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.      

Structural, electrical, and surface characteristics of La0.5Sr0.5CoO3 thin films prepared by pulsed-laser deposition

A parametric study of the growth of La_0.5Sr_0.5CoO₃ (LSCO) thin films on (100) MgO substrates by pulsed-laser deposition (PLD) is reported. Films are grown under a wide range of substrate temperature (450–800 °C), oxygen pressure (0.1–0.9 mbar), and incident laser fluence (0.8–2.6 J/cm²). The optimum ranges of temperature, oxygen pressure, and laser fluence to produce c-axis oriented films with smooth surface morphology and high metallic conductivity are identified. Films deposited at low temperature (500 °C) and post-annealed in situ at higher temperatures (600–800 °C) are also investigated with respect to their structure, surface morphology, and electrical conductivity. Received: 20 November 1998 / Accepted: 6 July 1999 / Published online: 21 October 1999     

Properties of pulsed laser deposited nanocomposite NiO:Au thin films for gas sensing applications

Nanocomposite thin films formed by gold nanoparticles embedded in a nickel oxide matrix have been synthesized by a new variation of the pulsed laser deposition technique. Two actively synchronized laser sources, a KrF excimer laser at 248 nm and an Nd:YAG laser at 355 nm, were used for the simultaneous ablation of nickel and gold targets in oxygen ambient. The structural, morphological, and electrical properties of the obtained nanocomposite films were investigated in relation to the fluence of the laser irradiating the gold target. The nanocomposite thin films were tested as electrochemical hydrogen sensors. It was found that the addition of the gold nanoparticles increased the sensor sensitivity significantly.     

Substitution mechanism of Ga for Zn site depending on deposition temperature for transparent conducting oxides

High quality transparent conductive gallium-doped zinc oxide (GZO) thin films were deposited on glass substrates using rf-magnetron sputtering system at the temperature ranging from room temperature (RT) to 500 °C. The temperature-dependence of Ga doping effect on the structural, optical and electrical properties in ZnO has been investigated. For the GZO thin films deposited at over 200 °C, (103) orientation was strongly observed by X-ray diffraction analysis, which is attributed to the substitution of Ga elements into Zn site. X-ray photoelectron spectroscopy measurements have confirmed that oxygen vacancies were generated at the temperature higher than 300 °C. This might be due to the effective substitution of Ga³⁺ for Zn site at higher temperature. It was also found that the optical band gap increases with deposition temperature. The optical transmittance of GZO thin films was above 87% in the visible region. The GZO thin films grown at 500 °C showed a low electrical resistivity of 4.50 × 10^?4 Ω cm, a carrier concentration of 6.38 × 10²⁰ cm^?3 and a carrier mobility of 21.69 cm²/V.     

Pulsed laser deposition of molybdenum oxide thin films

Thin films of molybdenum oxide were deposited in vacuum by pulsed laser ablation using a xenon fluoride (351 nm) and a krypton fluoride (248 nm) excimer lasers. The films were deposited on unheated substrates and were post-annealed in air in the temperature range 300–500°C. The structural, morphological, chemical, and optical properties of the films were studied. As-deposited films were found to be dark. The transparency of the films was improved with annealing in air. The films were polycrystalline with diffraction peaks that belong to the orthorhombic phase of MoO₃. The surface morphology of the films showed a layered structure. Both the grain size and surface roughness increased with annealing temperature. The stoichiometry of the films improved upon annealing in air, with the best stoichiometry of MoO_2.95 obtained for films deposited by the XeF laser and annealed at 400°C. Similarly, the best transparency, with a transmittance exceeding 80%, was obtained with the films annealed in the temperature range 400–450°C.     

Production of biologically inert Teflon thin layers on the surface of allergenic metal objects by pulsed laser deposition technology

Allergic-type diseases are current nowadays, and they are frequently caused by certain metals. We demonstrated that the metal objects can be covered by Teflon protective thin layers using a pulsed laser deposition procedure. An ArF excimer laser beam was focused onto the surface of pressed PTFE powder pellets; the applied fluences were 7.5–7.7 J/cm². Teflon films were deposited on fourteen-carat gold, silver and titanium plates. The number of ablating pulses was 10000. Post-annealing of the films was carried out in atmospheric air at oven temperatures between 320 and 500 °C. The thickness of the thin layers was around 5 μm. The prepared films were granular without heat treatment or after annealing at a temperature below 340 °C. At 360 °C a crystalline, contiguous, smooth, very compact and pinhole-free thin layer was produced; a melted and re-solidified morphology was observed above 420 °C. The adhesion strength between the Teflon films and the metal substrates was determined. This could exceed 1–4 MPa depending on the treatment temperature. It was proved that the prepared Teflon layers can be suitable for prevention of contact between the human body and allergen metals and so for avoidance of metal allergy. Received: 12 June 2002 / Accepted: 13 June 2002 / Published online: 4 November 2002 RID="*" ID="*"Corresponding author. E-mail: bhopp@physx.u-szeged.hu     

