Low-temperature growth of epitaxial ZnO films on (001) sapphire by ultraviolet- assisted pulsed laser deposition

ZnO thin films have been grown on thin Si₃N₄ membranes and (001) sapphire substrates by an ultraviolet-assisted pulsed laser deposition (UVPLD) technique. The microstructure of the films grown on Si₃N₄ membranes, investigated by transmission electron microscopy, showed that crystalline and textured films can be grown by UVPLD at a substrate temperature of only 100 °C. For deposition temperatures higher than 400 °C, ZnO films grown on sapphire substrates were found to be epitaxial by Rutherford backscattering (RBS) and X-ray diffraction measurements. The minimum yield of channeling RBS spectra recorded from films deposited at 550 °C was around 2% and the FWHM of the rocking curve for the (002) diffraction peak was 0.17°; these values are similar to those recorded from ZnO layers grown by conventional PLD at 750 °C.     

XRD study on the effect of the deposition condition on pulsed laser deposition of ZnO films

Using a pulsed laser deposition (PLD) process on a ZnO target in an oxygen atmosphere, thin films of this material have been deposited on Si(111) substrates. An Nd: YAG pulsed laser with a wavelength of 1064 nm was used as the laser source. The influences of the deposition temperature, laser energy, annealing temperature and focus lens position on the crystallinity of ZnO films were analyzed by X-ray diffraction. The results show that the ZnO thin films obtained at the deposition temperature of 400°C and the laser energy of 250 mJ have the best crystalline quality in our experimental conditions. The ZnO thin films fabricated at substrate temperature 400°C were annealed at the temperatures from 400°C to 800°C in an atmosphere of N₂. The results show that crystalline quality has been improved by annealing, the optimum temperature being 600°C. The position of the focusing lens has a strong influence on pulsed laser deposition of the ZnO thin films and the optimum position is 59.5 cm from the target surface for optics with a focal length of 70 cm.      

KTN thin films prepared by pulsed laser deposition on transparent single crystal quartz(100)

Using the Sol-Gel method to produce the KTN ultrafine powder and the sintering technique with K2O atmosphere to prepare KTN ceramics as the targets instead of the KTN single crystal, highly oriented KTN thin films were produced on the transparent single crystal quartz (100) by the pulsed laser deposition (PLD). Since the thermal stress sustained by the quartz is relatively small, the limit temperature of the quartz substrates (300℃) is much lower than that of the P-Si substrates (560℃); the prepared thin film is at amorphous state. Increasing the pulsed laser energy density in the process incorporated with annealing the film after deposition at different temperatures converts the amorphous films into crystal. The optimal pulsed laser energy density and annealing temperature were 2.0 J/cm2 and 600℃, respectively. A discussion was made to understand the mechanism of film production at relatively low substrate temperature by PLD and effects of the annealing temperatures on the forming of the perovskite p     

Effect of thermal annealing on the structure and microstructure of TiO2 thin films

Nanostructured TiO₂ thin films have been prepared through chemical route using sol-gel and spin coating techniques. The deposited films were annealed in the temperature range 400–1000°C for 1 h. The structure and microstructure of the annealed films were characterized by GAXRD, micro-Raman spectroscopy and AFM. The as-deposited TiO₂ thin films are found to be amorphous. Micro-Raman and GAXRD results confirm the presence of the anatase phase and absence of the rutile phase for films annealed up to 700°C. The diffraction pattern of the film annealed at 800 to 1000°C contains peaks of both anatase and rutile reflections. The intensity of all peaks in micro-Raman and GAXRD patterns increased and their width (FWHM) decreased with increasing annealing temperature, demonstrating the improvement in the crystallinity of the annealed films. Phase transformation at higher annealing temperature involves a competition among three events such as: grain growth of anatase phase, conversion of anatase to rutile and grain growth of rutile phase. AFM image of the asdeposited films and annealed films indicated exponential grain growth at higher temperature.      

