <3 nm for as deposited films and 3–25 nm for annealed films. The surface morphology of films using field emission scanning electron microscopy showed granular surface. The high resolution transmission electron microscopy of a crystallite of the film revealed lattice fringes which measured lattice spacing of 3.13 Å corresponding to (002) plane, indicating the lattice contraction effect, due to small size of CdSe nanocrystallite. The calculation of optical band gap using UV–visible absorption spectrum showed strong red-shift with increase in crystallite size, indicating to the charge confinement in CdSe nanocrystallite.     

Effect of deposition temperature on structural,optical properties and configuration of CdSe nanocrystalline thin films deposited by chemical bath deposition

CdSe nanoparticle thin films were deposited on glass substrates by the chemical bath deposition (CBD) method at low deposition temperature ranging from room temperature up to 50 °C while the pH of the bath was kept constant at 12.1. The structural and morphological variation were investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM) technique. The energy band gap and optical properties were characterized by the absorbance spectra. Rutherford backscattering spectroscopy (RBS) analysis reveals the excess of Cd rather than Se in depth profile along the thin film thickness. The prepared CdSe nanoparticles have cubic structure and by increasing the temperature the deposited films become continues, homogeneous and tightly adherent. The results also revealed that by increasing the deposition temperature from room temperature up to 50 °C, the band gap decreases from 3.52 eV up to 1.84 eV.     

Synthesis of mackinawite FeS thin films from acidic chemical baths

The growth of monophasic iron sulfide thin films onto glass substrates has been achieved by chemical bath deposition at acidic values of pH. Powder X-ray diffraction (p-XRD) confirms the deposition of tetragonal FeS (mackinawite) with preferred orientation along (001) plane. The crystallite size estimated by Scherrer equation was found to be 14 nm. Scanning electron microscopy (SEM) shows the formation of nanoflakes as base layer and nanoflowers as top layer. Energy Dispersive X-ray (EDX) analysis of the deposited iron sulfide thin films shows the iron to sulfur ratio close to 1:1 confirming the deposition of FeS. UV–vis absorption spectroscopy showed a blueshift due to the nanosize crystallites FeS with a band gap of 1.87 eV.     

Investigations on the structural and optical properties of Li,N and (Li,N) co-doped ZnO thin films prepared by sol–gel technique

Pure and doped zinc oxide thin films have been deposited on sapphire substrates by using the sol–gel method and spin coating technique. The X-ray diffraction pattern showed that the deposited films exhibit hexagonal zinc oxide structure. Room temperature photoluminescence measurements show the presence of two emission bands. The predominant near band edge ultraviolet emission is at 3.28 eV and a suppressed broad band of deep level emission in the range of 2.1–2.5 eV. The incorporation of nitrogen is indicative of p-type behavior as observed from X-ray photoelectron spectrum of nitrogen in the doped samples. The p-type conduction of Li, N:ZnO may be attributed to the formation of a LiZn–N complex acceptor.     

Effect of processing parameter on structural,optical and electrical properties of photovoltaic chalcogenide nanostructured RF magnetron sputtered thin absorbing films

The aim of this work was to develop high quality of CuIn_1−xGa_xSe₂ thin absorbing films with x (Ga/In+Ga)<0.3 by sputtering without selenization process. CuIn_0.8Ga_0.2Se₂ (CIGS) thin absorbing films were deposited on soda lime glass substrate by RF magnetron sputtering using single quaternary chalcogenide (CIGS) target. The effect of substrate temperature, sputtering power & working pressure on structural, morphological, optical and electrical properties of deposited films were studied. CIGS thin films were characterised by X-ray diffraction (XRD), Field emission scanning electron microscope (FE-SEM), Energy dispersive X-ray spectroscopy (EDAX), Atomic force microscopy (AFM), UV–vis–NIR spectroscopy and four probe methods. It was observed that microstructure, surface morphology, elemental composition, transmittance as well as conductivity of thin films were strongly dependent on deposition parameters. The optimum parameters for CIGS thin films were obtained at a power 100 W, pressure 5 mT and substrate temperature 500 °C. XRD revealed that thin film deposited at above said parameters was polycrystalline in nature with larger crystallite size (32 nm) and low dislocation density (0.97×10¹⁵ lines m⁻²). The deposited film also showed preferred orientation along (112) plane. The morphology of the film depicted by FE-SEM was compact and uniform without any micro cracks and pits. The deposited film exhibited good stoichiometry (Ga/In+Ga=0.19 and In/In+Ga=0.8) with desired Cu/In+Ga ratio (0.92), which is essential for high efficiency solar cells. Transmittance of deposited film was found to be very low (1.09%). The absorption coefficient of film was ~10⁵ cm⁻¹ for high energy photon. The band gap of CIGS thin film evaluated from transmission data was found to be 1.13 eV which is optimum for solar cell application. The electrical conductivity (7.87 Ω⁻¹ cm⁻¹) of deposited CIGS thin film at optimum parameters was also high enough for practical purpose.     

