Influence of annealing on structural, morphological, compositional and surface properties of magnetron sputtered nickel-titanium thin films

Thin films of NiTi were deposited by DC magnetron sputtering from an equiatomic alloy target (Ni/Ti: 50/50 at.%). The films were deposited without intentional heating of the substrates. The thickness of the deposited films was approximately 2 mu m. The structure and morphology of NiTi films annealed at different temperatures were analyzed in order to understand the effect of annealing on physical properties of the films. The compositional investigations of fresh and annealed films were also evaluated by energy dispersive X-ray spectroscopy (EDS) and X-ray photo-electron spectroscopy (XPS) techniques. X-ray diffraction (XRD) studies showed that as-deposited films were amorphous in nature whereas annealed films were found to poly-crystalline with the presence of Austenite phase as the dominant phase. AFM investigations showed higher grain size and surface roughness values in the annealed films. In annealed films, the grain size and film roughness values were increased from 10 to 85 nm and 2-18 nm. Film composition measured by EDS were found to 52.5 atomic percent of Ni and 47.5 atomic percent of Ti. XPS investigations, demonstrated the presence of Ni content on the surface of the films, in fresh films, whereas annealed films did not show any nickel. From HR-XPS investigations, it can be concluded that annealed NiTi films have higher tendency to form metal oxide (titanium dioxide) layer on the surface of the films than fresh NiTi films. (C) 2013 Elsevier B. V. All rights reserved.

Tuning the photoluminescence of ZnO thin films by indium doping

Zinc Oxide (ZnO) and indium doped ZnO (IZO) thin films with different indium compositions were grown on p-type boron doped Si substrates by pulsed laser deposition (PLD). The effect of indium concentration on the structural, optical and electrical properties of the film was studied. XRD, XPS and Raman studies confirm the single phase formation and successful doping of In in to ZnO. We observed various photoluminescence emissions, ranging from UV to visible, with the incorporation of In into ZnO. Room temperature Current-Voltage (I-V) characteristics showed good p-n junction properties for n-type-undoped and In doped ZnO with p-type substrates. The turn on voltage was observed to be decreasing with increase in In composition.

RF plasma MOCVD of Y2O3 thin films: Effect of RF self-bias on the substrates during deposition

Yttrium oxide (Y203) thin films have been deposited by radio frequency plasma assisted metal organic chemical vapor deposition (MOCVD) process using (2,2,6,6-tetramethy1-3,5-heptanedionate) yttrium (commonly known as Y(thd)3) precursor in a plasma of argon and oxygen gases at a substrate temperature of 350 C. The films have been deposited under influence of varying RF self-bias (-50 V to 175 V) on silicon, quartz, stainless steel and tantalum substrates. The deposited coatings are characterized by glancing angle X-ray diffraction (GIXRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), spectroscopic ellipsometry and scanning electron microscopy (SEM). GIXRD and FTIR results indicate deposition of Y2 03 (BCC structure) in all cases. However, XPS results indicate nonstoichiometric cubic phase deposition on the surface of deposited films. The degree of nonstoichiometry varies with bias during deposition. Ellipsometry results indicate that the refractive index for the deposited films is varying from 1.70 to 1.83 that is typical for Y203. All films are transparent in the investigated wavelength range 300-1200 nm. SEM results indicate that the microstructure of the films is changing with applied bias. Results indicate that it is possible to deposit single phase cubic Y203 thin films at low substrate temperature by RF plasma MOCVD process. RF self-bias that decides about the energy of impinging ions on the substrates plays an important role in controlling the texture of deposited Y203 films on the substrates. Results indicate that to control the structure of films and its texture, it is important to control the bias on the substrate during deposition. The films deposited at high bias level show degradation in the crystallinity and reduction of thickness. (C) 2013 Elsevier B.V. All rights reserved.

