Highly conductive and transparent laser ablated nanostructured Al: ZnO thin films

Al doped ZnO thin films are prepared by pulsed laser deposition on quartz substrate at substrate temperature 873 K under a background oxygen pressure of 0.02 mbar. The films are systematically analyzed using X-ray diffraction, atomic force microscopy, micro-Raman spectroscopy, UV-vis spectroscopy, photoluminescence spectroscopy, z-scan and temperature-dependent electrical resistivity measurements in the temperature range 70-300 K. XRD patterns show that all the films are well crystallized with hexagonal wurtzite structure with preferred orientation along (0 0 2) plane. Particle size calculations based on XRD analysis show that all the films are nanocrystalline in nature with the size of the quantum dots ranging from 8 to 17 nm. The presence of high frequency E₂ mode and longitudinal optical A₁ (LO) modes in the Raman spectra suggest a hexagonal wurtzite structure for the films. AFM analysis reveals the agglomerated growth mode in the doped films and it reduces the nucleation barrier of ZnO by Al doping. The 1% Al doped ZnO film presents high transmittance of ∼75% in the visible and near infrared region and low dc electrical resistivity of 5.94 × 10⁻⁶ Ω m. PL spectra show emissions corresponding to the near band edge (NBE) ultra violet emission and deep level emission in the visible region. Nonlinear optical measurements using the z-scan technique shows optical limiting behavior for the 5% Al doped ZnO film.     

Growth characteristics and properties of ZnO:Ga thin films prepared by pulsed DC magnetron sputtering

Transparent conductive ZnO:Ga thin films were deposited on Corning 1737 glass substrate by pulsed direct current (DC) magnetron sputtering. The effects of process parameters, namely pulse frequency and film thickness on the structural and optoelectronic properties of ZnO:Ga thin films are evaluated. It shows that highly c-axis (0 0 2) oriented polycrystalline films with good visible transparency and electrical conductivity were prepared at a pulsed frequency of 10 kHz. Increasing the film thickness also enlarged the grain size and carrier mobility which will subsequently lead to the decrease in resistivity. In summary, ZnO:Ga thin film with the lowest electrical resistivity of 2.01 × 10⁻⁴ Ω cm was obtained at a pulse frequency of 10 kHz with 500 nm in thickness. The surface RMS (root mean square) roughness of the film is 2.9 nm with visible transmittance around 86% and optical band gap of 3.83 eV.     

Effect of substrate and annealing on the structural and optical properties of ZnO:Al films

ZnO:Al thin films with c-axis preferred orientation were deposited on glass and Si substrates using RF magnetron sputtering technique. The effect of substrate on the structural and optical properties of ZnO:Al films were investigated. The results showed a strong blue peak from glass-substrate ZnO:Al film whose intensity became weak when deposited on Si substrate. However, the full width at half maxima (FWHM) of the Si-substrate ZnO:Al (0 0 2) peaks decreased evidently and the grain size increased. Finally, we discussed the influence of annealing temperature on the structural and optical properties of Si-substrate ZnO:Al films. After annealing, the crystal quality of Si-substrate ZnO:Al thin films was markedly improved and the intensity of blue peak (∼445 nm) increased noticeably. This observation may indicate that the visible emission properties of the ZnO:Al films are dependent more on the film crystallinity than on the film stoichiometry.     

A comparative study on structural and optical properties of ZnO and Al-doped ZnO thin films obtained by ultrasonic spray method using different solvents

Transparent conducting ZnO and Al doped ZnO thin films were deposited on glass substrate by ultrasonic spray method. The thin films with concentration of 0.1 M were deposited at 350 °C with 2 min of deposition time. The effects of ethanol and methanol solution before and after doping on the structural, optical and electrical properties were examined. The DRX analyses indicated that ZnO films have nanocrystalline nature and hexagonal wurtzite structure with (1 0 0) and (0 0 2) preferential orientation corresponding to ZnO films resulting from methanol and ethanol solution, respectively. The crystallinity of the thin films improved with methanol solution after doping to (0 0 2) oriented. All films exhibit an average optical transparency about 90%, in the visible range. The band gaps values of ZnO thin films are increased after doping from 3.10 to 3.26 eV and 3.27 to 3.30 eV upon Al doping obtained by ethanol and methanol solution, respectively. The electrical conductivity increase from 7.5 to 15.2 (Ω cm)⁻¹ of undoped to Al doped ZnO thin films prepared by using ethanol solution. However, for the methanol solution; the electrical conductivity of the film is stabilized after doping.     

