AFM surface analysis of ZnO layers prepared by pulsed laser deposition at different oxygen pressures

Polycrystalline thin films of zinc oxide were deposited by pulsed laser deposition onto silicon substrates at different oxygen partial pressures in the range of 1-35 Pa. For ablation of the sintered zinc oxide target a pulsed Nd:YAG laser was used. Other processing parameters such as laser pulse energy, pulse repetition rate, substrate temperature and deposition pressure were identical. The effect of oxygen pressure on the structural properties of the films was systematically studied by using atomic force microscopy. The surface morphology, average roughness S_a, root mean square S_q, and mean size of grains on selected places with 2 × 2 μm² area of prepared samples were evaluated. Detailed structural analysis confirmed that partial oxygen pressure leads to the modification of surface morphology. Mean grain size in height and lateral direction decreases with raising oxygen pressure from 1 to 5 Pa while the further increase of oxygen pressure from 5 to 35 Pa results in grain size enlargement. The zinc oxide film formed at oxygen partial pressure 5 Pa shows smallest values of evaluated parameters (S_a = 0.6 nm, S_q = 0.7 nm and mean size of grains 50 nm).     

Metal-semiconductor transition in Nb-doped ZnO thin films prepared by pulsed laser deposition

The structural, electrical and optical properties of Nb-doped ZnO films were investigated with different Nb contents (0, 0.15, 0.31, 0.46, 0.62, and 0.94 at.%) in this article. The film with 0.46 at.% Nb content showed the lowest resistivity of 8.95 × 10^− 4 Ω cm and high transmittance about 80% with high c-axis orientation. The undoped ZnO film showed a semiconducting behavior. And Nb-doped ZnO films showed a metal-semiconductor transition (MST), which was connected with localization of degenerate electrons. The films showed metallic conductivity at temperatures closer to the ambient temperature and semiconducting behavior at lower temperatures. It was noted that the NZO films with much lower Nb concentration of 0.15 at.% presented MST compared with other transparent conducting oxides films.     

Microstructure and magnetic properties of zinc ferrite thin films produced by pulsed laser deposition

Zinc ferrite thin films were deposited from a target of zinc ferrite onto a MgO substrate using XeCl excimer laser operating at 308 nm and frequency of 30 Hz. The crystallographic characterizations of the films were performed using X-ray diffraction (XRD). Microstructure, surface morphology, chemical composition and grain size, as well as surface roughness were obtained from scanning electron microscope (SEM), energy dispersive spectroscopy (EDS) and atomic force microscopy (AFM). The magnetic properties of the thin films were studied in the temperature range 5–300 K and in fields of up to 5 T using SQUID magnetometry. Data on temperature and field dependence of magnetization provide a strong evidence for superparamagnetism. Paper presented at 8 AGM of MRSI, BARC, Mumbai, 1997.     

ITO thin films deposited by advanced pulsed laser deposition

Indium tin oxide thin films were deposited by computer assisted advanced PLD method in order to obtain transparent, conductive and homogeneous films on a large area. The films were deposited on glass substrates. We studied the influence of the temperature (room temperature (RT)-180 °C), pressure (1-6 × 10^− 2 Torr), laser fluence (1-4 J/cm²) and wavelength (266-355 nm) on the film properties. The deposition rate, roughness, film structure, optical transmission, electrical conductivity measurements were done. We deposited uniform ITO thin films (thickness 100-600 nm, roughness 5-10 nm) between RT and 180 °C on a large area (5 × 5 cm²). The films have electrical resistivity of 8 × 10^− 4 Ω cm at RT, 5 × 10^− 4 Ω cm at 180 °C and an optical transmission in the visible range, around 89%.     

Growth process observation of homoepitaxial ZnO thin films using optical emission spectra during pulsed laser deposition

Homoepitaxial ZnO thin films were prepared on the Zn-polar or O-polar ZnO substrates by pulsed laser deposition method. Optical emission spectroscopy of the plume was carried out to estimate O/Zn flux ratio under the various deposition conditions such as oxygen pressure, laser fluence, and the distance between target and substrate. It is revealed that the O/Zn flux ratio could be controlled by laser fluence, oxygen pressure, and target-substrate distance. Zn-rich O/Zn flux promotes pit formation and O-rich flux yields the three-dimensional growth. The difference of the growth process on Zn-polar or O-polar substrates is also discussed.     

