Study of structural and optical properties of Ge doped ZnO films

The Ge doped ZnO films were deposited on quartz substrates by radio frequency magnetron sputtering. The effects of doping and substrate temperature on the structural and optical properties of the Ge doped ZnO films were investigated by means of X-ray diffraction (XRD), UV-visible transmission spectra, X-ray photoelectron spectroscopy and photoluminescence (PL) spectra. The XRD patterns showed that Zn₂GeO₄ phases were formed in the films. With the increase of substrate temperature the crystallization of Zn₂GeO₄ was improved, and that of ZnO phases turned worse, and no diffraction peak of ZnO was observed when the substrate temperature was 700 °C. Obvious ultraviolet (UV) light emission was found due to ZnO grains, and it was much stronger than that of un-doped ZnO films. The enhancement of UV light emission at about 380 nm may be caused by excitons which were formed at the interface between Zn₂GeO₄ and ZnO grains. In the visible region of the PL spectra, the green light emission peak of samples at about 512 nm was associated with defects in ZnO. A red shift of the green light emission peak was observed which can be explained by the fact that there is a luminescence center at about 548 nm taking the place of the defect emission of ZnO with the increase of substrate temperature. The red shift of the green light emission peak and the 548 nm green light emission peaks of the PL spectrum show that some Ge²⁺ should replace the Zn²⁺ positions during the Zn₂GeO₄ grains growth and form the Ge²⁺ luminescence centers in Zn₂GeO₄ grains.     

Optical characterization of ZnO thin films deposited by Sol-gel method

In this paper, ZnO thin film is deposited on Pt/TiO₂/SiO₂/Si substrate using the sol-gel method and the effect of annealing temperature on the structural morphology and optical properties of ZnO thin films is investigated. The ZnO thin films are crystallized by the heat treatment at over 400°C. The ZnO thin film annealed at 600°C exhibits the greatest c-axis orientation and the Full-Width-Half-Maximum (FWHM) of X-ray peak is 0.4360°. A dense ZnO thin film is deposited by the growth of uniform grains with the increase of annealing temperature but when the annealing temperature increases to 700°C, the surface morphology of ZnO thin film becomes worse by the aggregation of ZnO particles. In the results of surface morphology of ZnO thin film using atomic force microscope (AFM), the surface roughness of ZnO thin film annealed at 600°C is smallest, that is, approximately 1.048 nm. For the PL characteristics of ZnO thin film, it is observed that ZnO thin film annealed at 600°C exhibits the greatest UV (ultraviolet) exciton emission at approximately 378 nm, and the smallest visible emission at approximately 510 nm among ZnO thin films annealed at various temperatures. It is deduced that ZnO thin film annealed at 600°C is formed most stoichiometrically, since the visible emission at approximately 510 nm comes from either oxygen vacancies or impurities.     

Preparation of highly transparent conductive Al-doped ZnO thin films and annealing effects on properties

Aluminum-doped ZnO (ZAO) thin films were deposited on fused quartz substrates by radio frequency sputtering in pure argon ambient at 450 °C. Effects of in situ annealing temperature and annealing atmosphere on microstructure, electrical and optical properties of ZAO films have been investigated. Results showed that as-grown film without annealing treatments attained lowest resistivity of 1.1 × 10⁻⁴Ω cm. And all films performed high average transmittance greater than 90% in visible region. X-Ray diffraction (XRD), photoluminescence (PL), X-ray photoelectron spectroscopy (XPS) were utilized to characterize the microstructure properties of films. XRD results indicated that as-grown film had higher crystalline quality and larger grain size than annealed films. Al atoms replaced Zn efficiently to provide electrons stable in all samples. PL spectra revealed that high annealing temperature and oxygen atmosphere would generate more Zn vacancy (V_Zn) and oxide antisite defect (O_Zn), respectively and composition content results from XPS provided supports to this.     

