Substrate temperature influence on the properties of nanostructured ZnO transparent ultrathin films grown by PLD

Zinc oxide films of 40 nm thickness have been deposited on glass substrates by pulsed laser deposition using an excimer XeCl laser (308 nm) at different substrate temperatures ranging from room temperature to 650 °C. Surface investigations carried out by using atomic force microscopy have shown a strong influence of temperature on the films surface topography. UV-VIS transmittance measurements have shown that our ZnO films are highly transparent in the visible wavelength region, having an average transmittance of ∼90%. The optical band gap of the films was found to be 3.26 eV, which is lower than the theoretical value of 3.37 eV. Besides the normal absorption edge related to the transition between the valence and the conduction band, an additional absorption band was also recorded in the wavelength region around 364 nm (∼3.4 eV). This additional absorption band may be due to excitonic, impurity, and/or quantum size effects. Photoreduction/oxidation in ozone of the ZnO films lead to larger conductivity changes for higher deposition temperature. In conclusion, the ozone sensing characteristics as well as the optical properties of the ZnO thin films deposited by pulsed laser deposition are strongly influenced by the substrate temperature during growth. The sensitivity of the films towards ozone might be enhanced significantly by the control of the films deposition parameters and surface characteristics.     

The effect of heat treatment on the physical properties of sol-gel derived ZnO thin films

Zinc oxide (ZnO) thin films were deposited on microscope glass substrates by sol-gel spin coating method. Zinc acetate (ZnAc) dehydrate was used as the starting salt material source. A homogeneous and stable solution was prepared by dissolving ZnAc in the solution of monoethanolamine (MEA). ZnO thin films were obtained after preheating the spin coated thin films at 250 °C for 5 min after each coating. The films, after the deposition of the eighth layer, were annealed in air at temperatures of 300 °C, 400 °C and 500 °C for 1 h. The effect of thermal annealing in air on the physical properties of the sol-gel derived ZnO thin films are studied. The powder and its thin film were characterized by X-ray diffractometer (XRD) method. XRD analysis revealed that the annealed ZnO thin films consist of single phase ZnO with wurtzite structure (JCPDS 36-1451) and show the c-axis grain orientation. Increasing annealing temperature increased the c-axis orientation and the crystallite size of the film. The annealed films are highly transparent with average transmission exceeding 80% in the visible range (400-700 nm). The measured optical band gap values of the ZnO thin films were between 3.26 eV and 3.28 eV, which were in the range of band gap values of intrinsic ZnO (3.2-3.3 eV). SEM analysis of annealed thin films has shown a completely different surface morphology behavior.     

Structural, electrical and optical properties of Gd doped and undoped ZnO:Al (ZAO) thin films prepared by RF magnetron sputtering

The influence of the gadolinium doping on the structural features and opto-electrical properties of ZnO:Al (ZAO) films deposited by radio frequency (RF) magnetron sputtering method onto glass substrates was investigated. X-ray analysis showed that the films were polycrystalline fitting well with a hexagonal wurtzite structure and have preferred orientation in [0 0 2] direction. The Gd doped ZAO film with a thickness of 140 nm showed a high visible region transmittance of 90%. The optical band gap was found to be 3.38 eV for pure ZnO film and 3.58 eV for ZAO films while a drop in optical band gap of ZAO film was observed by Gd doping. The lowest resistivities of 8.4 × 10⁻³ and 10.6 × 10⁻³ Ω cm were observed for Gd doped and undoped ZAO films, respectively, which were deposited at room temperature and annealed at 150 °C.     

Wide band gap Cd0.83Mg0.15Al0.02O thin films by pulsed laser deposition

Magnesium and aluminum doped CdO thin films were deposited on quartz substrate using pulsed laser deposition technique. Magnesium is used to widen the band gap and aluminum is used to increase carrier concentration of CdO films. The effect of growth temperature on structural, optical, and electrical properties was studied. These films are crystalline in nature and their preferred orientation depends on growth temperature. These films are highly transparent (∼86%) in visible region. The band gap of the films varies from 3.1 eV to 3.4 eV. The electrical conductivity and carrier concentration were found to decrease with increase in growth temperature.     

