Characterization and Low Temperature Study of Iron Telluride Thin Films Upon Ageing and Oxygen Ion Irradiation

The occurrence of superconductivity in iron telluride thin films has been observed upon ageing. The superconducting transition is found to be very robust under an application of magnetic fields up to 10 T. Infrared and Raman spectroscopic characterization of the aged films reveal the formation of Fe_1+δTeO _x upon ageing. As an alternative method of introducing oxygen in FeTe thin film, oxygen ion irradiation has also been carried out It is found that the irradiated film becomes increasingly disordered and ultimately transforms to an amorphous phase upon increasing the irradiation dose. Investigation of electrical resistivity and optical reflectivity of the irradiated FeTe films indicates an interesting possibility of an ion irradiationinduced phase change memory material in analogy to the phase change characteristics of laserirradiated FeTe films.     

The large modification of phase transition characteristics of VO2 films on SiO2/Si substrates

The vanadium oxide (VO₂) films have been prepared on SiO₂/Si substrates by using a modified Ion Beam Enhanced Deposition (IBED) method. During the film deposition, high doses of Ar⁺ and H⁺ ions have been implanted into the deposited films from the implanted beam. The resistance change of the VO₂ films with temperature has been measured and the phase transition process has been observed by using the X-ray Diffraction technique. The phase transition of the IBED VO₂ films starts at a low temperature of 48 °C and ends at a high temperature of 78 °C. It is found that the phase transition characteristics can be adjusted by changing the annealing temperature or the time and the phase transition characteristics of the IBED VO₂ films depend on the quantity and location of argon atoms in the film matrix.     

Optical properties of thin films of amorphous vanadium oxides

The results of an experimental investigation of the optical properties of anodic vanadium oxide films are presented. It is shown that films of different phase composition (VO₂, V₂O₅, or a mixture of two phases) can be obtained, depending on the oxidation regime, and that the absorption and transmission spectra are modified significantly in accordance. The optical properties of the oxides, whose composition is close to stoichiometric vanadium dioxide, demonstrate the occurrence of a metal-semiconductor phase transition in the amorphous films. The results presented are important both from the standpoint of technical applications of thin film systems based on anodic vanadium oxides and for more detailed understanding of the physical mechanism of the metal-semiconductor phase transition and the influence of structural disorder on the transition. Pis’ma Zh. Tekh. Fiz. 25, 81–87 (April 26, 1999)     

Study on optical and electrical switching properties and phase transition mechanism of Mo6+-doped vanadium dioxide thin films

In the present work using V₂O₅ and MoO₃ powders as precursors, a novel method, the inorganic sol-gel method, was developed to synthesize Mo⁶⁺ doped vanadium dioxide (VO₂) thin films. The structure, valence state, phase transition temperature, magnitude of resistivity change and change in optical transmittance below and above the phase transition of these films are determined by XRD, XPS, four-point probe equipment and spectrophotometer. The results showed that the main chemical composition of the films was VO₂, the structure of MoO₃ in the films didn't change, and the phase transition temperature of the VO₂ was obviously lowered with increasing MoO₃ doped concentration. The magnitude of resistivity change and change in optical transmittance below and above phase transition were also decreased, of which the magnitude of resistivity change was more distinct. However, when the MoO₃ concentration was 5 wt%, the magnitude of resistivity change of doped thin films still reached more than 2 orders, and the change in optical transmittance below and above phase transition was maintained. Analysis showed that the VO₂ doped films formed local energy level, and then reduced the forbidden band gap of VO₂ as the donor defect changing its optical and electrical properties and lowering the phase transition temperature.     

Electron-beam modification of the parameters of the insulator-metal phase transition in vanadium dioxide films

Using optical spectroscopy, Raman scattering, and optical diffractometry, modification of the parameters of the insulator-metal transition in VO₂ films upon bombardment with a mean-energy (6–10 keV) electron beam is investigated. It is shown that growth of the irradiation dose leads to a decrease in the temperature of the phase transition, an increase in the reflectance and a decrease in its jump, a change of phonon peaks of the monoclinic phase for broad bands characteristic of the tetragonal phase in the Raman spectrum, and a shift of the reflection-spectrum features to the short-wavelength region by 65 nm. The modification is attributed to the generation of oxygen vacancies with the donor properties in the crystal lattice.     