Annealing effects on microstructural and optical properties of Nanostructured-TiO2 thin films prepared by sol-gel technique

In this paper we report on the effect of annealing on the microsctructural and optoelectronic properties of titanium dioxide (TiO₂) thin films prepared using sol-gel method onto silicon (Si) (100) and quartz substrates. The annealing temperatures range from 200 to 1000 °C. The Microstructural properties of annealed thin films were investigated by Thermal gravimetric analyses (TGA), X-ray diffraction (XRD) and Raman Spectroscopy. The surface morphology of the film was examined using Atomic Force Microscopy (AFM) method. The optical properties of TiO₂ thin films were characterized using UV-VIS and Spectroscopic ellipsometry. The results have shown that the TiO₂ thin films persist in the anatase phase even after annealing at 800 °C. The phase transformation from anatase to rutile occurred only when the films were annealed at 1000 °C. AFM studies revealed nanocrystalline structure where their shape and density depend strongly on the annealing temperatures. The elaborated nanostructured-TiO₂ thin films present a high transparency in the visible range. Spectroscopic ellipsometry (SE) study was used to determine the effect of annealing temperature on the thickness and on the optical constant of TiO₂ thin films. Spectroscopic ellipsometry and UV-VIS shows that the band gap of TiO₂ thin films was found to decrease when the annealing temperature increases. The Anatase phase was find to show higher photocatalytic activity than the rutile one.     

Effect of crystalline structure of TiO2 substrates on initial growth of atomic layer deposited Ru thin films

Ru thin films were grown on polymorphic TiO₂ thin film substrates at 230 and 250 °C by atomic layer deposition using 2,4-(dimethylpentadienyl)(ethylcyclopentadienyl)Ru and an O₂ gas. While the Ru films grown on amorphous and rutile TiO₂ substrates showed a relatively long incubation cycle number of approximately 350 and 100 at 230 and 250 °C, respectively, the Ru films grown on anatase TiO₂ substrates exhibited a significantly shorter incubation delay which was attributed to the catalytic activity of anatase TiO₂. This difference in the incubation cycle affected the surface morphology of the Ru films on different TiO₂ substrates.     

Fabrication of coaxial nanowire heterostructures: SiO x nanowires with conformal TiO2 coatings

Silica nanowires, grown via the active oxidation of a silicon substrate, have been coated with TiO₂ using two coating methods: solution-based deposition of Ti-alkoxides and atomic layer deposition. Analysis of as-deposited and annealed films shows that it is possible to produce stable conformal coatings of either the anatase or rutile phases of TiO₂ on nanowires with diameters greater than 100 nm when annealed between 500–600°C and 800–900°C, respectively, with annealing at higher temperatures (1050°C) producing coatings with a highly facetted rutile morphology. The efficacy of the process is shown to depend on nanowire diameter, with nanowires having diameters less than about 100 nm fusing together during solution-based coating and decomposing during TiO₂ atomic layer deposition. The use of a suitable buffer layer is shown to be an effective means of minimizing nanowire decomposition. Finally, annealing coated nanowires under active oxidation conditions (1100°C) is shown to be an effective technique for depositing additional conformal SiO _x coatings, thereby providing a means of fabricating multi-layered coaxial nanostructures.     

Studies on highly resistive ZnO thin films grown by DC-discharge-assisted pulsed laser deposition

It was found that by changing the substrate temperature from room temperature to ～850 °C, ZnO thin films with widely varying resistivity values could be grown on sapphire substrates using DC-discharge-assisted pulsed laser deposition (PLD) in oxygen ambient. The resistivity of the film grown at room temperature was too high to measure using our existing setup. However, as the growth temperature was increased from 550 °C to 750 °C, the resistivity first decreased slowly from ～14.0 to 4.4 Ω?m and then dropped suddenly to get saturated at ～2.0×10^?3 Ω?m as the growth temperature was further increased. In contrast to these, when there was no DC-discharge, the variation of resistivity for ZnO thin films grown by PLD was marginal up to the substrate temperature of ～850 °C. The reason for these observations was found to be the combined effects of reduction in donor defect densities like oxygen vacancies and zinc interstitials, introduction of acceptor type defects like interstitial oxygen and zinc vacancies, and the resultant poor carrier mobility at lower growth temperatures. At higher growth temperatures (800 °C and above), the appearance of oxygen vacancies and increase in mobility due to better crystalline quality were found to be responsible for reducing the resistivity. The PL of these films had significant emission in the green and red regions of the spectrum due to the aforesaid defect related transitions. Such highly resistive and luminescent films might be suited for applications such as resistive RAM, UV-photo detector, TFT, piezoelectric, transparent phosphor, and broadband LED applications.     