Low-temperature deposition of iridium thin films by pulsed laser deposition

Extremely smooth iridium (Ir) thin films were deposited on Si(1 0 0) substrate at lower temperature than 300 °C by pulsed laser deposition (PLD) technique using Ir target in a vacuum atmosphere. The crystal orientation, surface morphology, and resistivity of the Ir thin films were systematically determined as a function of substrate temperature. Well-crystallized and single-phase Ir thin films with (1 1 1) preferred orientation were obtained at substrate temperature of 200-300 °C. The surface roughness increased with the increasing of substrate temperature. Likewise, the room-temperature resistivity of Ir thin films decreased with increasing substrate temperature, showing a low value of (10.7±0.1) μΩ cm at 300 °C.     

Controlled growth and characteristics of single-phase Cu2O and CuO films by pulsed laser deposition

Copper oxide, Cu₂O and CuO, thin films have been synthesized on Si (100) substrates using pulsed laser deposition method. The influences of substrate temperature and oxygen pressure on the structural properties of copper oxide films were discussed. The X-ray diffraction results show that the structure of the films changes from Cu₂O to CuO phase with the increasing of the oxygen pressure. It is also found that the (200) and (111) preferred Cu₂O films can be modified by changing substrate temperature. The formation of Cu₂O and CuO films are further identified by Fourier transform infrared spectroscopy. For the Cu₂O films, X-ray photoelectron spectroscopic studies indicate the presence of CuO on the surface. In addition, the optical gaps of Cu₂O and CuO films have been determined by measuring the transmittance and reflectance spectra.     

Influence of thickness and growth temperature on the optical and electrical properties of ZnO thin films

Zinc oxide transparent conductive thin films were prepared using the pulsed laser deposition technique onto Corning glass substrates and the dependences of their optical and electrical properties on the thickness and the growth temperature were investigated. As shown, the films present 90% average transmittance, their energy gap position depending on the film thickness and the growth temperature. An additional absorption band was also observed near 3.44 eV, the position of its maximum also depending on the growth parameters. Finally, the electrical properties of the films were found to be affected mainly by the growth temperature and less by the thickness.     

A parametric study of AlN thin films grown by pulsed laser deposition

High quality AlN thin films were grown at 200–450°C on sapphire substrates by laser ablation of Al targets in nitrogen reactive atmosphere. The nitrogen pressure was varied between 10⁻³ and 10⁻¹ mbar. The reactive gas pressure during irradiation and the temperature of the substrate were found to essentially influence the quality of the layers. X-ray diffraction analysis evidenced the formation of highly orientated layers for a very restrictive set of parameters. Other analysis techniques, like X-ray photoelectron spectroscopy, secondary ion mass spectroscopy, optical transmission spectroscopy have been used to evidence the good stoichiometry and purity of the films. The characteristics of these films were compared with those of AlN thin films deposited in similar experimental conditions, on Si (100) and Si (111) substrates.     

Correlations between optical properties, microstructure, and processing conditions of Aluminum nitride thin films fabricated by pulsed laser deposition

Aluminum nitride (AlN) films were deposited using pulsed laser deposition (PLD) onto sapphire (0001) substrates with varying processing conditions (temperature, pressure, and laser fluence). We have studied the dependence of optical properties, structural properties and their correlations for these AlN films. The optical transmission spectra of the produced films were measured, and a numerical procedure was applied to accurately determine the optical constants for films of non-uniform thickness. The microstructure and texture of the films were studied using various X-ray diffraction techniques. The real part of the refractive index was found to not vary significantly with processing parameters, but absorption was found to be strongly dependent on the deposition temperature and the nitrogen pressure in the deposition chamber. We report that low optical absorption, textured polycrystalline AlN films can be produced by PLD on sapphire substrates at both low and high laser fluence using a background nitrogen pressure of 6.0 × 10^− 2 Pa (4.5 × 10^− 4 Torr) of 99.9% purity.     

Reversible wettability of ZnO nanostructured thin films prepared by pulsed laser deposition

This work reports on the photoinduced wettability changes of high quality nanostructured ZnO films grown on Si by pulsed laser deposition (PLD) under different growth parameters. The wetting behavior of the resulting films can be reversibly switched from hydrophobic to hydrophilic, through alternation of UV illumination and dark storage. The kinetics of this wetting transition are studied by monitoring the time evolution of the corresponding contact angles. Finally, the influence of the film properties over the observed wetting response is discussed.     