Electrical and optical properties of Ga doped zinc oxide thin films deposited at room temperature by continuous composition spread

Ga doped ZnO (GZO) thin films were deposited on glass substrates at room temperature by continuous composition spread (CCS) method. CCS is thin films growth method of various Ga_xZn_1−xO(GZO) thin film compositions on a substrate, and evaluating critical properties as a function position, which is directly related to material composition. Various compositions of Ga doped ZnO deposited at room temperature were explored to find excellent electrical and optical properties. Optimized GZO thin films with a low resistivity of 1.46 × 10⁻³ Ω cm and an average transmittance above 90% in the 550 nm wavelength region were able to be formed at an Ar pressure of 2.66 Pa and a room temperature. Also, optimized composition of the GZO thin film which had the lowest resistivity and high transmittance was found at 0.8 wt.% Ga₂O₃ doped in ZnO.     

Effect of substrate temperature on the structural and optical properties of ZnO and Al-doped ZnO thin films prepared by dc magnetron sputtering

ZnO and Al-doped ZnO(ZAO) thin films have been prepared on glass substrates by direct current (dc) magnetron sputtering from 99.99% pure Zn metallic and ZnO:3 wt%Al₂O₃ ceramic targets, the effects of substrate temperature on the crystallization behavior and optical properties of the films have been studied. It shows that the surface morphologies of ZAO films exhibit difference from that of ZnO films, while their preferential crystalline growth orientation revealed by X-ray diffraction remains always the (0 0 2). The optical transmittance and photoluminescence (PL) spectra of both ZnO and ZAO films are obviously influenced by the substrate temperature. All films exhibit a transmittance higher than 86% in the visible region, while the optical transmittance of ZAO films is slightly smaller than that of ZnO films. More significantly, Al-doping leads to a larger optical band gap (E_g) of the films. It is found from the PL measurement that near-band-edge (NBE) emission and deep-level (DL) emission are observed in pure ZnO thin films. However, when Al was doped into thin films, the DL emission of the thin films is depressed. As the substrate temperature increases, the peak of NBE emission has a blueshift to region of higher photon energy, which shows a trend similar to the E_g in optical transmittance measurement.     

Influence of Al-doping on the structure and optical properties of ZnO films

Al-doped ZnO (ZnO:Al) thin films with c-axis preferred orientation were deposited on glass substrates using the radio frequency reactive magnetron sputtering technique. The effect of Al concentrations on the microstructure and the luminescence properties of the ZnO:Al thin films were studied by atomic force microscopy (AFM), X-ray diffraction (XRD), and fluorescence spectrophotometer. The results showed that the crystallization of the films was promoted by appropriate Al concentrations; the photoluminescence spectra (PL) of the samples were measured at room temperature. Strong blue peak located at 437 nm (2.84 eV) and two weak green peaks located at about 492 nm (2.53 eV) and 524 nm (2.37 eV) were observed from the PL spectra of the four samples. The origin of these emissions was discussed. In addition, absorption and transmittance properties of the samples were researched by UV spectrophotometer; the UV absorption edge shifted to a shorter wavelength first as Al was incorporated, and then to a longer wavelength with the increasing Al concentrations. The optical band gaps calculated based on the quantum confinement model are in good agreement with the experimental values.     