Strain effects and phase separation tendency in highly strained La0.7Ba0.3MnO3 thin films on LaAlO3 substrates

The magnetic and transport properties of epitaxial La_0.7Ba_0.3MnO₃ films on LaAlO₃ substrates have been investigated and compared with those on SrTiO₃ substrates. It is found that the ferromagnetic and metallic transition temperature of the highly compressive strained films on LaAlO₃ substrates decreases steadily with decreasing film thickness, while it changes little in the lightly strained films on SrTiO₃ substrates. The properties of the films on LaAlO₃ substrates are more sensitive to a post-annealing procedure. A tendency to phase separation, which induces a difference between the insulator-metal transition temperature T_MI and the Curie temperature T_C, is observed for the films with a medium oxygen annealing process. We argue that the phase separation is due to both the highly compressive strain and oxygen deficiency in the films.     

Direct current electric field adjustable phase transformation behavior in (Pb,La)(Zr,Ti)O3 antiferroelectric thick films

(Pb,La)(Zr,Ti)O₃ antiferroelectric 1.4 μm-thick films have been prepared on Pt (111)/Ti/SiO₂/Si(100) substrates by sol–gel process. The structures and dielectric properties of the antiferroelectric thick films were investigated. The films displayed pure perovskite structure with (100)-preferred orientation. The surface of the films was smooth, compact and uniform. The antiferroelectric (AFE) characterization have been demonstrated by P (polarization)-E (electric field) and C(capacitance)-V (DC bias) curves. The AFE–ferroelectric (FE) and FE-to-paraelectric (PE) phase transition were also investigated as coupling functions of temperature and direct current electric field. With the applied field increased, the temperature of AFE-to-FE phase transition decreased and the FE-to-PE phase shifted to high temperature. The AFE-to-FE phase transition was adjustable by direct current electric field. (Pb,La) (Zr,Ti) O₃ antiferroelectric films have broad application prospects in microelectromechanical systems because of the phase transition.     

Influence of ion irradiation effects on the hydriding behavior of nanocrystalline Mg-Ni films

Mg-Ni films were grown on a silicon substrate using two magnetron sputter deposition sources and simultaneous Ar ion irradiation. X-ray diffraction microstructure and phase composition, EDX elemental composition and atomic force microscopy surface topography analysis showed that under low-energy Ar ion irradiation (bias voltages from 0 to −120 V), the Mg₂Ni phase was dominant and on the contrary with the increase of ion energy (bias voltages from −120 to −200 V), the MgNi₂ phase appeared. The Mg content changed from 63 at% down to 42 at% in films grown under bias voltages of 0 and −200 V, respectively. During hydrogenation at 8 bar, 270 °C for 3 h, films with a dominant phase of Mg₂Ni were transformed into Mg₂NiH₄. Hydrogen in MgNi₂ films was mainly in interstitials and tended to form bubbles.     

TiO2 anatase thin films deposited by spray pyrolysis of an aerosol of titanium diisopropoxide

Titanium dioxide thin films were deposited on crystalline silicon (100) and fused quartz substrates by spray pyrolysis (SP) of an aerosol, generated ultrasonically, of titanium diisopropoxide. The evolution of the crystallization, studied by X-ray diffraction (XRD), atomic force (AFM) and scanning electron microscopy (SEM), reflection and transmission spectroscopies, shows that the deposition process is nearly close to the classical chemical vapor deposition (CVD) technique, producing films with smooth surface and good crystalline properties. At deposition temperatures below 400 °C, the films grow in amorphous phase with a flat surface (roughness∼0.5 nm); while for equal or higher values to this temperature, the films develop a crystalline phase corresponding to the TiO₂ anatase phase and the surface roughness is increased. After annealing at 750 °C, the samples deposited on Si show a transition to the rutile phase oriented in (111) direction, while for those films deposited on fused quartz no phase transition is observed.     