Composition, structural and electrical properties of thin films prepared by laser ablation of neodymium-doped potassium gadolinium tungstate

Thin films were grown on (001) SiO₂, SiO₂/(100) Si or (100) MgO substrates by laser ablation of neodymium-doped potassium gadolinium tungstate (Nd:KGW) single crystal target. The films were deposited at temperatures between room temperature and 750 °C and pressures between 1 × 10^− 4 Pa and 50 Pa of oxygen ambient. The influence of the deposition conditions on the composition, structure, morphology and electrical properties of the films was investigated. Special attention was paid to the films deposited in vacuum (1 × 10^− 4 Pa) or at very low oxygen pressures. Under such conditions, the potassium (K), gadolinium (Gd) and oxygen (O) content decreased strongly as the temperature was increased. At room temperature, the films were K and O stoichiometric, in contrast with Gd, which showed a concentration twice higher. The films were polycrystalline, with the exception of those deposited at temperatures below 500 °C, which were amorphous. However, all were smooth and dense. The films grown in vacuum and at temperatures between 500 and 700 °C consist mainly of “â-tungsten” - tungsten oxide (W₃O) phase. The films grown on SiO₂/Si possessed the best surface quality with nano-size relief. The resistivity measurements as a function of the temperature showed that the films produced in vacuum and at temperatures below 500 °C were highly insulating, whereas at 600 °C they exhibited semiconducting behavior or a metallic one at 700 °C. This behavior can be attributed to the existence of various valence states for tungsten below W⁶⁺ in the films and to their crystal structure.     

Annealing and recrystallization of amorphous ZnO thin films deposited under cryogenic conditions by pulsed laser deposition

This article deals with the annealing of amorphous ZnO thin films prepared by pulsed laser deposition (PLD) under cryogenic conditions. The substrate holder was cooled by liquid nitrogen. X-ray diffraction analysis evidenced that as-deposited films had amorphous structures: analysis by scanning electron microscopy (SEM) revealed their fine grained surface and inner structure. Annealing at temperatures in the range of 200-800 °C resulted in a transition in the thin film crystal structure from amorphous to polycrystalline. Various properties of the ZnO films were found depending on the recrystallization temperature. In depth investigations employing SEM, X-ray diffraction, atomic force microscopy and secondary ion mass spectroscopy provided comparisons of the recrystallizations of undoped ZnO thin films during the phase transition processes from amorphous to hexagonal wurtzite structures.     

Composition controlling of KNbO3 thin films prepared by pulsed laser deposition

The composition of KNbO₃ thin films prepared by pulsed laser deposition is crucially influenced by the deposition configuration. In the present study, the composition of KNbO₃ thin films grown on Si (100) substrates by pulsed laser ablation was tried to be controlled by adjusting the target-substrate distance and the oblique angle of substrate from the plume axial direction. It was found that the K deficiency in the films can be effectively avoided by setting the substrate at an appropriate oblique angle from the plume axial direction. The stoichiometric KNbO₃ thin films with a K/Nb molar ratio of 0.98 were successfully obtained, where the substrates were set at an oblique angle of 3-12° from the plume axis while the target-substrate distance was kept at 40 mm.     

A study of microstructural and optical properties of nanocrystalline ceria thin films prepared by pulsed laser deposition

Thin films of cerium oxide (CeO₂) have been deposited on (100) Si substrates using pulsed laser deposition technique at various substrate temperatures from room temperature (RT) to 973 K at an optimized oxygen partial pressure of 3 Pa. Structural, morphological and optical properties have been carried out using X-ray diffraction (XRD), Raman, ellipsometry and atomic force microscopy techniques. XRD results showed that the deposited films are polycrystalline with cubic structure. At room temperature, the film showed preferred orientation along (111) plane, while at higher temperatures, it exhibited preferred orientation along (200). The crystallite sizes were calculated and were found to be in the range 17-52 nm. The texture coefficient for (200) reflection increased until 573 K, and then decreased in the temperature range 673-973 K. The Raman peak appeared at 463 cm^− 1 due to the F_2g active mode also confirmed the formation of CeO₂ with a cubic structure. There was a systematic variation in the Raman peak intensity, frequency shift and line broadening with the increase of temperature. The ellipsometry studies showed that the refractive index and band gap increased from 2.2 to 2.6 and 3.4 to 3.6 eV, respectively with increasing substrate temperature from RT to 973 K.     

