Oxygen deficiency in oxide films grown by PLD

The incorporation of oxygen atoms in oxide films grown by pulsed laser deposition depends upon the oxygen pressure and laser power density. By carefully controlling these two parameters it is possible to control the oxygen deficiency in the samples, and thus to change their physical properties from insulating and transparent to absorbing and conducting. By using X-ray diffraction, Rutherford backscattering spectroscopy and resistivity measurements, we show that depending upon the oxide materials oxygen deficiency in the films can induce either the growth of stable sub-oxide phases or the formation of nanocomposite films by phase separation. The first case corresponds to oxides with a mixed valency cation like Ti, which leads to the formation of stable, crystalline and highly conductive TiO_x sub-oxide phases. The second case is well described by the indium tin oxides (ITO) in which a large oxygen deficiency leads to metallic clusters embedded into a stoichiometric matrix, i.e. nanocomposite films. This phenomenon is due to the fact that sub-oxides of these compounds are not stable and thus the oxygen deficiency induced a phase separation.     

Electrical, structural, and optical properties of ITO thin films prepared at room temperature by pulsed laser deposition

Indium tin oxide (ITO) thin films were prepared by pulsed laser deposition (PLD) on glass substrate at room temperature. Structural, optical, and electrical properties of these films were analyzed in order to investigate its dependence on oxygen pressure, and rapid thermal annealing (RTA) temperature. High quality ITO films with a low resistivity of 3.3 × 10⁻⁴ Ω cm and a transparency above 90% were able to be formed at an oxygen pressure of 2.0 Pa and an RTA temperature of 400 °C. A four-point probe method, X-ray diffraction (XRD), atomic force microscopy (AFM), and UV-NIR grating spectrometer are used to investigate the properties of ITO films.     

Optical and electrical properties of aluminum-doped ZnO thin films grown by pulsed laser deposition

Transparent aluminum-doped zinc oxide (AZO) thin films were deposited on quartz glass substrates by pulsed laser deposition (PLD) from ablating Zn-Al metallic targets. The structural, electrical and optical properties of these films were characterized as a function of Al concentration (0-8 wt.%) in the target. Films were deposited at a low substrate temperature of 150 °C under 11 Pa of oxygen pressure. It was observed that 2 wt.% of Al in the target (or 1.37 wt.% of Al doped in the AZO film) is the optimum concentration to achieve the minimum film resistivity and strong ultraviolet emission. The presence of Al in the ZnO film changes the carrier concentration and the intrinsic defects.     

Effect of the duty ratio on the indium tin oxide (ITO) film deposited by in-line pulsed DC magnetron sputtering method for resistive touch panel

The indium tin oxide (ITO) film was deposited on PET (polyethylene terephthalate) film using in-line pulsed DC magnetron sputtering system with different duty ratios. The reverse time and the frequency of pulsed DC power were changed to obtain the different duty ratios. From the electrical and optical properties such as the sheet resistance, resistivity, thickness and transmittance, the pulsed DC sputtered ITO/PET films were also superior to the DC sputtered ITO/PET films. The reverse time had little effect on the properties of the ITO/PET film and the frequency of pulsed DC power had an immerse effect on the properties of the ITO/PET films. The optimal ITO/PET film was obtained when the frequency was 200 kHz, the reverse time was 1 μs, and the duty ratio was about 80%.     

Epitaxial growth of delafossite CuFeO2 thin films by pulse laser deposition

CuFeO₂ (CFO) is a delafossite-type compound and is a well known p-type semiconductor. Epitaxial CuFeO₂ thin films were prepared on Al₂O₃ (0 0 0 1) substrates by pulsed laser deposition. The deposition, performed at 500 °C and 10 Pa leads to epitaxial phase with extremely low roughness and high density. The oxygen pressure modulates the band energy properties of Cu 2p, Fe 3p and O1s. The results show that the low deposition oxygen pressure contributes to the chemistry ingredient and magnetization properties. Furthermore, spin-glass behavior is identified and weak-ferromagnetization property is found at a low temperature about ∼5 K.     