Effects of the substrate and oxygen partial pressure on the microstructures and optical properties of Ti-doped ZnO thin films

Ti-doped ZnO (ZnO:Ti) thin films were deposited on the glass and Si substrates using radio frequency reactive magnetron sputtering. The effects of substrate on the microstructures and optical properties of ZnO:Ti thin films were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and a fluorescence spectrophotometer. The structural analyses of the films indicated that they were polycrystalline and had a hexagonal wurtzite structure on different substrates. When ZnO:Ti thin film was deposited on Si substrate, the film had a c-axis preferred orientation, while preferred orientation of ZnO:Ti thin film deposited on glass substrate changed towards (1 0 0). Finally, we discussed the influence of the oxygen partial pressures on the structural and optical properties of glass-substrate ZnO:Ti thin films. At a high ratio of O₂:Ar of 18:10 sccm, the intensity of (0 0 2) diffraction peak was stronger than that of (1 0 0) diffraction peak, which indicated that preferred orientation changed with the increase of O₂:Ar ratios. The average optical transmittance with over 93% in the visible range was obtained independent of the O₂:Ar ratio. The photoluminescence (PL) spectra measured at room temperature revealed four main emission peaks located at 428, 444, 476 and 527 nm. Intense blue-green luminescence was obtained from the sample deposited at a ratio of O₂:Ar of 14:10 sccm. The results showed that the oxygen partial pressures had an important influence for PL spectra and the origin of these emissions was discussed.     

Nano-star formation in Al-doped ZnO thin film deposited by dip-dry method and its characterization using atomic force microscopy, electron probe microscopy, photoluminescence and laser Raman spectroscopy

Zinc oxide doped with Al (AZO) thin films were prepared on borosilicate glass substrates by dip and dry technique using sodium zincate bath. Effects of doping on the structural and optical properties of ZnO film were investigated by XRD, EPMA, AFM, optical transmittance, PL and Raman spectroscopy. The band gap for ZnO:Al (5.0 at. wt.%) film was found to be 3.29 eV compared with 3.25 eV band gap for pure ZnO film. Doping with Al introduces aggregation of crystallites to form micro-size clusters affecting the smoothness of the film surface. Al³⁺ ion was found to promote chemisorption of oxygen into the film, which in turn affects the roughness of the sample. Six photoluminescence bands were observed at 390, 419, 449, 480, 525 and 574 nm in the emission spectra. Excitation spectra of ZnO film showed bands at 200, 217, 232 and 328 nm, whereas bands at 200, 235, 257 and 267 nm were observed for ZnO:Al film. On the basis of transitions from conduction band or deep donors (CB, Zn_i or V_OZn_i) to valence band and/or deep acceptor states (VB, V_Zn or O_i or O_Zn), a tentative model has been proposed to explain the PL spectra. Doping with Al³⁺ ions reduced the polar character of the film. This has been confirmed from laser Raman studies.     

Effect of doping on structural,optical and electrical properties of nanostructure ZnO films deposited onto a-Si:H/Si heterojunction

We investigated the structural; optical and electrical properties of ZnO thin films as the n-type semiconductor for silicon a-Si:H/Si heterojunction photodiodes. The ZnO film forms the front contact of the super-strata solar cell and has to exhibit good electrical (high conductivity) and optical (high transmittance) properties. In this paper we focused our attention on the influence of doping on device performance. The results show that the X-ray diffraction (XRD) spectra revealed a preferred orientation of the crystallites along c-axis. SEM images show that all films display a granular, polycrystalline morphology and the ZnO:Al exhibits a better grain uniformity. The transmittance of the doped films was found to be higher when compared to undoped ZnO. A low resistivity of the order of 2.8 × 10⁻⁴ Ω cm is obtained for ZnO:Al using 0.4 M concentration of zinc acetate. The photoluminescence (PL) spectra exhibit a blue band with two peaks centered at 442 nm (2.80 eV) and 490 nm (2.53 eV). It is noted that after doping the ZnO films a shift of the band by 22 nm (0.15 eV) is recorded and a high luminescence occurs when using Al as a dopant. Dark I–V curves of ZnO/a-Si:H/Si structure showed large difference, which means there is a kind of barrier to current flow between ZnO and a-Si:H layer. Doping films was applied and the turn-on voltages are around 0.6 V. Under reverse bias, the current of the ZnO/a-Si:H/Si heterojunction is larger than that of ZnO:Al/a-Si:H/Si. The improvement with ZnO:Al is attributed to a higher number of generated carriers in the nanostructure (due to the higher transmittance and a higher luminescence) that increases the probability of collisions.     