Structural, electrical and optical properties of thermochromic VO2 thin films obtained by reactive electron beam evaporation

We present the structural and physical characterization of vanadium dioxide (VO₂) thin films prepared by reactive electron beam evaporation from a vanadium target under oxygen atmosphere. We correlate the experimental parameters (substrate temperature, oxygen flow) with the films structural properties under a radiofrequency incident power fixed to 50 W. Most of the obtained layers exhibit monocrystalline structures matching that of the monoclinic VO₂ phase. The temperature dependence of the electrical resistivity and optical transmission for the obtained films show that they present thermoelectric and thermochromic properties, with a phase transition temperature around 68 °C. The results show that for specific experimental conditions the VO₂ layers exhibit sharp changes in electrical and optical properties across the phase transition.     

Compositional and metal-insulator transition characteristics of sputtered vanadium oxide thin films on yttria-stabilized zirconia

Vanadium dioxide (VO₂) thin films have been shown to undergo a rapid electronic phase transition near 70 °C from a semiconductor to a metal, making it an interesting candidate for exploring potential application in high speed electronic devices such as optical switches, tunable capacitors, and field effect transistors. A critical aspect of lithographic fabrication in devices utilizing electric field effects in VO₂ is the ability to grow VO₂ over thin dielectric films. In this article, we study the properties of VO₂ grown on thin films of Yttria-Stabilized Zirconia (YSZ). Near room temperature, YSZ is a good insulator with a high dielectric constant ($\epsilon _{\rm r} > 25$\epsilon _{\rm r} > 25). We demonstrate the sputter growth of polycrystalline VO₂ on YSZ thin films, showing a three order resistivity transition near 70 °C with transition and hysteresis widths of approximately 7 °C each. We examine the relationship between chemical composition and transition characteristics of mixed phase vanadium oxide films. We investigate changes in composition induced by low temperature post-deposition annealing in oxidizing and reducing atmospheres, and report their effects on electronic properties.     

Some features of the formation of structure and properties of transition metal diboride and boronitride films

The formation of structure and the development of mechanical properties in films of transition metal diborides (MeB₂) and boronitrides (MeBN) grown by rf magnetron sputtering have been studied. The most characteristic features are (i) the formation of a columnar structure and axial texture on (00.1) planes in MeB₂ films grown by nonreactive magnetron sputtering and (ii) the formation of a composite that consists of a nanocrystalline MeB₂ phase and an amorphous BN phase in films grown by the reactive sputtering in Ar + N₂ gas mixtures.     

Investigation on the structure of TiO2 films sputtered on alloy substrates

Titanium dioxide (TiO₂) films have been successfully deposited on metal alloy substrates by radio-frequency magnetron reactive sputtering in an Ar+O₂ gas mixture. The effects of gas total pressure on the structure and phase transition of TiO₂ films were studied by X-ray diffraction and Raman spectra. It is suggested that the film structure changes from rutile to anatase while work gas total pressure changes from 0.2 to 2 Pa. The structure of TiO₂ films is not affected by the film thickness.     

Effects of Heat Treatment on the Microstructure and Optical Properties of Sputtered GeO2 Thin Films

Microstructure and composition significantly influence the physical properties of thin films. Therefore, these can be adapted to enhance the functionality of thin films for practical applications. Herein, the anomalous microstructural evolution of sputtered GeO₂ thin films based on postdepositional heat treatments is reported. Temperature-dependent microstructural variations are investigated systematically via a combinatorial postdepositional heat treatment employing a natural thermal gradient in a tube furnace. Heat treatment under an oxidizing atmosphere results in a transition from the amorphous phase to the quartz phase, and subsequent heat treatments under a reducing atmosphere cause H₂O-incorporated chemical reactions. Hence, these conditions create unique microstructural features and yield optical transmittance variations in the GeO₂ thin films. The phase transition induces the formation of spherulitic hexagonal GeO₂ crystallites, and further increase in the temperature promotes the agglomeration of crystallites in the amorphous matrix. The incorporation of H₂O results in the growth of the microstructure, and the chemical reduction to Ge metal begins to generate small granules from the boundary of the microstructures. The experimental results and proposed mechanisms presented herein for the microstructural and compositional changes serve as references for designing the physical properties of thin films.     

Structural and optical properties of GaGeTe thin films

Smooth and pinhole-free thin films of Ga₅Ge₁₉Te₇₆ have been obtained by vacuum evaporation. The as-deposited films are amorphous. Thermal annealing at 222°C leads to an amorphous-to-crystalline transition. A maximum contrast of 30% in reflectivity (measured at 1 µm) has been obtained on phase transition from amorphous to crystalline state. The optical constants and the bandgap are reported.     