Radio-frequency assisted pulsed laser deposition of nanostructured WOx films

The synthesis of tungsten oxide films with large surface area is promising for gas sensing applications. Thin WO_x films were obtained by radio-frequency assisted pulsed laser deposition (RF-PLD). A tungsten target was ablated at 700 and 900 Pa in reactive oxygen, or in a 50% mixed oxygen-helium atmosphere at the same total pressure values. Corning glass was used as substrate, at temperatures including 673, 773 and 873 K. Other deposition parameters such as laser fluence (4.5 J cm⁻²), laser wavelength (355 nm), radiofrequency power (150 W), target to substrate distance (4 cm), laser spot area (0.7 mm²), and number of laser shots (12,000) were kept fixed. The sensitivity on the deposition conditions of morphology, nanostructure, bond coordination, and roughness of the obtained films were analyzed by scanning and transmission electron microscopy, micro-Raman spectroscopy, and atomic force microscopy.     

In situ grown epitaxial YBa2Cu3O7 − x thin films by pulsed laser deposition under reduced oxygen pressure during cool-down time

We report novel pulsed laser deposition conditions that were used to obtain superconducting epitaxial YBCO thin films, grown in situ using an oxygen pressure lower than the usual one during the cool-down time. We studied the influence of the PLD conditions as substrate temperature, oxygen pressure, laser fluence, and number of laser pulses on the crystallographic and morphological features, and on the superconducting properties of the films. Good superconducting properties were obtained without a high temperature post-deposition annealing process. A maximum critical temperature of 88.6 K was obtained.     

Effect of substrate temperature and oxygen partial pressure on microstructure and optical properties of pulsed laser deposited yttrium oxide thin films

Yttrium oxide thin films were deposited on Si (1 1 1) and quartz substrates by pulsed laser deposition technique at different substrate temperature and oxygen partial pressure. XRD analysis shows that crystallite size of the yttrium oxide thin films increases as the substrate temperature increases from 300 to 873 K. However the films deposited at constant substrate temperature with variable oxygen partial pressure show opposite effect on the crystallite size. Band gap energies determined from UV-visible spectroscopy indicated higher values than that of the reported bulk value.     

Cobalt and tantalum additions for enhanced electrochromic performances of nickel-based oxide thin films grown by pulsed laser deposition

Aiming at improving the durability of anodic electrochromic nickel oxide thin films, Ni-M-O (M = Co, Ta) thin films were grown by pulsed laser deposition (PLD), using optimized conditions, namely room temperature and 10⁻¹ mbar oxygen pressure. For low Co and Ta contents (<5%), both additions lead to a loss of the [1 1 1] preferred orientation of the NiO rock-salt structure followed by a film amorphization with increasing Ta amount. Among the two series of metal additions (M ≤ 20%), the Ni-Co-O (5% Co) and Ni-Ta-O (10% Ta) thin films show the highest electrochemical performances especially in respect of improved durability. If the enhanced properties are associated with a limited dissolution of the oxidized phase for the Ni-Ta-O system, the opposite trend is observed for the Ni-Co-O system as compared to pure NiO.     

Growth of oxide thin films for optical gas sensor applications

Tungsten trioxide and titanium dioxide thin films were synthesised by pulsed laser deposition. We used for irradiations of oxide targets an UV KrF* (λ = 248 nm, τ_FWHM ≅ 20 ns, ν = 2 Hz) excimer laser source, at 2 J/cm² incident fluence value. The experiments were performed in low oxygen pressure. The (0 0 1) SiO₂ substrates were heated during the thin film deposition process at temperature values within the 300-500 °C range. The structure and crystalline status of the obtained oxide thin films were investigated by high resolution transmission electron microscopy. Our analyses show that the films are composed by nanoparticles with average diameters from a few to a few tens of nm. Moreover, the films deposited at substrate temperatures higher than 300 °C are crystalline. The tungsten trioxide films consist of a mixture of triclinic and monoclinic phases, while the titanium dioxide films structure corresponds to the tetragonal anatase phase. The oxide films average transmittance in the visible-infrared spectral range is higher than 80%, which makes them suitable for sensor applications.     