The effect of different ambient gases, pressures, and substrate temperatures on TiO2 thin films grown on Si(100) by laser ablation technique

Pure titanium dioxide (TiO₂) thin films were deposited on single-crystal Si(100) substrates by laser ablation. We investigated the effects of ambient gas (O₂ or Ar), pressures, and substrate temperatures on film quality. From the annealing experiment of the deposited TiO₂ thin film under Ar or O₂ ambient gas, we see the chemical effect of ambient gas on film quality. The crystallinity of the deposited TiO₂ thin film is best at 700 °C in the substrate temperature range attempted, 400-700 °C, and at pressures of 0.1 Torr and below. The rutile phase is dominant under most experimental conditions. Only under very extreme conditions did we obtain a thin film of the anatase phase.     

Effect of process parameters and post-deposition annealing on the microwave dielectric and optical properties of pulsed laser deposited Bi<Subscript>1.5</Subscript>Zn<Subscript>1.0</Subscript>Nb<Subscript>1.5</Subscript>O<Subscript>7</Subscript> thin films

Bismuth Zinc niobate (Bi_1.5Zn_1.0Nb_1.5O₇) thin films were deposited by pulsed laser deposition (PLD) method on fused silica substrates at different oxygen pressures. The structural, microwave dielectric and optical properties of these thin films were systematically studied for both the as-deposited and the annealed films at 600°C. The as-deposited films were all amorphous in nature but crystallized on annealing at 600°C in air. The surface morphology as studied by atomic force microscopy (AFM) reveals ultra-fine grains in the case of as-deposited thin films and cluster grain morphology on annealing. The as-deposited films exhibit refractive index in the range of 2.36–2.53 (at a wavelength of 750 nm) with an optical absorption edge value of 3.30–3.52 eV and a maximum dielectric constant of 11 at 12.15 GHz. On annealing the films at 600°C they crystallize to the cubic pyrochlore structure accompanied by an increase in band gap, refractive index and microwave dielectric constant.     

Effects of thermally induced anatase-to-rutile phase transition in MOCVD-grown TiO2 films on structural and optical properties

Titanium dioxide (TiO₂) films with a thickness of 550 nm were deposited on quartz glass at 300 °C by metalorganic chemical vapor deposition. The effects of post-annealing between 600 °C and 1000 °C were investigated on the structural and optical properties of the films. X-ray diffraction patterns revealed that the anatase phase of as-grown TiO₂ films began to be transformed into rutile at the annealing temperature of 900 °C. The TiO₂ films were entirely changed to the rutile phase at 1000 °C. From scanning electron spectroscopy and atomic force microscopy images, it was confirmed that the microstructure of as-deposited films changed from narrow columnar grains into wide columnar ones. The surface composition of the TiO₂ films, which was analyzed by X-ray photoelectron spectroscopy data, was nearly constant although the films were annealed at different temperatures. When the annealing temperature increased, the transmittance of the films decreased, whereas the refractive index and the extinction coefficient calculated by the envelope method increased at high temperature. The values of optical band gap decreased from 3.5 eV to 3.25 eV at 900 °C. This abrupt decrease was consistent with the anatase-to-rutile phase transition. Received: 4 October 2000 / Accepted: 4 December 2000 / Published online: 23 May 2001     

Use of atomic layer deposition to improve the stability of silver substrates for in situ,high‐temperature SERS measurements

A method to stabilize silver surface‐enhanced Raman spectroscopy (SERS) substrates for in situ, high‐temperature applications is demonstrated. Silver island films grown by thermal evaporation were coated with a thin layer (from 2.5 to 5 nm) of alumina by atomic layer deposition (ALD), which protects and stabilizes the SERS‐active substrate without eliminating the Raman enhancement. The temporal stability of the alumina‐coated silver island films was examined by measurement of the Raman intensity of rhodamine 6G molecules deposited onto bare and alumina‐coated silver substrates over the course of 34 days. The coated substrates showed almost no change in SERS enhancement, while the uncoated substrates exhibited a significant decrease in Raman intensity. To demonstrate the feasibility of the alumina‐coated silver substrate as a probe of adsorbates and reactions at elevated temperatures, an in situ SERS measurement of calcium nitrate tetrahydrate on bare and alumina‐coated silver was performed at temperatures ranging from 25 to 400 °C. ALD deposition of an ultrathin alumina layer significantly improved the thermal stability of the SERS substrate, thus enabling in situ detection of the dehydration of the calcium nitrate tetrahydrate at an elevated temperature. Despite some loss of Raman signal, the coated substrate exhibited greater thermal stability compared to the uncoated substrate. These experiments show that ALD can be used to synthesize stable SERS substrates capable of measuring adsorbates and processes at high temperature. Copyright © 2009 John Wiley & Sons, Ltd.     