Enhanced photocatalytic activity of Mg0.05Zn0.95O thin films prepared by sol–gel method through a cycle

Mg_0.05Zn_0.95O thin films were prepared on silicon substrates by a sol–gel dip-coating technique. Microstructure, surface topography and optical properties of the thin films were characterized by X-ray diffraction, atom force microscopy, Fourier transform infrared spectrophotometer and fluorescence spectrometer. The results show that the thin film annealed at 700 °C has the largest average grain size and exhibits the best c-axis preferred orientation. As annealing temperature increases to 800 °C, the grain along c-axis has been suppressed. Roughness factor and average particle size increase with the increase of annealing temperature. The IR absorption peak appearing at about 416 cm^?1 is assigned to hexagonal wurtzite ZnO. The thin film annealed at 700 °C has the maximum oxygen vacancy, which can be inferred from the green emission intensity. Photocatalytic results show that the thin film annealed at 700 °C exhibits remarkable photocatalytic activity, which may be attributed to the larger grain size, roughness factor and concentration of oxygen vacancy. Enhanced photocatalytic activity of Mg_0.05Zn_0.95O thin films after a cycle may be attributed to the increase of surface oxygen vacancy and photocorrosion of amorphous MgO on the surface of thin film under UV irradiation.     

Structure and photoluminescence of SiC/ZnO nanocomposites prepared by radio frequency alternate sputtering

SiC/ZnO nanocomposites were prepared by radio frequency alternate sputtering followed by annealing in N₂ ambient. Well-crystallized ZnO matrix was obtained after annealed at 750 °C according to X-ray diffractometer patterns. Transmission electron microscopy analyses indicated that the SiC thin layer aggregated to form SiC nanoclusters with the average size of 7.2 nm when the annealing temperature was 600 °C. When the annealing temperatures increased above 900 °C, some of the SiC nanoclusters changed into SiC nanocrystals and surfacial atoms of the SiC nanoparticles were surrounded by a layer of SiO _x (x ≤ 2) according to the Fourier transform infrared spectrums. The SiC/ZnO nanocomposites annealed at 750 °C exhibit strong photoluminescence bands ranging from 250 to 600 nm. UV light originates from the near band edge emission of ZnO and the blue emission peaked at around 465 nm (2.7 eV) may be due to the formation of emission centers caused by the defects in Si–O network, while the green-emission peak at around 550 nm (2.3 eV) may be attributed to the deep level recombination luminescence caused by the vacancies of oxygen and zinc.     

Rapid Thermal Annealing of ZnO Nanocrystalline Films for Dye-Sensitized Solar Cells

Nanocrystalline ZnO thin films were prepared by the sol–gel method and annealed at 600 °C by conventional (CTA) and rapid thermal annealing (RTA) processes on fluorine-doped tin oxide (FTO)-coated glass substrates for application as the work electrode for a dye-sensitized solar cell (DSSC). ZnO films were crystallized using a conventional furnace and the proposed RTA process at annealing rates of 5 °C/min and 600 °C/min, respectively. The ZnO thin films were characterized by X-ray diffraction (XRD) and atomic force microscopy (AFM) analyses. Based on the results, the ZnO thin films crystallized by the RTA process presented better crystallization than films crystallized in a conventional furnace. The ZnO films crystallized by RTA showed higher porosity and surface area than those prepared by CTA. The results show that the short-circuit photocurrent (J _sc) and open-circuit voltage (V _oc) values increased from 4.38 mA/cm² and 0.55 V for the DSSC with the CTA-derived ZnO films to 5.88 mA/cm² and 0.61 V, respectively, for the DSSC containing the RTA-derived ZnO films.     