Effect of indium doping in CdO thin films prepared by spray pyrolysis technique

Preparation of transparent and conducting indium doped CdO thin films by spray pyrolysis on glass substrate is reported for various concentration of indium (2-8 wt%) in the spray solution. The electrical, optical and structural properties of indium doped CdO films were investigated using different techniques such as Hall measurement, optical transmission, X-ray diffraction and scanning electron microscope. X-ray analysis shows that the undoped CdO films are preferentially orientated along (2 0 0) crystallographic direction. Increase of indium doping concentration increases the films packing density and reorient the crystallites along (1 1 1) plane. A minimum resistivity of 4.843×10⁻⁴ Ω cm and carrier concentration of 3.73×10²⁰ cm⁻³ with high transmittance in the range 300-1100 nm were achieved for 6 wt% indium doping. The band gap value increases with doping concentration and reaches a maximum of 2.72 eV for 6 wt% indium doping from 2.36 eV of that of undoped film. The minimum resistivity achieved in the present study is found to be the lowest among the reported values for In-doped CdO films prepared by spray pyrolysis method.     

Highly conducting and transparent Ti-doped CdO films by pulsed laser deposition

Titanium-doped cadmium oxide thin films were deposited on quartz substrate by pulsed laser deposition technique. The effect of substrate temperature on structural, optical and electrical properties was studied. The films grown at high temperature show (2 0 0) preferred orientation, while films grown at low temperature have both (1 1 1) and (2 0 0) orientation. These films are highly transparent (63-79%) in visible region, and transmittance of the films depends on growth temperature. The band gap of the films varies from 2.70 eV to 2.84 eV for various temperatures. It is observed that resistivity increases with growth temperature after attaining minimum at 150 °C, while carrier concentration continuously decreases with temperature. The low resistivity, high transmittance and wide band gap titanium-doped CdO films could be an excellent candidate for future optoelectronic and photovoltaic applications.     

Fabrication and vacuum annealing of transparent conductive Ga-doped Zn0.9Mg0.1O thin films prepared by pulsed laser deposition technique

In this study, highly transparent conductive Ga-doped Zn_0.9Mg_0.1O (ZMO:Ga) thin films have been deposited on glass substrates by pulsed laser deposition (PLD) technique. The effects of substrate temperature and post-deposition vacuum annealing on structural, electrical and optical properties of ZMO:Ga thin films were investigated. The properties of the films have been characterized through Hall effect, double beam spectrophotometer and X-ray diffraction. The experimental results show that the electrical resistivity of film deposited at 200 °C is 8.12 × 10⁻⁴ Ω cm, and can be further decreased to 4.74 × 10⁻⁴ Ω cm with post-deposition annealing at 400 °C for 2 h under 3 × 10⁻³ Pa. In the meantime, its band gap energy can be increased to 3.90 eV from 3.83 eV. The annealing process leads to improvement of (0 0 2) orientation, wider band gap, increased carrier concentration and blue-shift of absorption edge in the transmission spectra of ZMO:Ga thin films.     

Dependence of film thickness on the structural and optical properties of ZnO thin films

ZnO thin films are prepared on glass substrates by pulsed filtered cathodic vacuum arc deposition (PFCVAD) at room temperature. Optical parameters such as optical transmittance, reflectance, band tail, dielectric coefficient, refractive index, energy band gap have been studied, discussed and correlated to the changes with film thickness. Kramers-Kronig and dispersion relations were employed to determine the complex refractive index and dielectric constants using reflection data in the ultraviolet-visible-near infrared regions. Films with optical transmittance above 90% in the visible range were prepared at pressure of 6.5 × 10⁻⁴ Torr. XRD analysis revealed that all films had a strong ZnO (0 0 2) peak, indicating c-axis orientation. The crystal grain size increased from 14.97 nm to 22.53 nm as the film thickness increased from 139 nm to 427 nm, however no significant change was observed in interplanar distance and crystal lattice constant. Optical energy gap decreased from 3.21 eV to 3.19 eV with increasing the thickness. The transmission in UV region decreased with the increase of film thickness. The refractive index, Urbach tail and real part of complex dielectric constant decreased as the film thickness increased. Oscillator energy of as-deposited films increased from 3.49 eV to 4.78 eV as the thickness increased.     