Effects of crystallinity on laser-induced voltage effect from Zn0.9Co0.1O thin film

Co-doped ZnO epilayer films were grown by pulsed laser deposition (PLD) on vicinal cut silicon and sapphire substrates. Changes in deposition time were observed as a moderate effect on the quality of the films, and the influence of the thickness on thermoelectric signals from Zn_0.9Co_0.1O thin films were discussed. The effect of one of the main deposition parameters, the deposition time, on the crystallinity and electron mobility properties of the Zn_0.9Co_0.1O thin films grown on sapphire was investigated by means of X-ray diffraction (XRD) and laser-induced voltage (LIV) effect. It shown that the XRD rocking curve full-width half-maximun (FWHM) decreased as time increasing, and the LIV signals were observed along the tilting angle of the substrate orientation when the pulsed KrF excimer laser of 248 nm were irradiated on the films. When the films illuminated in pulse lasers, the highest signals occurred in the films with best crystalline quality, and the signals were higher in the films grown on sapphire than those on silicon substrates. It suggested that the electrical resistivity and electron mobility have close relations with not only the crystallinity but also with the interface of the thin films.     

Thermal recrystallization of physical vapor deposition based germanium thin films on bulk silicon (100)

We demonstrate a simple, low‐cost, and scalable process for obtaining uniform, smooth surfaced, high quality mono‐crystalline germanium (100) thin films on silicon (100). The germanium thin films were deposited on a silicon substrate using plasma‐assisted sputtering based physical vapor deposition. They were crystallized by annealing at various temperatures ranging from 700 °C to 1100 °C. We report that the best quality germanium thin films are obtained above the melting point of germanium (937 °C), thus offering a method for in‐situ Czochralski process. We show well‐behaved high‐κ /metal gate metal–oxide–semiconductor capacitors (MOSCAPs) using this film. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

LiFePO4 thin films grown by pulsed laser deposition: Effect of the substrate on the film structure and morphology

Well crystallized and homogeneous LiFePO₄/C (LFPO) thin films have been grown by pulsed laser deposition (PLD). The targets were prepared by the sol-gel process at 600 °C. The structure of the polycrystalline powders was analyzed with X-ray powder diffraction (XRD) data. The XRD patterns were indexed having a single phase olivine structure (Pnma). LFPO thin films have been deposited on three different substrates: aluminum (Al), stainless steel (SS) and silicon (Si) by pulsed laser deposition (PLD). The structure of the films was analyzed by X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and atomic force microscopy (AFM). It is found that the crystallinity of the thin films depends on the substrate temperature which was set at 500 °C. When annealed treatments were used, secondary phases were found, so, one step depositions at 500 °C were made.Stainless steel is demonstrated to be the best choice to act as substrate for phosphate deposition. LiFePO₄ thin films grown on stainless steel plates exhibited the presence of carbon, inducing a slight conductivity enhancement that makes these films promising candidates as one step produced cathodes in Li-ion microbatteries.     