Structural characterization and magnetoresistance of manganates thin films and Fe-doped manganates thin films

Perovskites thin films with the composition La_0.6Ca_0.4MnO₃ doped with 20% Fe, were prepared by pulsed reactive crossed beam laser ablation, where a synchronized reaction gas pulse interacts with the ablation plume. The films were grown on various substrates and the highest colossal magnetoresistance ratio (CMR) was detected by Hall measurements for films grown on LaAlO₃ (1 0 0), which was selected as substrate for further investigations.Several growth parameters, such as substrate temperature and target to substrate distance were varied to analyze their influence on the film properties.The structure of the deposited thin films was characterized by X-ray diffraction and atomic force microscope, while Rutherford backscattering (RBS) was used to determine the film stoichiometry. The electrical properties were determined by Hall effect measurements in a magnetic field of 0.51 T.These measurements reveal that the amplitude of the CMR ratio depends strongly on the substrate and that the oxygen content influences the temperature where the transition from semiconductor to metal is observed.     

Preparation and characterization of indium tin oxide films formed by oxygen ion beam assisted deposition

Indium tin oxide (ITO) films were produced by low-energy oxygen ion beam assisted electron-beam evaporation. The dependence of surface morphology, electrical and optical properties on evaporation rate, oxygen ion beam energy and density, as well as substrate temperatures was characterized by atomic force microscopy, X-ray photoelectron spectroscopy, Hall-effect and optical transmittance measurements. The results show that high-quality ITO films (resistivity of 7.0×10⁻⁴ Ω cm, optical transmittance above 85% at wavelength 550 nm, surface roughness of 0.6 nm in root mean square) can be obtained at room temperature.     

Role of vanadium content in ZnO thin films grown by pulsed laser deposition

Vanadium-doped ZnO films (Zn_1−xV_xO, where x = 0.02, 0.03, 0.05 and 0.07), were formed from ceramic targets on c-cut sapphire substrates using pulsed laser deposition at substrate temperature of 600 °C and oxygen pressure of 10 Pa. In order to clarify how the vanadium concentration influences the films’ properties, structural and magnetic investigations were performed. All films crystallised in wurtzite phase and presented a c-axis preferred orientation at low concentrations of vanadium. The results implied that the doping concentration and crystalline microstructure influence strongly the system's magnetic characteristics. Weak ferromagnetism was registered for the film with the lowest doping concentration (2 at.%), which exhibited a ferromagnetic behavior at Curie temperature higher than 300 K. Increasing the vanadium content in the film caused degradation of the magnetic ordering.     

Characterization of tungsten-titanium oxide electrode for electrochromic applications

Titanium oxide films are of critical importance for the electrochromic device technology. The substrate, a conductive glass being coated with indium tin oxide (ITO) thin films, was deposited tungsten and titanium oxide by pulsed co-sputtering deposition system. The film thickness increased with the ion beam power. However, the slope of the curve of thickness against power at an ion beam power of less than 300 W was greater than that at a power of 400 or 500 W. A high ion beam power resulted produced a crystalline structure, as revealed by X-ray diffraction (XRD). Moreover, increasing the ion beam power resulted in the high Li-ions transport. The electrochromic behavior was optimal at an ion beam power of 200 W.     

Structural and optical properties of ZnO thin films deposited on quartz glass by pulsed laser deposition

ZnO thin films with typical c-axis (0 0 2) orientation were successfully deposited on quartz glass substrates by pulse laser ablation of Zn target in oxygen atmosphere at a relatively low temperature range of 100-250 °C. The structural and optical properties of the films were studied. In photoluminescence (PL) spectra at room temperature, single ultraviolet emission (without deep-level emission) was obtained from ZnO film deposited at the temperature of 200 °C. This was attributed to its low intrinsic defects.     

Influence of substrate temperature and post-treatment on the properties of ZnO:Al thin films prepared by pulsed laser deposition

Highly transparent conductive Al₂O₃ doped zinc oxide (AZO) thin films have been deposited on the glass substrate by pulsed laser deposition technique. The effects of substrate temperature and post-deposition annealing treatment on structural, electrical and optical properties of AZO thin films were investigated. The experimental results show that the electrical resistivity of films deposited at 240 °C is 6.1 × 10⁻⁴ Ω cm, which can be further reduced to as low as 4.7 × 10⁻⁴ Ω cm by post-deposition annealing at 400 °C for 2 h in argon. The average transmission of AZO films in the visible range is 90%. The optical direct band gap of films was dependent on the substrate temperature and the annealing treatment in argon. The optical direct band gap value of AZO films increased with increasing annealing temperature.     