A simplified reactive thermal evaporation method for indium tin oxide electrodes

Indium tin oxide (ITO) films approximately 120 nm thick were deposited onto unheated glass substrates by using reactive thermal evaporation (RTE) and in situ post-evaporation annealing in oxygen. We show that this simplified method can be used to produce high quality ITO thin films with low electrical resistivity (10⁻³ Ω cm) and high transmittance (approximately 80% at 550 nm). The refractive index is approximately 2.0 and the direct optical band gap of the films (above 3.0 eV) is in good agreement with previously reported values. Since this deposition method does not require heating the substrates or furnace annealing at high temperatures, it can be advantageous when it is necessary to decrease the thermal budget on underlying devices or layers.     

Band gap energy and bowing parameter of In-rich InAlN films grown by magnetron sputtering

The crystal structure, band gap energy and bowing parameter of In-rich In_xAl_1−xN (0.7 < x < 1.0) films grown by magnetron sputtering were investigated. Band gap energies of In_xAl_1−xN films were obtained from absorption spectra. Band gap tailing due to compositional fluctuation in the films was observed. The band gap of the as-grown InN measured by optical absorption method is 1.34 eV, which is larger than the reported 0.7 eV for pure InN prepared by molecular beam epitaxy (MBE) method. This could be explained by the Burstein-Moss effect under carrier concentration of 10²⁰ cm⁻³ of our sputtered films. The bowing parameter of 3.68 eV is obtained for our In_xAl_1−xN film which is consistent with the previous experimental reports and theoretical calculations.     

Laser synthesis of nanostructures based on transition metal oxides

Nanostructures based on iron oxides in the form of thin films were synthesized while laser chemical vapor deposition (LCVD) of elements from iron carbonyl vapors (Fe(CO)₅) under the action of Ar⁺ laser radiation (λ_L = 488 nm) on the Si substrate surface with power density about 10² W/cm² and vapor pressure 666 Pa. Analysis of surface morphology and relief of the deposited films was carried out with scanning electron microscopy (SEM) and atomic force microscopy (AFM). This analysis demonstrated their cluster structure with average size no more than 100 nm. It was found out that the thicker the deposited film, the larger sizes of clusters with more oxides of higher oxidized phases were formed. The film thickness (d) was 10 and 28 nm. The deposited films exhibited semiconductor properties in the range 170-340 K which were stipulated by oxide content with different oxidized phases. The width of the band gap E_g depends on oxide content in the deposited film and was varied in the range 0.30-0.64 eV at an electrical field of 1.6 × 10³ V/m. The band gap E_g was varied in the range 0.46-0.58 eV at an electrical field of 45 V/m. The band gap which is stipulated by impurities in iron oxides E_i was varied in the range 0.009-0.026 eV at an electrical field of 1.6 × 10³ V/m and was varied in the range 0-0.16 eV at an electrical field 45 V/m. These narrow band gap semiconductor thin films displayed of the quantum dimensional effect.     

Chemical spray pyrolysis deposition and characterization of p-type CuCr1−xMgxO2 transparent oxide semiconductor thin films