Pulsed laser deposition of tantalum pentoxide film

We report thin tantalum pentoxide (Ta₂O₅) films grown on quartz and silicon substrates by the pulsed laser deposition (PLD) technique employing a Nd:YAG laser (wavelength 5=532 nm) in various O₂ gas environments. The effect of oxygen pressure, substrate temperature, and annealing under UV irradiation using a 172-nm excimer lamp on the properties of the grown films has been studied. The optical properties determined by UV spectrophotometry were also found to be a sensitive function of oxygen pressure in the chamber. At an O₂ pressure of 0.2 mbar and deposition temperatures between 400 and 500 °C, the refractive index of the films was around 2.18 which is very close to the bulk Ta₂O₅ value of 2.2, and an optical transmittance around 90% in the visible region of the spectrum was obtained. X-ray diffraction measurements showed that the as-deposited films were amorphous at temperatures below 500 °C and possessed an orthorhombic (#-Ta₂O₅) crystal structure at temperatures above 600 °C. The most significant result of the present study was that oxygen pressure could be used to control the composition and modulate optical band gap of the films. It was also found that UV annealing can significantly improve the optical and electrical properties of the films deposited at low oxygen pressures (<0.1 mbar).     

Phase growth control in low temperature PLD Co: TiO2 films by pressure

This paper reports on the structural and optical properties of Co-doped TiO₂ thin films grown onto (0001)Al₂O₃ substrates by non-reactive pulsed laser deposition (PLD) using argon as buffer gas. It is shown that by keeping constant the substrate temperature at as low as 310 °C and varying only the background gas pressure between 7 Pa and 70 Pa, it is possible to grow either epitaxial rutile or pure anatase thin films, as well as films with a mixture of both polymorphs. The optical band gaps of the films are red shifted in comparison with the values usually reported for undoped TiO₂, which is consistent with n-type doping of the TiO₂ matrix. Such band gap red shift brings the absorption edge of the Co-doped TiO₂ films into the visible region, which might favour their photocatalytic activity. Furthermore, the band gap red shift depends on the films’ phase composition, increasing with the increase of the Urbach energy for increasing rutile content.     

The effect of nitrogen pressure on the two-step method deposition of GaN films

GaN thin films were deposited on sapphire (0001) substrates at different nitrogen pressures by pulsed laser deposition (PLD) of GaN target in nitrogen atmosphere. Good single crystal GaN thin films were obtained after annealing at 1000 °C for 15 min in a NH₃ atmosphere. An Nd:YAG pulsed laser with a wavelength of 1064 nm was used as the laser source. The influence of nitrogen pressure on the thickness, crystallinity and surface morphology of GaN films were characterized by X-ray diffraction (XRD), atomic force microscopy (AFM) and Raman spectroscopy. The results show that at low nitrogen pressure, the surface diffusion of adatoms can be influenced by the collisions between the nitrogen gas molecules and the activated atoms, which can influence the kinetic energy of the activated atoms. However, at high nitrogen pressure, the kinetic energy of adatoms is decided by the annealing temperature. In our experimental conditions, the GaN thin films deposited at 0.75 and 7.5 Pa have a high surface morphology and crystalline quality. PACS 71.55.Eq; 74.62.Fj     

ZnS thin films grown by atomic layer deposition on GaAs and HgCdTe substrates at very low temperature

ZnS films grown on GaAs and HgCdTe substrates by atomic layer deposition (ALD) under very low temperature were investigated in this work. ZnS films were grown under several temperatures lower than 140 °C. The properties of the films were investigated with high-resolution X-ray diffraction (HRXRD), scanning electron microscope (SEM), atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS). The results showed the ZnS films were polycrystalline. The growth rate monotonically decreased with temperature, as well as the root mean square (r.m.s) roughness measured by AFM. XPS measurement revealed the films were stoichiometric in Zn and S.     

Dispersion of laser droplets using H+ ions and annealing effect on pulsed laser deposited nickel ferrite thin films

Nickel ferrite thin films were deposited by a pulsed laser deposition (PLD) technique on silicon substrate at room temperature in a vacuum of 5×10⁻⁵ mbar. The films were subjected to different annealing temperatures from 300–900°C and were also exposed to single shot energetic hydrogen ions using a Dense Plasma Focus (DPF) device. The changes induced in the films exposed at different distances from the top of the anode were investigated. The structural, morphological and magnetic properties of the annealed and exposed samples were investigated. X-ray diffraction (XRD) studies reveal the presence of a single phase of nickel ferrite after annealing. SEM micrographs indicate an increase in the grain size, both on annealing as well as on exposure to hydrogen ions. Annealing and hydrogen ion irradiation induced an enhancement in the magnetic moments. Laser droplets which are inherent in films deposited by laser ablation were found to be dispersed as a result of single shot hydrogen ion irradiation from the DPF.