Effect of chemical treatment on surface characteristics of sputter deposited Ti-rich NiTi shape memory alloy thin-films

NiTi thin-films were deposited by DC magnetron sputtering from single alloy target (Ni/Ti: 45/55 aL.%). The rate of deposition and thickness of sputter deposited films were maintained to similar to 35 nm min(-1) and 4 mu m respectively. A set of sputter deposited NiTi films were selected for specific chemical treatment with the solution comprising of de-ionized water, HF and HNO3 respectively. The influence of chemical treatment on surface characteristics of NiTi films before and after chemical treatment was investigated for their structure, micro-structure and composition using different analytical techniques. Prior to chemical treatment, the composition of NiTi films using energy dispersive X-ray dispersive spectroscopy (EDS), were found to be 51.8 atomic percent of Ti and 48.2 atomic percent of Ni. The structure and morphology of these films were investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM). XRD investigations, demonstrated the presence of dominant Austenite (110) phase along with Martensite phase, for untreated NiTi films whereas some additional diffraction peaks viz. (100), (101), and (200) corresponding to Rutile and Anatase phase of Titanium dioxide (TiO2) along with parent Austenite (110) phase were observed for chemically treated NiTi films. FTIR studies, it can be concluded that chemically treated films have higher tendency to form metal oxide/hydroxide than the untreated NiTi films. XPS investigations, demonstrated the presence of Ni-free surface and formation of a protective metal oxide (TiO2) layer on the surface of the films, in both the cases. The extent of the formation of surface oxide layer onto the surface of NiTi films has enhanced after chemical treatment. (C) 2014 Elsevier B.V. All rights reserved.

Effect of post-deposition annealing on composition and electrical properties of dc reactive magnetron sputtered Al2O3 thin films

We have investigated the effect of post- deposition annealing on the composition and electrical properties of alumina (Al2O3) thin films. Al2O3 were deposited on n-type Si < 100 >. substrates by dc reactive magnetron sputtering. The films were subjected to post- deposition annealing at 623, 823 and 1023 K in vacuum. X-ray photoelectron spectroscopy results revealed that the composition improved with post- deposition annealing, and the film annealed at 1023 K became stoichiometric with an O/Al atomic ratio of 1.49. Al/Al2O3/Si metal-oxide-semiconductor (MOS) structures were then fabricated, and a correlation between the dielectric constant epsilon(r) and interface charge density Q(i) with annealing conditions were studied. The dielectric constant of the Al2O3 thin films increased to 9.8 with post- deposition annealing matching the bulk value, whereas the oxide charge density decreased to 3.11 x 10(11) cm(-2.) Studies on current-voltage IV characteristics indicated ohmic and Schottky type of conduction at lower electric fields (<0.16 MV cm(-1)) and space charge limited conduction at higher electric fields.

Effect of film thickness and annealing on optical properties of TiO2 thin films and electrical characterization of MOS capacitors

Titanium dioxide (TiO2) thin films were deposited on glass and silicon (100) substrates by the sol-gel method. The influence of film thickness and annealing temperature on optical transmittance/reflectance of TiO2 films was studied. TiO2 films were used to fabricate metal-oxide-semiconductor capacitors. The capacitance-voltage (C-V), dissipation-voltage (D-V) and current-voltage (I-V) characteristics were studied at different annealing temperatures and the dielectric constant, current density and resistivity were estimated. The loss tangent (dissipation) increased with increase of annealing temperature.

Probing a spin-glass state in SrRuO3 thin films through higher-order statistics of resistance fluctuations

The complex perovskite oxide SrRuO3 shows intriguing transport properties at low temperatures due to the interplay of spin, charge, and orbital degrees of freedom. One of the open questions in this system is regarding the origin and nature of the low-temperature glassy state. In this paper we report on measurements of higher-order statistics of resistance fluctuations performed in epitaxial thin films of SrRuO3 to probe this issue. We observe large low-frequency non-Gaussian resistance fluctuations over a certain temperature range. Our observations are compatible with that of a spin-glass system with properties described by hierarchical dynamics rather than with that of a simple ferromagnet with a large coercivity.

Enhancing the photocatalytic efficiency of sprayed ZnO thin films through double doping (Sn plus F) and annealing under different ambiences

Doubly (Sn + F) doped zinc oxide (ZnO:Sn:F) thin films were deposited onto glass substrates using a simplified spray pyrolysis technique. The deposited films were annealed at 400 degrees C under two different ambiences (air and vacuum) for 2 h. The photocatalytic activity of these films was assessed through photocatalytic decolorization kinetics of Methylene Blue (MB) dye and the decolorization efficiency of the annealed films was compared with that of their as-deposited counterpart. The photocatalytic studies reveal that the ZnO:Sn:F films annealed under vacuum environment exhibits better photocatalytic efficiency when compared with both air annealed and as-deposited films. The SEM and TEM images depict that the surface of each of the films has an overlayer comprising of nanobars formed on a bottom layer, having spherical grains. The studies show that the diameter of the nanobars plays crucial role in enhancing the photocatalytic activity of the ZnO:Sn:F films. The structural, optical and electrical studies substantiate the discussions on the photocatalytic ability of the deposited films. (C) 2014 Elsevier B.V. All rights reserved.