A chemical spray pyrolysis technique for deposition of p-type Mg-doped CuCrO₂ transparent oxide semiconductor thin films using metaloorganic precursors is described. As-deposited films contain mixed spinel CuCr₂O₄ and delafossite CuCrO₂ structural phases. Reduction in spinel CuCr₂O₄ fraction and formation of highly crystalline films with single phase delafossite CuCrO₂ structure is realized by annealing at temperatures ?700 °C in argon. A mechanism of synthesis of CuCrO₂ films involving precursor decomposition, oxidation and reaction between constituent oxides in the spray deposition process is presented. Post-annealed CuCr_0.93Mg_0.07O₂ thin films show high (?80%) visible transmittance and sharp absorption at band gap energy with direct and indirect optical band gaps 3.11 and 2.58 eV, respectively. Lower (∼450 °C) substrate temperature formed films are amorphous and yield lower direct (2.96 eV) and indirect (2.23 eV) band gaps after crystallization. Electrical conductivity of CuCr_0.93 Mg_0.07O₂ thin films ranged 0.6-1 S cm⁻¹ and hole concentration ∼2×10¹⁹ cm⁻³ determined from Seebeck analysis. Temperature dependence of conductivity exhibit activation energies ∼0.11 eV in 300-470 K and ∼0.23 eV in ?470 K region ascribed to activated conduction and grain boundary trap assisted conduction, respectively. Heterojunction diodes of the structure Au/n-(ZnO)/p-(CuCr_0.93Mg_0.07O₂)/SnO₂ (TCO) were fabricated which show potential for transparent wide band gap junction device.     

Influence of films thickness and structure on the photo-response of ZnO films

ZnO thin films were grown using Successive Ionic Layer Adsorption and Reaction (SILAR) method on glass substrates at room temperature. Annealing temperatures and film thickness effect on the structural, morphological, optical and electrical properties of the films were studied. For this as-deposited films were annealed at 200, 300, 400 and 500 °C for 30 min in oxygen atmosphere. The X-ray diffraction (XRD) and scanning electron microscopy (SEM) studies showed that the films are covered well with glass substrates and have good polycrystalline structure and crystalline levels. The film thickness effect on band gap values was investigated and band gap values were found to be within the range of 3.49-3.19 eV. The annealing temperature and light effect on electrical properties of the films were investigated and it was found that the current increased with increasing light intensity. The resistivity values were found as 10⁵ Ω-cm for as-deposited films from electrical measurements. The resistivity decreased decuple with annealing temperature and decreased centuple with light emission for annealed films.     

Deposition and characterization of transparent and conductive sprayed ZnO:B thin films

Highly transparent and conductive Boron doped zinc oxide (ZnO:B) thin films were deposited using chemical spray pyrolysis (CSP) technique on glass substrate. The effect of variation of boron doping concentration in reducing solution on film properties was investigated. Low angle X-ray analysis showed that the films were polycrystalline fitting well with a hexagonal wurtzite structure and have preferred orientation in [002] direction. The films with resistivity 2.54×10⁻³ Ω-cm and optical transmittance >90% were obtained at optimized boron doping concentration. The optical band gap of ZnO:B films was found ∼3.27 eV from the optical transmittance spectra for the as-deposited films. Due to their excellent optical and electrical properties, ZnO:B films are promising contender for their potential use as transparent window layer and electrodes in solar cells.     

Characterization of the laser ablation plasma used for the deposition of amorphous carbon

The plasma produced by laser ablation of a graphite target was studied by means of optical emission spectroscopy and a Langmuir planar probe. Laser ablation was performed using a Nd:YAG laser with emission at the fundamental line with pulse length of 28 ns. In this work, we report the behavior of the mean kinetic energy of plasma ions and the plasma density, as a function of the laser fluence (J/cm²), and the target to probe (substrate) distance. The characterized regimes were employed to deposit amorphous carbon at different values of kinetic energy of the ions and plasma density. The mean kinetic energy of the ions could be changed from 40 to 300 eV, and the plasma density could be varied from 1 × 10¹² to 7 × 10¹³ cm⁻³. The main emitting species were C⁺ (283.66, 290.6, 299.2 and 426.65 nm) and C⁺⁺ (406.89 and 418.66 nm) with the C⁺ (426.65 nm) being the most intense and that which persisted for the longest times. Different combinations of the plasma parameters yield amorphous carbon with different structures. Low levels (about 40 eV) of ion energy produce graphitic materials, while medium levels (about 200 eV) required the highest plasma densities in order to increase the CC sp³ bonding content and therefore the hardness of the films. The structure of the material was studied by means of Raman spectroscopy, and the hardness and elastic modulus by depth sensitive nanoindentation.     