Optical and structural properties of ZnO + Zn<Subscript>2</Subscript>TiO<Subscript>4</Subscript> thin films prepared by the sol–gel method

ZnO + Zn₂TiO₄ thin films were obtained by the sol–gel method using precursor solutions with different Ti/Zn ratios in the 0.18–2.13 range. The films were deposited on glass substrates and annealed in an open atmosphere at 550 °C. The oxide was characterized by X-ray diffraction and photoacoustic (PA) spectroscopy. The films were constituted of polycrystalline ZnO for the lowest Ti/Zn ratio (0.18), polycrystalline Zn₂TiO₄ for the 0.70 and 1.0 ratios, and mixes of both oxides for the intermediate ratios (0.32 and 0.50). For the highest ratios studied (1.44 and 2.13), the films were amorphous. The energy band gap (E_g) values were determined from optical absorption spectra, measured by means of the PA technique spectra. E_g varied in the 3.15 eV (ZnO) to 3.70 eV (Zn₂TiO₄) range.     

Effect of growth temperature on structural, electrical and optical properties of dual ion beam sputtered ZnO thin films

ZnO epitaxial thin films were grown on p-type Si(100) substrates by dual ion beam sputtering deposition system. The crystalline quality, surface morphology, optical and electrical properties of as-deposited ZnO thin films at different growth temperatures were studied. Substrate temperature was varied from 100 to 600 °C at constant oxygen percentage O₂/(O₂ + Ar) % of 66.67 % in a mixed gas of Ar and O₂ with constant chamber pressure of 2.75 × 10^?4 mBar. X-Ray diffraction analyses revealed that all the films had (002) preferred orientation. The minimum value of stress was reported to be ?0.32 × 10¹⁰ dyne/cm² from ZnO film grown at 200 °C. Photoluminescence measurements demonstrated sharp near-band-edge emission (NBE) was observed at ~375 nm along with deep level emission (DLE) in the visible spectral range at room temperature. The DLE Peak was found to have decrement as ZnO growth temperature was increased from 200 to 600 °C. The minimum FWHM of the NBE peak of 16.76 nm was achieved at 600 °C growth temperature. X-Ray photoelectron spectroscopy study revealed presence of oxygen interstitials and vacancies point defects in ZnO film grown at 400 °C. The ZnO thin film was found to be highly resistive when grown at 100 °C. The ZnO films were found to be n-type conducting with decreasing resistivity on increasing substrate temperature from 200 to 500 °C and again increased for film grown at 600 °C. Based on these studies a correlation between native point defects, optical and electrical properties has been established.     

Anomalous behavior in ZnMgO thin films deposited by sol-gel method

The magnesium doped zinc oxide is a promising optical material to enhance the luminescence for possible application in solid state lighting. Magnesium doped zinc oxide thin films (Zn_0.85Mg_0.15O) were deposited by sol-gel route on p-type silicon and annealed at different temperatures in oxygen environment for an hour. The doping of magnesium in zinc oxide was confirmed by X-Ray diffraction and the samples were found to have wurtzite crystal structure with (002) preferred orientation. The films were characterized by Hall-effect, atomic force microscopy, UV-VIS spectroscopy, photoluminescence (PL) and work function measurements. The different studies exhibited an anomalous behavior for the film annealed at 900 °C. The Hall effect, work function measurements and UV-VIS spectroscopy indicated that the resistivity, work function and optical band gap increased as a function of annealing temperature (from 300 °C to 700 °C) however these parameters were found to decrease for the films annealed above 700 °C. The particle size increased with the annealing but for the samples annealed at 900 °C, the shape of the grains changed and became elongated like fibers as observed by the atomic force microscopy. The PL measurements displayed the existence of oxygen vacancies defects for the samples annealed at and above 600 °C. The possible mechanism for this anomaly has been discussed in this work.     