Superconducting beryllium films

Resistance-vs.-temperature measurements were made on a series of beryllium films condensed on liquid-helium cooled surfaces. Two vapor sources designed to reduce contamination were used and films were prepared on both crystalline quartz and glass substrates. The samples were superconducting with a transition temperature ofT _c =9.6±0.1 K as indicated by a sharp falloff of resistance on cooling. This qualitatively confirms earlier reports of the superconductivity of quenched beryllium films. The transition curves were, however, appreciably sharper and the transition temperature about a degree higher than previously reported. Good agreement found from sample to sample indicates that the residual impurity concentration was small enough to be unimportant and that the observed transition temperature is characteristic of pure beryllium. The phase of beryllium responsible for the highT _c value disappeared on annealing in the range 40–60 K. No indication was found of a reportedT _c 6-K phase. Beryllium films thicker than about 750 Å broke up during deposition, indicating the presence of large stresses.The work at Karlsruhe was supported by the Deutsche Forschungsgemeinschaft, Germany.     

Surface modification of yttria-stabilized-zirconia thin films under various oxygen partial pressures

This report discusses the structural and spectroscopic analysis of yttria-stabilized-zirconia (YSZ) thin films grown on Al₂O₃(0001) substrates. It is found that the changes of oxygen partial pressure during the growth are closely related to the surface chemical compositions and the surface crystal orientations of the thin films. The presence of oxygen partial pressure produces a polycrystalline structure on the thin film while a preferred orientation of crystal structures is formed under no oxygen partial pressure. Difficulty arises in identifying the structure of the thin films due to the broad characteristics of the x-ray diffraction (XRD) peaks; however, the XRD rocking scan suggests the existence of two lateral domain sizes. The chemical analysis of the thin films from x-ray photoelectron spectroscopy measurements indicates the enrichment of surface yttrium-oxide as the oxygen partial pressure increases. The detailed analysis of valence band spectra also suggests that the thin films undergo a surface structural phase transition, i.e., transforming from a single tetragonal structure to a mixed (cubic + monoclinic) structure. Furthermore, the optical data display the small increments of the band gap as the oxygen partial pressure increases, which reflects the presence of the structural phase transition of the thin films.     

Properties of tungsten-doped vanadium oxide films

The structure and properties of tungsten-doped vanadium pentoxide and dioxide films grown by the sol-gel method have been studied. The data of x-ray diffraction investigation and the temperature dependences of conductivity measured in a broad temperature range (50–380 K) are presented. The temperature of the metalsemiconductor phase transition in vanadium dioxide decreases with an increase in the dopant concentration. The phase transition is not observed in the films with tungsten concentrations above 6%. The radius of electron localization on vanadium ions in V_1?x W _x O₂ has been estimated. The results of the investigation of the switching effect in tungsten-doped vanadium pentoxide hydrate are reported.     

Tailoring Materials for Mottronics: Excess Oxygen Doping of a Prototypical Mott Insulator

The Mott transistor is a paradigm for a new class of electronic devices—often referred to by the term Mottronics—which are based on charge correlations between the electrons. Since correlation‐induced insulating phases of most oxide compounds are usually very robust, new methods have to be developed to push such materials right to the boundary to the metallic phase in order to enable the metal–insulator transition to be switched by electric gating. Here, it is demonstrated that thin films of the prototypical Mott insulator LaTiO₃ grown by pulsed laser deposition under oxygen atmosphere are readily tuned by excess oxygen doping across the line of the band‐filling controlled Mott transition in the electronic phase diagram. The detected insulator to metal transition is characterized by a strong change in resistivity of several orders of magnitude. The use of suitable substrates and capping layers to inhibit oxygen diffusion facilitates full control of the oxygen content and renders the films stable against exposure to ambient conditions. These achievements represent a significant advancement in control and tuning of the electronic properties of LaTiO_3+x thin films making it a promising channel material in future Mottronic devices.     

R.F. and D.C. reactive sputtering for crystalline and amorphous VO2 thin film deposition

The experimental conditions for depositing VO₂ thin films with a semiconductor-to-metal phase transition are described and the influence of the film deposition parameters on the transition properties are analysed.