Excimer laser processing of ZnO thin films prepared by the sol-gel process

ZnO thin films were prepared on soda-lime glass from a single spin-coating deposition of a sol-gel prepared with anhydrous zinc acetate [Zn(C₂H₃O₂)₂], monoethanolamine [H₂NC₂H₄OH] and isopropanol. The deposited films were dried at 50 and 300 °C. X-ray analysis showed that the films were amorphous. Laser annealing was performed using an excimer laser. The laser pulse repetition rate was 25 Hz with a pulse energy of 5.9 mJ, giving a fluence of 225 mJ cm⁻² on the ZnO film. Typically, five laser pulses per unit area of the film were used. After laser processing, the hexagonal wurtzite phase of zinc oxide was observed from X-ray diffraction pattern analysis. The thin films had a transparency of greater than 70% in the visible region. The optical band-gap energy was 3.454 eV. Scanning electron microscopy and profilometry analysis highlighted the change in morphology that occurred as a result of laser processing. This comparative study shows that our sol-gel processing route differs significantly from ZnO sol-gel films prepared by conventional furnace annealing which requires temperatures above 450 °C for the formation of crystalline ZnO.     

Characterisation of porous doped ZnO thin films deposited by spray pyrolysis technique

Al or Sn doped ZnO films were deposited by spray pyrolysis using aqueous solutions. The films were deposited on either indium tin oxide coated or bare glass substrates. ZnCl₂, AlCl₃ and SnCl₂ were used as precursors. The effect of ZnCl₂ molar concentration (0.1-0.3 M) and doping percentage (2-4% AlCl₃ or SnCl₂) have been investigated. The main goal of this work being to grow porous ZnO thin films, small temperature substrates (200-300 °C) have been used during the spray pyrolysis deposition. It is shown that, if the X-ray diffraction patterns correspond to ZnO, the films deposited onto bare glass substrate are only partly crystallized while those deposited onto ITO coated glass substrate exhibit better crystallization. The homogeneity of the films decreases when the molar concentration of the precursor increases, while the grain size and the porosity decrease when the Al doping increases. The optical study shows that band tails are present in the absorption spectrum of the films deposited onto bare glass substrate, which is typical of disordered materials. Even after annealing 4 h at 400 °C, the longitudinal resistivity of the films is quite high. This result is attributed to the grain boundary effect and the porosity of the films. Effectively, the presence of an important reflection in the IR region in samples annealed testifies of a high free-carriers density in the ZnO crystallites. Finally it is shown that when deposited in the same electrochemical conditions, the transmission of a polymer film onto the rough sprayed ZnO is smaller than that onto smooth sputtered ZnO.     

Photoluminescence, FTIR and X-ray diffraction studies on undoped and Al-doped ZnO thin films grown on polycrystalline α-alumina substrates by ultrasonic spray pyrolysis

Undoped and aluminum-doped zinc oxide (ZnO) thin films have been grown on polycrystalline α-alumina substrates by ultrasonic spray pyrolysis (USP) technique using zinc acetate dihydrate and aluminum chloride hexahydrate (Al source) dissolved in methanol, ethanol and deionized water. A number of techniques, including X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, and photoluminescence (PL) were used to characterize the obtained ZnO thin films. It was seen that the orientation changed with increase in substrate temperature. During the ZnO deposition Zn source reacted with polycrystalline α-Al₂O₃ substrate to form an intermediate ZnAl₂O₄ spinel layer. It has been interestingly found that the intensity of green emission at 2.48 eV remarkably increased when the obtained ZnO:Al films were deposited at 380 °C. The FTIR absorbance intensity of spectroscopic band at 447±6 cm⁻¹ is very sensitive to oxygen sublattice disorder resulting from non-stoichiometry, which is consistent with the result of PL characterization.     