Post annealing effect on structural and optical properties of ZnO thin films derived by sol–gel route

Zinc oxide thin films have been spun coated on p-Si (100) substrates by sol–gel route. These films were annealed at different annealing temperatures from 300 to 1,000 °C in the oxygen ambient. In this way a suitable annealing temperature window for the sol–gel derived ZnO films exhibiting minimum defects (points and dislocations) and better quality (crystal and optical) was investigated. The structural and optical features of ZnO thin films have been examined by X-ray diffraction, atomic force microscopy, UV–Vis spectroscopy, and photoluminescence spectra. The results revealed that the crystallization in the films initiated at 300 °C, improved further with annealing. All the deposited films exhibited wurtzite phase with c-axis orientations. The variations in the position of characteristic (002) peak, stress, strain and lattice parameters are investigated as a function of annealing temperature. The optical band gap is not significantly affected with annealing as observed by UV–Vis transmission spectroscopy. The Photoluminescence spectra exhibited three luminescence centers. The near band edge esmission was observed in UV region which enhanced with the heat treatment, is an indication of improvement in the optical quality of films. The other two visible emissions are related to native defects in ZnO lattice were appeared only for higher annealing (≥700 °C).     

Analysis of Li-related defects in ZnO thin films influenced by annealing ambient

Li-doped ZnO thin films were grown on quartz substrates by radio frequency magnetron sputtering and in situ annealing under O₂ or Ar ambient. Li-related defects in ZnO films strongly depend on the annealing ambient. AFM and XRD indicated that ZnO films possessed a good crystallinity with c-axis orientation, uniform thickness and dense surface. Electrical and optical properties demonstrated that, an amount of Li_Zn defect had existed in ZnO annealed under O₂ambient and an amount of Li_i(o) defect had existed in ZnO annealed under Ar ambient. First-principle calculations were performed to calculate formation energies of Li-doped ZnO in order to explain the formation mechanism of Li-related defects in ZnO.     

Fabrication of LiCoO2 thin film cathodes by DC magnetron sputtering method

LiCoO₂ thin films were fabricated on Al substrate by direct current magnetron sputtering method. The effects of Ar/O₂ gas rates and annealing temperatures were investigated. Crystal structures and surface morphologies of the deposited films were investigated by X-ray diffraction, Raman scattering spectroscopy and field emission scanning electron microscopy. The as-deposited LiCoO₂ thin films exhibited amorphous structure. The crystallization starts at the annealing temperature over 400 °C. However, the annealed films have the partially disordered structure without completely ordered crystalline structure even at 600 °C annealing. The electrochemical properties of the LiCoO₂ films were investigated by the charge–discharge and cycle measurements. The 500 °C annealing film has the highest capacity retention rate of 78.2% at 100th cycles.     

Structural analysis and luminescent study of thin film zinc germanate doped with manganese

Thin films of zinc germanate doped with manganese (Zn₂GeO₄:Mn) were fabricated by radio frequency magnetron sputtering, and their structural characteristics and luminescent properties were studied. The Zn₂GeO₄:Mn films exhibited a pronounced absorption edge at around 271 nm and a high optical transparency in the visible wavelength region with a peak transmittance of 0.927 at 691 nm. While the as-deposited Zn₂GeO₄:Mn films had an amorphous structure, the annealed films possessed a rhombohedral polycrystalline structure with a random crystallographic orientation of grains. The broad-band photoluminescence (PL) emission was observed from the annealed Zn₂GeO₄:Mn films. The PL emission spectrum showed a peak maximum at around 537 nm in the green range, which was accounted for by the intrashell transition of 3d⁵ orbital electrons from the ⁴T₁ lowest excitation state to the ⁶A₁ ground state in the divalent manganese ions. Two discrete peaks were observed in the PL excitation spectrum at 256 and 296 nm, which are considered to be associated with the band-to-band absorption of the host and the sub-band absorption from defect states, respectively. The green cathodoluminescence (CL) emission was obtained from the annealed Zn₂GeO₄:Mn films with a peak centered at around 534 nm, analogous to the PL emission spectrum.     