SnO2 thin films grown by pulsed Nd:YAG laser deposition

SnO₂ thin films have been deposited on glass substrates by pulsed Nd:YAG laser at different oxygen pressures, and the effects of oxygen pressure on the physical properties of SnO₂ films have been investigated. The films were deposited at substrate temperature of 500°C in oxygen partial pressure between 5.0 and 125 mTorr. The thin films deposited between 5.0 to 50 mTorr showed evidence of diffraction peaks, but increasing the oxygen pressure up to 100 mTorr, three diffraction peaks (110), (101) and (211) were observed containing the SnO₂ tetragonal structure. The electrical resistivity was very sensitive to the oxygen pressure. At 100 mTorr the films showed electrical resistivity of 4×10⁻² Ω cm, free carrier density of 1.03×10¹⁹ cm⁻³, mobility of 10.26 cm² V⁻¹ s⁻¹ with average visible transmittance of ∼87%, and optical band gap of 3.6 eV.     

Effects of deposition temperature and post-annealing on structure and electrical properties in (La<Subscript>0.5</Subscript>Sr<Subscript>0.5</Subscript>)CoO<Subscript>3</Subscript> films grown on silicon substrate

(La_0.5Sr_0.5)CoO₃ (LSCO) thin films have been fabricated on silicon substrate by the pulsed laser deposition method. The effects of substrate temperature and post-annealing condition on the structural and electrical properties are investigated. The samples grown above 650°C are fully crystalline with perovskite structure. The film deposited at 700°C has columnar growth with electrical resistivity of about 1.99×10⁻³ Ω cm. The amorphous films grown at 500°C were post-annealed at different conditions. The sample post-annealed at 700°C and 10⁻⁴ Pa has similar microstructure with the sample in situ grown at 700°C and 25 Pa. However, the electrical resistivity of the post-annealed sample is one magnitude higher than that of the in situ grown sample because of the effect of oxygen vacancy. The temperature dependence of resistivity exhibits semiconductor-like character. It was found that post-annealing by rapid thermal process will result in film cracks due to the thermal stress. The results are referential for the applications of LSCO in microelectronic devices.     

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.     

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.     

Development of conductive transparent indium tin oxide (ITO) thin films deposited by direct current (DC) magnetron sputtering for photon-STM applications

Highly conductive and transparent indium tin oxide (ITO) thin films, each with a thickness of 100 nm, were deposited on glass and Si(100) by direct current (DC) magnetron sputtering under an argon (Ar) atmosphere using an ITO target composed of 95% indium oxide and 5% tin oxide for photon-STM use. X-ray diffraction, STM observations, resistivity and transmission measurements were carried out to study the formation of the films at substrate temperatures between 40 and 400 °C and the effects of thermal annealing in air between 200 and 400 °C for between1 and 5 h. The film properties were highly dependent on deposition conditions and on post-deposition film treatment. The films deposited under an Ar atmosphere pressure of ∼1.7×10^-3 Torr by DC power sputtering (100 W) at substrate temperatures between 40 and 400 °C exhibited resistivities in the range 3.0–5.7×10^-5 Ω m and transmissions in the range 71–79%. After deposition and annealing in air at 300 °C for 1 h, the films showed resistivities in the range 2.9–4.0×10^-5 Ω m and transmissions in the range 78–81%. Resistivity and transmission measurements showed that in order to improve conductive and transparent properties, 2 h annealing in air at 300 °C was necessary. X-ray diffraction data supported the experimental measurements of resistivity and transmission on the studies of annealing time. The surface roughness and film uniformity improve with increasing substrate temperature. STM observations found the ITO films deposited at a substrate temperature of 325 °C, and up to 400 °C, had domains with crystalline structures. After deposition and annealing in air at 300 °C for 1 h the films still exhibited similar domains. However, after deposition at substrate temperatures from 40 °C to 300 °C, and annealing in air at 300 °C for 1 h, the films were shown to be amorphous. More importantly, the STM studies found that the ITO film surfaces were most likely to break after deposition at a substrate temperature of 325 °C and annealing in air at 300 °C for 2 or 3 h. Such findings give some inspiration to us in interpreting the effects of annealing on the improvement of conductive and transparent properties and on the transition of phases. In addition, correlations between the conductive/transparent properties and the phase transition, the annealing time and the phase transition, and the conductive/transparent properties and the annealing time have been investigated. Received: 10 July 2000 / Accepted: 27 October 2000 / Published online: 9 February 2001     