Transparent nano composite PVA–TiO2 and PMMA–TiO2 thin films: Optical and dielectric properties

Transparent nano composite PVA–TiO₂ and PMMA–TiO₂ thin films were prepared by an easy and cost effective dip coating method. Al/PVA–TiO₂/Al and Al/PMMA–TiO₂/Al sandwich structures were prepared to study the dielectric behavior. The presence of metal–oxide (Ti–O) bond in the prepared films was confirmed by Fourier transform infrared spectroscopy. X-ray diffraction pattern indicated that the prepared films were predominantly amorphous in nature. Scanning electron micrographs showed cluster of TiO₂ nanoparticles distributed over the film surface and also there were no cracks and pin holes on the surface. The transmittance of the films was above 80% in the visible region and the optical band gap was estimated to be about 3.77 eV and 3.78 eV respectively for PVA–TiO₂ and PMMA–TiO₂ films by using Tauc's plot. The determined refractive index (n) values were between 1.6 and 2.3. High value of dielectric constant (?′ = 24.6 and ?′ = 26.8) was obtained for the prepared composite films. The conduction in the composite films was found to be due to electrons. The observed amorphous structure, good optical properties and dielectric behavior of the prepared nano composite thin films indicated that these films could be used in opto-electronic devices and in thin film transistors.     

Structural and optical characteristics of spin-coated ZnO thin films

Zinc oxide (ZnO) thin films were deposited onto glass substrates by spin-coating method, from a precursor solution containing zinc acetate, ethanol and ammonium hydroxide. After deposition, the films were heated at a temperature of 100 °C in order to remove unwanted materials. Finally, the films were annealed at 500 °C for complete oxidation. X-ray diffraction showed that ZnO films were polycrystalline and have a hexagonal (wurtzite) structure. The crystallites are preferentially oriented with (0 0 2) planes parallel to the substrate surface. The films have a high transparency (more than 75%) in the spectral range from 450 nm to 1300 nm. The analysis of absorption spectra shows the direct nature of band-to-band transitions. The optical bandgap energy ranges between 3.15 eV and 3.25 eV.Some correlations between the processing parameters (spinning speed, temperature of post deposition heat treatment) and structure and optical characteristics of the respective thin films were established.     

Characterization of ZnO-SnO2 thin film composites prepared by pulsed laser deposition

Thin films of ZnO-SnO₂ composites have been deposited on Si(1 0 0) and glass substrates at 500 °C by pulsed laser ablation using different composite targets with ZnO amount varying between 1 and 50 wt%. The effect of increasing ZnO-content on electrical, optical and structural properties of the ZnO-SnO₂ films has been investigated. X-ray diffraction analysis indicates that the as-deposited ZnO-SnO₂ films can be both crystalline (for ZnO <1 wt%) and amorphous (for ZnO ≥ 10 wt%) in nature. Atomic force microscopy studies of the as-prepared composite films indicate that the surfaces are fairly smooth with rms roughness varying between 3.07 and 2.04 nm. The average optical transmittance of the as-deposited films in the visible range (400-800 nm), decreases from 90% to 72% for increasing ZnO concentration in the film. The band gap energy (E_g) seems to depend on the amount of ZnO addition, with the maximum obtained at 1 wt% ZnO. Assuming that the interband electron transition is direct, the optical band gap has been found to be in the range 3.24-3.69 eV for as-deposited composite films. The lowest electrical resistivity of 7.6 × 10⁻³ Ω cm has been achieved with the 25 wt% ZnO composite film deposited at 500 °C. The photoluminescence spectrum of the composite films shows a decrease in PL intensity with increasing ZnO concentration.     