Effect of annealing time on microstructure and morphology of thin films by sputtering deposition with (Ba<Subscript>0.3</Subscript>Sr<Subscript>0.7</Subscript>)(Zn<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript> target

The ceramic thin films have been fabricated by radio frequency (RF) magnetron sputtering technique on SiO₂ (110) substrates with (Ba_0.3Sr_0.7)(Zn_1/3Nb_2/3)O₃ target, and then the thin films were annealed at 1,150 °C for different times at O₂ atmosphere. The microstructure and morphology of the thin films were investigated as a function of the annealing times using the X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, and atomic force microscopy techniques. The results show that the microstructure, morphology, and crystallinity of the thin films can be affected by the annealing times significantly. The main phases of the samples are indexed to be Ba_0.5Sr_0.5Nb₂O₆ and Ba_0.27Sr_0.75Nb₂O_5.78, which are different from component of the (Ba_0.3Sr_0.7)(Zn_1/3Nb_2/3)O₃ target due to the volatilization of ZnO. The crystalline quality of the thin films decreases when the annealing time is shorter or longer than 30 min, and the roughness and grain size of the thin films reaches a maximum value when the annealing time is 30 min.     

Synthesis and optical characterization of n-ZnO and p-Cu2ZnSnS4 nanocrystalline thin films for low cost solar cells

High quality ZnO/Cu₂ZnSnS₄ thin films as a window/absorber layers were successfully synthesized via spin coating the sol-gel precursor of each composition without using any vacuum facilities. In this study, the impact of annealing temperature (400 °C, 3 h) on the ZnO window layer and different thickness (3 and 5 layers) of the Cu₂ZnSnS₄ (CZTS) absorber layer were investigated. X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDX), scanning electron microscope (SEM) and UV–vis–NIR spectroscopy were used for the structural, compositional, morphological and optical absorption analysis of each layer. ZnO exhibits wurtzite hexagonal crystal structure with particle size equals to 8.60 and 28.59 nm for fresh and annealed films, respectively. Micro-strain and dislocations density decreased with the annealing temperature. X-ray diffraction patterns for CZTS films show small peak at (112) according to the kesterite structure with particle size in nano-scale for the two thicknesses. ZnO films demonstrated direct optical band gap of 3.23 and 3.21 eV for fresh and annealed films, respectively. CZTS films (3 and 5 layers) also have direct optical band with optimum value (1.51 eV) for thickness of 5 layers. The J-V characteristics of the CZTS-based thin film solar cells (CZTS/ZnO/ZnO:Ag) were measured under air mass AM 1.5 and 100 mW/cm² illumination. The values of the short circuit current (J_sc), open circuit voltage (V_oc) and fill factor (FF) also have been obtained.     

Annealing Induced Enhancement in Magnetic Properties of Co0.5Zn0.5Fe2O4 Nanoparticles

In this paper, cobalt zinc ferrite (Co_0.5Zn_0.5Fe₂O₄) nanoparticles (NPs) have been prepared using chemical co-precipitation method. In order to investigate the annealing induced effects on their various physical properties, the prepared samples have been annealed at 500 °C, 650 °C and 1000 °C and then compared with as-prepared sample. X-ray diffraction (XRD) patterns of as-prepared and annealed samples at various temperatures exhibit single phase spinel structure. Enhancement in crystallinity and crystallite size is observed with the increase in annealing temperature. The annealing has also greatly influence the morphology and grain size of prepared NPs. The Co_0.5Zn_0.5Fe₂O₄ NPs have shown remarkable enhancement in magnetic moment with increase in annealing temperature. The bandgap energies of Co_0.5Zn_0.5Fe₂O₄ NPs have been measured via UV Spectrometer and observed to decrease with annealing temperature. FTIR spectra of the samples reveal the presence of both high frequency and low-frequency bands due to tetrahedral and octahedral sites, which corroborate well with the XRD results. The observed characteristics of cobalt zinc ferrite NPs as a function of annealing temperature are the rising contender for many data storage and nanodevice applications. Finally, the genotoxicity of prepared nanoferrites has been checked via comet assay.     