High c-axis preferred orientation ZnO thin films prepared by oxidation of metallic zinc

Thin films of zinc oxide were grown on glass substrates by thermal oxidation. The metallic zinc films were thermally oxidized at different temperatures ranging from 300 to 600 °C to yield ZnO thin films. The structural property of the thin films was characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The X-ray diffraction measurements showed that the films oxidized at 300 °C were not oxidized entirely, and the films deposited at 600 °C had better crystalline quality than the rest. When the oxidation temperature increased above 400 °C, the films exhibited preferred orientation along (002) and high transmittance ranging from 85% to 98% in vis–near-infrared band. Meanwhile, the films showed a UV emission at about 377 nm and green emission. With the increasing of oxidation temperature, the intensity of green emission peak was enhanced, and then decreased, disappearing at 600 °C, and the case of UV emission increased. Furthermore, a strong green emission was observed in the film sintered in pure oxygen atmosphere.     

Effects of aluminum doping and substrate temperature on zinc oxide thin films grown by pulsed laser deposition

Aluminum-doped zinc oxide (AZO) thin films have been deposited on amorphous fused silica substrates by pulsed laser ablation of a Zn:Al metallic targets. We varied the film growth condition such as the substrate temperature and Al concentrations. The films were deposited at substrate temperatures ranging from 20 to 600°C with oxygen partial pressure of 1 torr. The characteristics of the deposited films were examined by analyzing their photoluminescence (PL), X-ray diffraction (XRD), and UV–visible spectra. It is observed that the optical bandgap energy of the deposited films increased with the increase of Al concentration and substrate temperature. Besides, the PL peak energy shifted to blue and the Stokes shift became larger as the Al content increased.     

Indium oxide thin-film holographic recorders grown by excimer laser reactive sputtering

2 O₃) thin films on glass substrates is performed by pulsed laser ablation of a metallic indium target in an oxygen atmosphere. X-ray diffraction analysis verifies that a transition, from amorphous to polycrystalline film growth, occurs at a temperature of 150 °C. Films grown under optimized conditions exhibit optical transmission higher than 80% in the visible light. Ultraviolet radiation (λ= 325 nm) induced dynamic holographic recording in films deposited at specific temperature and oxygen pressure settings is also demonstrated. Received: 25 April 1997/Accepted: 27 May 1997     

Production and characterization of Nd,Cr:GSGG thin films on Si(001) grown by pulsed laser ablation

Nd,Cr:Gd₃Sc₂Ga₃O₁₂ (GSGG) thin films have been produced for the first time. They were grown on Si(001) substrates at 650 °C by pulsed laser ablation at 248 nm of a crystalline Nd,Cr:GSGG target rod. The laser plume was analyzed using time-of-flight quadrupole mass spectroscopy, and consisted of elemental and metal oxide fragments with kinetic energies typically in the range 10 to 40 eV, though extending up to 100 eV. Although films deposited in vacuum using laser fluences of 0.8±0.1 J cm⁻² reproduced the Nd,Cr:GSGG bulk stoichiometry, those deposited using fluences above ≈3 J cm⁻² resulted in noncongruent material transfer and were deficient in Ga and Cr. Attempts to grow films using synchronized oxygen or oxygen/argon pulses yielded mixed oxide phases. Under optimal growth conditions, the films were heteroepitaxial, with GSGG(001)[100]∥Si(001)[100], and exhibited Volmer–Weber-type growth. Room-temperature emission spectra of the films suggest efficient non-radiative energy transfer between Cr³⁺ and Nd³⁺ ions, similar to that of the bulk crystal. Received: 1 October 1999 / Accepted: 15 October 1999 / Published online: 23 February 2000     

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).     