Structural and optical properties of zinc nitride films prepared by rf magnetron sputtering

Zinc nitride films were prepared on quartz substrates by rf magnetron sputtering using pure zinc target in N₂-Ar plasma. X-ray diffraction (XRD) analysis indicates that the films just after deposition are polycrystalline with a cubic structure and a preferred orientation of (4 0 0). X-ray photoelectron spectroscopy (XPS) analysis also confirms the formation of N-Zn bonds and the substitution incorporation of oxygen for nitrogen on the surface of the films. The optical band gap is calculated from the transmittance spectra of films just after deposition, and a direct band gap of 1.01 ± 0.02 eV is obtained. Room temperature PL measurement is also performed to investigate the effect of defect on the band gap and quality of the zinc nitride films.     

Optical band gap of zinc nitride films prepared on quartz substrates from a zinc nitride target by reactive rf magnetron sputtering

Polycrystalline zinc nitride films have been synthesized onto quartz substrates from the zinc nitride target and the nitrogen working gas by reactive rf magnetron sputtering at room temperature. X-ray diffraction study indicates that polycrystalline zinc nitride films are of cubic structure with the lattice constant a = 0.979(1) nm and have preferred orientations with (3 2 1) and (4 4 2). Its absorption coefficients as well as the film thickness are calculated from the transmission spectra, which are measured with a double beam spectrophotometer. The optical band gap has been determined from the photon energy dependence of absorption coefficient, an indirect transition optical band gap of 2.12(3) eV has been obtained.     

Ion-induced secondary electron emission from ZnS thin films deposited by closed-spaced sublimation

ZnS thin films were deposited on soda lime glass and aluminum substrates by close-spaced sublimation technique. The change in composition, structural and optical properties of the films was investigated as a function of the substrate temperature. The deposited films were stoichiometric and crystalline in nature having cubic structure oriented only along (1 1 1) plane. The energy band gap of the films deposited at the substrate temperature of 150, 250 and 350 °C was 3.52, 3.58 and 3.63 eV respectively. These films were then bombarded with 2-10 keV energy pulsed Ar⁺ beam and their electron yield was determined from impinging ion and emitted electron currents. The electron yield of ZnS films was much high as compared to the metals. The electron yield of ZnS films increased with energy of the incident ion and got saturated at about 8 keV. The most important result of this study was that the electron yield of ZnS films having same composition was different. Monte Carlo simulations performed to interpret these experimental findings showed that the dissimilar electron yields of ZnS films is due to the combined effect of energy band gap, surface barrier potential and density of the films.     

Influence of temperature annealing on optical properties of SrTiO3/BaTiO3 multilayered films on indium tin oxide

We have prepared SrTiO₃/BaTiO₃ thin films with multilayered structures deposited on indium tin oxide (ITO) coated glass by a sol-gel deposition and heating at 300-650 °C. The optical properties were obtained by UV-vis spectroscopy. The films show a high transmittance (approximately 85%) in the visible region. The optical band gap of the films is tunable in the 3.64-4.19 eV range by varying the annealing temperature. An abrupt decrease towards the bulk band gap value is observed at annealing temperatures above 600 °C. The multilayered film annealed at 650 ° C exhibited the maximum refractive index of 2.09-1.91 in the 450-750 nm wavelength range. The XRD and AFM results indicate that the films annealed above 600 ° C are substantially more crystalline than the films prepared at lower temperatures which were used to change their optical band gap and complex refractive index to an extent that depended on the annealing temperature.     

Modifications in structural and optical properties of Mn-ion implanted CdS thin films

In this paper, we report on modifications in structural and optical properties of CdS thin films due to 190 keV Mn-ion implantation at 573 K. Mn-ion implantation induces disorder in the lattice, but does not lead to the formation of any secondary phase, either in the form of metallic clusters or impurity complexes. The optical band gap was found to decrease with increasing ion fluence. This is explained on the basis of band tailing due to the creation of localized energy states generated by structural disorder. Enhancement in the Raman scattering intensity has been attributed to the enhancement in the surface roughness due to increasing ion fluence. Mn-doped samples exhibit a new band in their photoluminescence spectra at 2.22 eV, which originates from the d-d (⁴T₁ → ⁶A₁) transition of tetrahedrally coordinated Mn²⁺ ions.