High quality amorphous indium zinc oxide thin films synthesized by pulsed laser deposition

Indium zinc oxide films were grown from targets with two different In atomic concentration [In/(In + Zn)] of 40% and 80% by the pulsed laser deposition technique on glass substrates from room temperature up to 100 °C. X-ray diffraction and reflectometry investigations showed that films were amorphous and dense. Thin films (thickness < 100 nm) exhibited higher optical transmittance and resistivities than thick films (thickness > 1000 nm), probably caused by a significant decrease of oxygen vacancies due to atmosphere exposure. Films deposited from the In rich target under an oxygen pressure of 1 Pa exhibited optical transmittance higher than 85%, resistivities around 5- 7 × 10^− 4 Ω cm and mobilities in the 47-54 cm²/V s range.     

Cryogenic pulsed laser deposition of ZnO

The paper deals with the pulsed laser deposition technology and in this special case the substrate was cooled at cryogenic temperature by liquid nitrogen during the deposition process. This approach is proper for growth of highly disordered structures with new physical properties and zinc oxide was applied as experimental example for demonstration. Films were deposited on different substrates: Si (100) and sapphire (0001) and subsequently annealed at different temperatures (200-800 °C). Their properties were investigated by various analytical methods. X-ray diffraction (XRD) proved fully amorphous structure of as-grown ZnO layers which were cooled during the deposition process. Annealing of these amorphous layers changed their properties according to temperature level and annealing time. XRD and scanning electron microscopy (SEM) revealed recrystallized structure. According to the secondary ion mass spectroscopy (SIMS) the layers has homogenous chemical composition along the depth profile with improved homogeneity after annealing.     

ZnO thin films grown on platinum (111) buffer layers by pulsed laser deposition

C-axis oriented ZnO layers were grown by pulsed-laser deposition on the surface of a platinum (111) epitaxial thin film supported by a c-sapphire substrate. The Pt bottom layer provides good in-plane lattice matching with c-ZnO, enabling epitaxial re-growth of the latter, as shown by X-ray diffraction data. Room- and low-temperature reflectance and photoluminescence measurements have been performed on such ZnO/Pt heterostructures for the first time. Intense resonances, corresponding to the A and B free excitons, are clearly evidenced in the reflectance measurements at 30 K, while the deconvolved full widths at half maximum of the bound excitonic lines, observed in the photoluminescence spectra at 28 K, range between 3 and 7 meV. This report clearly demonstrates that ZnO epitaxial thin films with very good structural and optical properties can be grown on a Pt bottom electrode and, thus, establishes the potential of this material system for use in ZnO-based optoelectronic devices.     

Comparison of structural and photoluminescence properties of ZnO thin films grown by pulsed laser deposition and ultrasonic spray pyrolysis

ZnO thin films have been deposited by pulsed laser deposition (PLD) and ultrasonic spray pyrolysis (USP) method, respectively. X-ray diffraction and transmission electron microscopy characterizations indicate that ZnO film grown by PLD exhibits better crystallinity than that grown by USP. Photoluminescence spectra show that the near-band edge ultraviolet emission of film grown by PLD is narrower and shifts to higher energy, compared with that of film grown by USP. In the visible range, ZnO film grown by PLD exhibits four local level emission centered at 470 nm, 486 nm, 544 nm, and 613 nm, respectively, while the film grown by USP only presents a weak broad band emission centered at 502 nm. Hall measurement shows higher carrier density and lower hall mobility in ZnO film grown by PLD than that in film grown by USP. The higher density of intrinsic defects as well as higher crystallintiy is considered to account for the difference of photoluminescence in ZnO film grown by PLD with that in film grown by USP.     

Annealing effect on properties of transparent and conducting ZnO thin films

This work presents the effect of postdeposition annealing on the structural, electrical and optical properties of undoped ZnO (zinc oxide) thin films, prepared by radio-frequency sputtering method. Two samples, 0.17 and 0.32 µm-thick, were annealed in vacuum from room temperature to 350 °C while another 0.32 µm-thick sample was annealed in air at 300 °C for 1 h. X-ray diffraction analysis revealed that all the films had a c-axis orientation of the wurtzite structure normal to the substrate. Electrical measurements showed that the resistivity of samples annealed in vacuum decreased gradually with the increase of annealing temperature. For the 0.32 µm-thick sample, the gradual decrease of the resistivity was essentially due to a gradual increase in the mobility. On the other hand, the resistivity of the sample annealed in air increased strongly. The average transmission within the visible wavelength region for all films was higher than 80%. The band gap of samples annealed in vacuum increased whereas the band gap of the one annealed in air decreased. The main changes observed in all samples of this study were explained in terms of the effect of oxygen chemisorption and microstructural properties.