Effects of preannealing temperature of ZnO thin films on the performance of dye-sensitized solar cells

The preferred (002) orientation zinc oxide (ZnO) nanocrystalline thin films have been deposited on FTO-coated glass substrates by sol–gel spin-coating technology and rapid thermal annealing for use in dye-sensitized solar cells (DSSC). The effects of preannealing temperature (100 and 300°C) on the microstructure, morphology and optical properties of ZnO thin films were studied. The ZnO thin films were characterized by X-ray diffraction (XRD), scanning electron microscopic (SEM) and Brunauer–Emmett–Teller (BET) analysis. The photoelectric performance of DSSC was studied by I–V curve and the incident photon-to-current conversion efficiency (IPCE), respectively. From the results, the intensities of (002) peaks of ZnO thin films increases with increasing preannealing temperature from 100°C to 300°C. The increase in pore size and surface area of ZnO films crystallized at the increased preannealing temperature contributed to the improvement on the absorption of N3 dye onto the films, the short-circuit photocurrent (J _sc) and open-circuit voltage (V _oc) of DSSC. The higher efficiency (η) of 2.5% with J _sc and V _oc of 8.2 mA/cm² and 0.64 V, respectively, was obtained by the ZnO film preannealed at 300°C.     

Structural and optical properties of pulsed laser deposited ZnO thin films

Nanocrystalline ZnO thin films were grown by means of pulsed laser deposition. The ablation process was carried out at relatively low background oxygen gas pressure (10 Pa) and by varying the substrate temperature up to 600 °C. Information on the structural and morphological properties of the deposited thin films have been obtained by means of X-ray photoelectron, Raman spectroscopies, X-ray diffraction (XRD) and atomic force microscopy (AFM). The results showed that all the deposited films are sub-stoichiometric in oxygen and with a hexagonal wurtzite crystalline structure, characterized by features of some tens of nanometers in size. An improvement of the films' crystalline quality was observed for the deposition temperature of 300 °C while the further increase of the deposition temperature up to 600 °C induces a worsening of the material's structural properties with the development of a large amount of nanoparticle's clusters. The analysis of the XRD patterns shows a growth crystallographic preferential direction as a function of the deposition temperature, in agreement with the appearance of the only E₂ optical phonon mode in the Raman spectra. Such findings are compatible with the changes observed in the photoluminescent (PL) optical response and was related to the modification of the ZnO thin film structural quality.     

Transparent conducting AZO and ITO films produced by pulsed laser ablation at 355 nm

Thin films of aluminium-doped zinc oxide (AZO) and indium tin oxide (ITO) were deposited on glass substrates by laser ablation in an oxygen environment. The electrical and optical properties of films grown at various oxygen pressures were compared. With no substrate heating, highly transparent and conducting films were obtained with oxygen pressures between 15 and 23 mTorr for both materials. We obtained a specific resistivity of 1.8᎒^-3 Q cm for AZO and 1.1᎒^-3 Q cm for ITO. By heating the substrate to 160 °C or 200 °C, the resistivity was further reduced to 1.1᎒^-3 Q cm for AZO and 3.9᎒^-4 Q cm for ITO. The average transmission of visible light (450-750 nm) was between 82% and 98% in most cases. The results suggest that AZO is a promising alternative to ITO.     

Studies on pyrolytically sprayed SnO2 and Sb-SnO2 thin films for LPG sensor applications

Undoped and antimony doped tin oxide thin films of different thicknesses were prepared on mineral glass substrate by spray pyrolysis method via sol-gel route. Both the films show good transmittance in the visible region. Band gap energy of both films lies between 3 to 3.5 eV. X-ray diffraction studies of undoped and antimony doped tin oxide thin films for various annealing temperature show polycrystalline tetragonal structure of SnO₂ with preferred orientation of (110) and (101), respectively and from the XRD data, grain size were also evaluated. AFM images of Undoped and antimony doped tin oxide thin films annealed at 375 °C depict the film thickness and indicate uniform surface pattern without dark pits and with strains of some ups exceeding the specified limit. The prepared films were tested in a specially developed test rig for Liquefied Petroleum Gas detection at different operating temperatures. The response characteristics of the films for LPG detection show maximum sensitivity and minimum response time at the operating temperature 400 °C. Studies indicate that antimony doped tin oxide thin film are one among the suitable candidates for LPG detection with a detection sensitivity and response time (t90) of 11 and 140 seconds, respectively. Paper presented at the 2nd International Conference on Ionic Devices, Anna University, Chennai, India, Nov. 28–30, 2003.