Effect of annealing temperature on structural,optical and humidity sensing properties of indium tin oxide (ITO) thin films

Tin doped indium oxide (ITO) thin films were prepared by sol–gel spin coating method with In (NO₃)·3H₂O and SnCl₄·5H₂O as indium and tin sources, respectively. The as deposited samples were annealed at various temperature such as, 300, 400, 500 and 600?°C for 2 h in ambient atmosphere. The grown ITO thin films are polycrystalline in nature with cubic structure of In₂O₃ with the space group La3 and the results are in good agreement with the standard JCPDS data (card no#06-0416). In addition crystalline size increases with increasing annealing temperature from 25 to 55 nm. Polycrystalline with uniform smooth surface was observed by SEM micrographs. The optical band gap energy was found to be decreased from 3.85 to 3.23 eV as the annealing temperature is increased from 300 to 600?°C. The humidity sensing performance (high sensitivity and fast response time) was significantly improved for 600?°C thin films samples, which is probably due to smaller energy band gap and physisorption between the water molecules and the surface of the thin films. The films were further characterized by PL and EDS analysis. The effect of temperature on humidity sensing mechanism of ITO thin films is also discussed.     

Phase transformation behavior of zinc metastannates obtained by aqueous precipitation at different temperatures

Phase transformation studies in ZnO–SnO₂ system from zinc metastannate (ZnSnO₃) to zinc orthostannate (Zn₂SnO₄) with annealing temperature are reported. Non-centrosymmetric oxides show unique symmetry dependent and spontaneous polarization properties, which are technologically important. ZnSnO₃ particles were synthesized by a simple aqueous synthesis at low temperatures designed with the assistance of potential–pH diagrams. ZnSnO₃ particles synthesized at 4 °C are more porous losing the ilmenite structure upon annealing at 200 °C, while the other samples prepared at higher temperatures (25–65 °C) becomes amorphous at 300 °C. The phase transformation into the inverse spinel orthostannate phase occurs around 750 °C in all the samples.     

The effect of annealing temperature on the properties of ZnO films with preferential nonpolar plane orientation by SSCVD

The effect of annealing temperature on the structural morphology and optical properties of preferential nonpolar plane orientated ZnO thin films on Si (100) substrates by single source chemical vapor deposition (SSCVD) was investigated. The structural and morphological properties of the films were characterized by X-ray diffraction (XRD) and atomic force microscope (AFM) measurements respectively. All the ZnO films annealed at the selected temperatures (500–800 °C) exhibiting a–b axis orientation, but with preferential nonpolar (100) plane orientation. It is found that the intensity of the (100) peak depends strongly on the annealing temperature, while that of (101) peak shows a variation in a very small scale. The surface morphology demonstrates that the film is of the uniform grains except for that annealed at 800 °C, for the aggregation of the ZnO particles occurred. The film shows a superior smooth surface annealed at 600 and 700 °C in comparison with other thermal annealed. It is also found from the photoluminescence(PL) measurements that the film annealed at 700 °C exhibits the lowest deep-level emission(DLE). However, the intensity of the near band edge emissions (NBE) and DLE show a wavelike variation, which are consistent to the variation of the intensity of (100) peak in the XRD results.     

Aerosol assisted chemical vapour deposition of germanium thin films using organogermanium carboxylates as precursors and formation of germania films

Diethyl germanium bis-picolinate, [Et₂Ge(O₂CC₅H₄N)₂], and trimethyl germanium quinaldate, [Me₃Ge(O₂CC₉H₆N)], have been used as precursors for deposition of thin films of germanium by aerosol assisted chemical vapour deposition (AACVD). The thermogravimetric analysis revealed complete volatilization of complexes under nitrogen atmosphere. Germanium thin films were deposited on silicon wafers at 700°C employing AACVD method. These films on oxidation under an oxygen atmosphere at 600°C yield GeO₂. Both Ge and GeO₂ films were characterized by XRD, SEM and EDS measurements. Their electrical properties were assessed by current?Cvoltage (I?CV) characterization.