Effect of Pt doping on the gas sensing properties of porous chromium oxide films through a kinetic response analysis approach

The effect of doping trace amounts of noblemetals (Pt) on the gas sensing properties of chromium oxide thin films, is studied. The sensors are fabricated by depositing chromium oxide films on a glass substrate using a modified spray pyrolysis technique and characterized using X-ray diffraction, scanning electron microscopy, transmission electron microscopy and X-ray photoelectron spectroscopy. The films are porous and nanocrystalline with an average crystallite size of similar to 30 nm. The typical p-type conductivity arises due to the presence of Cr vacancies, formed as a result of Cr non-stoichiometry, which is found to vary upon Pt doping. In order to analyze the effect of doping on the gas sensing properties, we have adopted a kinetic response analysis approach, which is based on Langmuir Adsorption isotherm (LA) theory. The sensor response is analyzed with equations obtained from LA theory and time constants as well as energies of adsorption-desorption are evaluated. It is seen that, Pt doping lowers the Schottky barrier height of the metal oxide semiconductor sensor from 222 meV to 172 meV. Subsequently the reduction in adsorption and desorption energies led to enhancement in sensor response and improvement in the kinetics of the sensor response i.e. the response time as well as recovery times of the sensor.

Inductively coupled reactive ion etching studies on sputtered yttria stabilized zirconia thin films in SF6, Cl-2, and BCl3 chemistries

Downscaling of yttria stabilized zirconia (YSZ) based electrochemical devices and gate oxide layers requires successful pattern transfer on YSZ thin films. Among a number of techniques available to transfer patterns to a material, reactive ion etching has the capability to offer high resolution, easily controllable, tunable anisotropic/isotropic pattern transfer for batch processing. This work reports inductively coupled reactive ion etching studies on sputtered YSZ thin films in fluorine and chlorine based plasmas and their etch chemistry analyses using x-ray photoelectron spectroscopy. Etching in SF6 plasma gives an etch rate of 7 nm/min chiefly through physical etching process. For same process parameters, in Cl-2 and BCl3 plasmas, YSZ etch rate is 17 nm/min and 45 nm/min, respectively. Increased etch rate in BCl3 plasma is attributed to its oxygen scavenging property synergetic with other chemical and physical etch pathways. BCl3 etched YSZ films show residue-free and smooth surface. The surface atomic concentration ratio of Zr/Y in BCl3 etched films is closer to as-annealed YSZ thin films. On the other hand, Cl-2 etched films show surface yttrium enrichment. Selectivity ratio of YSZ over silicon (Si), silicon dioxide (SiO2) and silicon nitride (Si3N4) are 1:2.7, 1:1, and 1:0.75, respectively, in BCl3 plasma. YSZ etch rate increases to 53 nm/min when nonoxygen supplying carrier wafer like Si3N4 is used. (C) 2015 American Vacuum Society.

A transmission electron microscopy and X-ray photoelectron spectroscopy study of annealing induced gamma-phase nucleation, clustering, and interfacial dynamics in reactively sputtered amorphous alumina thin films

Pure alpha-Al2O3 exhibits a very high degree of thermodynamical stability among all metal oxides and forms an inert oxide scale in a range of structural alloys at high temperatures. We report that amorphous Al2O3 thin films sputter deposited over crystalline Si instead show a surprisingly active interface. On annealing, crystallization begins with nuclei of a phase closely resembling gamma-Alumina forming almost randomly in an amorphous matrix, and with increasing frequency near the substrate/film interface. This nucleation is marked by the signature appearance of sharp (400) and (440) reflections and the formation of a diffuse diffraction halo with an outer maximal radius of approximate to 0.23 nm enveloping the direct beam. The microstructure then evolves by a cluster-coalescence growth mechanism suggestive of swift nucleation and sluggish diffusional kinetics, while locally the Al ions redistribute slowly from chemisorbed and tetrahedral sites to higher anion coordinated sites. Chemical state plots constructed from XPS data and simple calculations of the diffraction patterns from hypothetically distorted lattices suggest that the true origins of the diffuse diffraction halo are probably related to a complex change in the electronic structure spurred by the a-gamma transformation rather than pure structural disorder. Concurrent to crystallization within the film, a substantially thick interfacial reaction zone also builds up at the film/substrate interface with the excess Al acting as a cationic source. (C) 2015 AIP Publishing LLC.