Properties of Zn3N2-doped ZnO films deposited by pulsed laser deposition

The optical properties of N-doped ZnO films grown by pulsed laser deposition are examined for which zinc nitride is used as the source of nitrogen. The motivation for this study is to determine if nitrogen-related acceptor state formation can be achieved in ZnO films using Zn₃N₂ doping in the ablation target. The films were deposited in oxygen or nitrogen on c-plane sapphire. Photoluminescence measurements at 20 K reveal a 3.31 eV acceptor-bound exciton emission due to nitrogen substitution on the oxygen site, donor-acceptor pair emission at 3.23 ± 1 eV and free electron-acceptor at 3.27 eV. The binding energy of the N-related acceptor is estimated to be in the range of 170-15 meV. While the as-deposited films were n-type, thermal annealing in oxygen yielded insulating behavior, consistent with compensating acceptor states.     

Effect of substrate temperature on the growth of ITO thin films

Indium tin oxide (ITO) thin films were deposited onto glass substrates by rf magnetron sputtering of ITO target and the influence of substrate temperature on the properties of the films were investigated. The structural characteristics showed a dependence on the oxygen partial pressure during sputtering. Oxygen deficient films showed (4 0 0) plane texturing while oxygen-incorporated films were preferentially oriented in the [1 1 1] direction. ITO films with low resistivity of 2.05 × 10⁻³ Ω cm were deposited at relatively low substrate temperature (150 °C) which shows highest figure of merit of 2.84 × 10⁻³ square/Ω⋅     

Electron transport in semiconducting nanoparticle and nanocluster carbon-polymer composites

The electron transport properties of two types of carbon-polyimide (C-PI) nanocomposite thin films have been evaluated. Conductive nanocomposites formed by incorporation of 30 nm carbon particles prior to polymer cross linking (ex situ formation) has been compared to high energy ion beam irradiation in situ formation of nanoscale carbon clusters within the polymer composite. Addition of carbon nanoparticles were able to reduce the resistivity by 13 orders of magnitude for 8 vol% carbon content. The irradiated in situ formed film showed a comparable resistivity to this 8% C-PI film. All the films exhibited negative temperature coefficient of resistance (NTCR) behaviour. While in the ex situ films the NTCR decreased progressively with increasing temperature above 350 K, the in situ film exhibited a constant NTCR value at ambient as well as elevated temperatures indicating that films formed by ion beam irradiation eliminate possible clustering of nanoparticles prior to crosslinking seen in the ex situ films. The optimum hop energies for the ex situ films ranged from 23.1 to 8.05 meV when carbon content increased from 1 to 8 vol% and the corresponding value for the in situ formed film was 34.94 meV. These films had appreciable NTCR values, and were evaluated for their thermistor behaviour as a class of material with potential for temperature sensing devices.     

Investigation of diffusion and crystallization processes in thin ITO films by temperature and time resolved grazing incidence X-ray diffractometry

Oxygen diffusion into metallic In/Sn films and crystallite growth of thin indium tin oxide (ITO) films were investigated by in situ high temperature grazing incidence X-ray diffractometry (HT-GIXRD) at temperatures ranging from 100 to 300 °C. The investigated films were deposited by dc magnetron sputtering from a metallic target at different oxygen flows and bias voltages. The deposition process influences not only the film properties but also the film reactions during the post-deposition annealing process.

The ITO formation is determined by two processes: the diffusion of oxygen into the metallic grains and a fast crystallization process. Kinetic parameters for both processes were derived. A model was developed which allows the determination of the diffusion coefficient D from the time dependence of the integral intensity of the ITO X-ray reflection. Diffusion coefficients as well as the activation energies are influenced by the bias voltage but not by the oxygen flow.

According to the Johnson–Mehl–Avrami theory, the crystallization can be described as a two-dimensional process.