Variation of the structural,optical and electrical properties of CBD CdO with processing temperature

Nanostructures of CdO thin films are prepared by chemical bath deposition (CBD) technique. The synthesized film is annealed in static air by using the hotplate at 373, 473, 573 and 673 K for 10 min. The effect of annealing temperature on structural, morphological, optical and electrical properties of CdO thin films has been investigated. The prepared thin films are characterised by X-ray diffraction (XRD), atomic force microscope (AFM), optical reflection microscope (ORM), UV–Visible Spectrophotometer and electrical resistivity. XRD shows the emergence of the cubic phase of CdO film in a preferred orientation (111) plane at 573 K. The AFM and ORM show that CdO films have smooth homogeneous surface in the formula with the emergence of nanoclusters gathering as nanoparticles with the average of grain size about 100 nm at 573 K. The optical properties prove that deposited films have high transparency within the visible range of the spectrum that reaches to more than 85% with a wide band gap that extends from 2.42 eV to 2.7 eV. The electrical properties of the CdO films show that resistivity decreases with increased annealing temperatures. In addition, it is proved that more than one activation energy appears and they change according to the temperature of annealing and this comes as a result of the polycrystalline structure. This study indicates that the properties of CdO thin films could be improved with annealing temperature and these films can be used in many technological applications.     

Effect of pH on the properties of electrochemically prepared ZnO thin films

Zinc Oxide (ZnO) thin films have been electrochemically deposited on fluorine doped tin oxide (FTO) coated glass substrates from an aqueous electrolyte. Deposition potential −0.96 V was optimized by cyclic voltammetry experiment for slow scan rate 5 mV/s with moderate agitation of electrolyte. The effect of pH on the electrodeposition of ZnO is studied by cyclic voltammetry, X-ray diffraction (XRD), scanning electron microscopy (SEM), optical spectroscopy and photoelectrochemical I-t transient characteristics. It is revealed that the pH of the electrolyte has significant influence on the surface morphology and structural properties. Highly crystalline ZnO layers with hexagonal crystal structure deposited for all pH of the solutions. A systematic shift observed in the reflections (002) and (101) is correlated with an effective tensile strain developed in the crystal lattice. A remarkable improvement in the crystallinity was noticed in the as-deposited ZnO samples with increasing pH and upon heat treatment. Optical direct band gap ~ 3.26–3.33 eV and transmittance ~70 −80% was measured by optical spectroscopy. PL measurement showed the band edge emission at 375–382 nm and a visible light emission at 410–550 nm. The intensities of emission peaks are found to be affected by the pH of bath. The compact, densely packed and well adherent thin films of ZnO electrodeposited in zinc nitrate bath for pH 2.0, 3.5 and 6.0. The surface morphology has been changed from granular to disc shaped and finally a large hexagonal sheets were obtained with an increase in the pH of bath. Nearly stoichiometric ZnO thin films are electrodeposited at −0.96 V versus Ag/AgCl reference electrode for pH 6.0. The photoelectrochemical (PEC) measurement (I-t transient curve) shows the enhancement in photocurrent with increasing the pH of zinc nitrate solution. After heat treatment the photocurrent is increased by 54%, 98% and 130% in the samples deposited from 2.0, 3.5 and 6.0 pH of the bath. I-V measurements were further confirmed the current enhancement in all samples after heat treatment.     

Enhancement in optical characteristics of c-axis-oriented radio frequency–sputtered ZnO thin films through growth ambient and annealing temperature optimization

High-quality radio frequency–sputtered ZnO were grown on Si substrates at 400 °C at various partial gas pressures (Ar/Ar+O2). Subsequently, to remove as-grown defects, high temperature annealing from 700 to 900 °C on as-grown samples in constant oxygen flow for 10 s was performed. X-ray diffraction study confirmed the formation of highly crystalline films with a dominant peak at (002). The sample grown in 50% Ar and 50% O₂ ambient exhibited the lowest linewidth (2θ=~0.2728°) and highest stoichiometry. Grain size of the as grown samples decreased with increase in the partial pressure of oxygen till a certain ratio (1:1), and photoluminescence (PL) improved with increase in annealing temperature. Low-temperature (18 K) PL measurements showed a near-band-edge emission peak at 3.37 eV, and the highest peak intensity (more than six orders compared to others with narrow linewidth of ~0.01272 eV) was exhibited by the sample annealed at 900 °C and was six orders higher than that of the as-grown sample. All as-grown samples exhibited dominant visible-range peaks due to emission from defect states.     

Properties of CuAlO2 thin films deposited by polyacrylamide gel route

CuAlO₂ films were deposited on clean glass substrates by the acrylamide sol–gel dip coating technique. The coated films were dried in air oven for 30 min followed by heat treatment in air at different temperatures in the range of 350–500 °C. The films annealed at low temperatures exhibited weak x-ray diffraction (XRD) peaks. As the post anneal temperature increased beyond 375 °C, the XRD pattern exhibited the diffraction peaks of rhombohedral CuAlO₂. Surface morphology of the films indicated that the films annealed at low temperatures exhibit small grains. As the annealing temperature increases larger grains are observed. The root mean square (rms) value of the surface roughness increases with annealing temperature. The films exhibited optical transmission above 75%. The films post annealed at low temperature exhibited lower transmission. Optical band gap in the range of 3.43–3.75 eV was obtained for the films annealed at different temperature. Hall measurements indicated p-type conductivity. Resistivity of the films decreased from 25.0 to 2.0 Ω cm as the anneal temperature increased. Mobility and carrier density increased with annealing temperature.