Single-step synthesis of carbon nanotubes/iron/iron oxide composite films through inert-ambient CVD using ferric acetylacetonate as a precursor

We have developed a unique single-step chemical vapor deposition (CVD) route for the synthesis of composite thin films containing carbon nanotubes (CNTs). CVD was carried out in an inert ambient using only iron(III) acetylacetonate as the precursor. Depositions were conducted at 700 degrees C on stainless steel substrates in argon ambient in the absence of any reactive gases (such as oxygen, hydrogen). By changing the deposition parameters, especially the pressure in the CVD reactor, the form of carbon deposited could be changed from amorphous to carbon nanotubes, the latter resulting in Fe-Fe3O4-CNT films. X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, and electron microscopy together confirm the formation of the three-component composite and illustrate the nanoscale mixing of the components. Elemental iron formed in this process was protected from oxidation by the co-deposited carbon surrounding it. Irrespective of the substrate used, a composite coating with CNTs was formed under optimum conditions, as verified by analyses of the film formed on polycrystalline alumina and silicon substrates.

Growth stress induced tunability of dielectric permittivity in thin films

Stress is inevitable during thin film growth. It is demonstrated here that the growth stress has a significant effect on the dielectric constant of high-k thin films. ZrO2 thin films were deposited on Ge by reactive direct current sputtering. Stress in these films was measured using in-situ curvature measurement tool. The growth stress was tuned from -2.8 to 0.1 GPa by controlling deposition rate. Dielectric permittivity of ZrO2 depends on temperature, phase, and stress. The correct combination of parameters-phase, texture, and stress-is shown to yield films with an equivalent oxide thickness of 8 angstrom. Growth stresses are shown to affect the dielectric constant both directly by affecting lattice parameter and indirectly through the effect on phase stability of ZrO2. (c) 2016 AIP Publishing LLC.

Effect of W addition on the electrical switching of VO2 thin films

Vanadium Oxide has been a frontrunner in the field of oxide electronics because of its metal-insulator transition (MIT). The interplay of different structures of VO2 has played a crucial role in deciding the magnitude of the first order MIT. Substitution doping has been found to introduce different polymorphs of VO2. Hence the role of substitution doping in stabilizing the competing phases of VO2 in the thin film form remains underexplored. Consequently there have been reports both discounting and approving such a stabilization of competing phases in VO2. It is reported in the literature that the bandwidth of the hysteresis and transition temperature of VO2 can be tuned by substitutional doping of VO2 with W. In this work, we have adopted a novel technique called, Ultrasonic Nebulized Spray Pyrolysis of Aqueous Combustion Mixture (UNSPACM) to deposit VO2 and W- doped VO2 as thin films. XRD and Raman spectroscopy were used to investigate the role of tungsten on the structure of VO2 thin films. Morphology of the thin films was found to be consisting of globular and porous nanoparticles of size similar to 20nm. Transition temperature decreased with the addition of W. We found that for 2.0 at % W doping in VO2, the transition temperature has reduced from 68 degrees C to 25 degrees C. It is noted that W-doping in the process of reducing the transition temperature, alters the local structure and also increases room temperature carrier concentration. (c) 2016 Author(s).

Critical investigation of high performance spin-coated high-kappa titania thin films based MOS capacitor

We report the tunable dielectric constant of titania films with low leakage current density. Titanium dioxide (TiO2) films of three different thicknesses (36, 63 and 91 nm) were deposited by the consecutive steps of solution preparation, spin-coating, drying, and firing at different temperatures. The problem of poor adhesion between Si substrate and TiO2 insulating layer was resolved by using the plasma activation process. The surface roughness was found to increase with increasing thickness and annealing temperature. The electrical investigation was carried out using metal-oxide-semiconductor structure. The flat band voltage (V-FB), oxide trapped charge (Q(ot)), dielectric constant (kappa) and equivalent oxide thicknesses are calculated from capacitance-voltage (C-V) curves. The C-V characteristics indicate a thickness dependent dielectric constant. The dielectric constant increases from 31 to 78 as thickness increases from 36 to 91 nm. In addition to that the dielectric constant was found to be annealing temperature and frequency dependent. The films having thickness 91 nm and annealed at 600 A degrees C shows the low leakage current density. Our study provides a broad insight of the processing parameters towards the use of titania as high-kappa insulating layer, which might be useful in Si and polymer based flexible devices.