Preparation and characterization of iron oxide thin films by spray pyrolysis using methanolic and ethanolic solutions

Iron oxide thin films have been obtained by spray pyrolysis using 100% methanolic and ethanolic solutions of iron tri-chloride. The films were deposited onto ITO-coated glass substrates. The preparative conditions have been optimized to obtain compact, pin-hole-free and smooth thin films which are adherent to the substrate. The structural, morphological and compositional characterizations have been carried out by X-ray diffraction, scanning electron microscopy and energy dispersive X-ray analysis. The films deposited using ethanolic solution results into pure hematite; α-Fe₂O₃ thin films, however, films deposited using methanolic solution consists of hematite and maghemite-c phases of iron oxide. The films are nanocrystalline with particle size of 30-40 nm. The optical absorbance of the film was of the order of 10⁵ cm⁻¹. The optical band gap of films was found to be 2.26 and 2.20 eV for the films deposited using methanolic and ethanolic solutions, respectively.     

Influence of air annealing on the structural, morphological, optical and electrical properties of chemically deposited ZnSe thin films

Zinc selenide nanocrystalline thin films are grown onto amorphous glass substrate from an aqueous alkaline medium, using chemical bath deposition (CBD) method. The ZnSe thin films are annealed in air for 4 h at various temperatures and characterized by structural, morphological, optical and electrical properties. The as-deposited ZnSe film grew with nanocrystalline cubic phase alongwith some amorphous phase present in it. After annealing metastable nanocrystalline cubic phase was transformed into stable polycrystalline hexagonal phase with partial conversion of ZnSe into ZnO. The optical band gap, E_g, of as-deposited film is 2.85 eV and electrical resistivity of the order of 10⁶-10⁷ Ω cm. Depending upon annealing temperature, decrease up to 0.15 eV and 10² Ω cm were observed in the optical band gap, E_g, and electrical resistivity, respectively.     

Pure UV photoluminescence from ZnO thin film by thermal retardation and using an amorphous SiO2 buffer layer

ZnO/SiO₂ thin films were fabricated on Si substrates by E-beam evaporation with thermal retardation. The as-prepared films were annealed for 2 h every 100 °C in the temperature range 400-800 °C under ambient air. The structural and optical properties were investigated by X-ray diffraction (XRD), atomic force microscopy (AFM) and photoluminescence (PL). The XRD analysis indicated that all ZnO thin films had a highly preferred orientation with the c-axis perpendicular to the substrate. From AFM images (AFM scan size is 1 μm×1 μm), the RMS roughnesses of the films were 3.82, 5.18, 3.65, 3.40 and 13.2 nm, respectively. PL measurements indicated that UV luminescence at only 374 nm was observed for all samples. The optical quality of the ZnO film was increased by thermal retardation and by using an amorphous SiO₂ buffer layer.     

Influence of Al concentration on electrical, structural and optical properties of Al-As codoped p-ZnO thin films

We report the influence of Al concentration on electrical, structural, optical and morphological properties of Al-As codoped p-ZnO thin films using RF magnetron sputtering. Al-As codoped p-ZnO films with different Al concentrations were fabricated using As back diffusion from the GaAs substrate and sputtering Al₂O₃ mixed ZnO targets (1, 2 and 4 at%). The grown films were investigated by Hall effect measurement, X-ray diffraction (XRD), electron probe microanalysis (EPMA), energy dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), photoluminescence (PL) and atomic force microscopy (AFM) to study the electrical, structural, optical and morphological properties of the films. From the XRD, it was observed that both full-width at half-maximum (FWHM) and c-axis lattice constant have similar trends with respect to Al concentration. Hall measurements showed that the hole concentration increases as the Al concentration increases from 10¹⁵ to 10²⁰ cm⁻³. The increase in hole concentration upon codoping was supported by the red shift in the near-band-edge (NBE) emission observed from room temperature PL spectra. The proposed p-type mechanism due to As_Zn-2V_Zn complex was confirmed by low temperature PL and XPS analysis. The low FWHM, resistivity and peak-to-valley roughness observed by XRD, Hall measurement and AFM, respectively, suggest that 1 at% Al-doped ZnO:As film is the best codoped film.