Effect of oxygen segregation on the surface structure of single-crystalline niobium films on sapphire

Single-crystalline Nb films are grown on (1120) oriented sapphire substrates by electron-beam evaporation in ultra-high vacuum. The films are studied in-situ by RHEED and Auger analysis. At a substrate temperature T _S=750° C the RHEED pattern shows a smooth growth of bcc-Nb in the [110] direction. In addition to the fundamental streaks, we observe superlattice streaks of fractional order in several azimuthal directions. The reciprocal lattice of the surface is determined. The basic vectors of the superlattice in real space are given by b ₁=2a ₁, b ₂=–a ₁+3a ₂ where a ₁ and a ₂ are the basic vectors of the Nb (110) surface. Auger analysis shows that the surface of these films is contaminated with oxygen. Therefore, the superstructure is attributed to a modified surface structure due to segregated oxygen, possibly having diffused from the sapphire to the film surface. The superstructure dissappears during further evaporation of Nb at T _S<450° C with a concomitant decrease of the oxygen signal. Nb films on sapphire with a clean, oxygen-free surface can only be prepared at lower temperatures in an island-growth mode.     

Microstructural investigations of Y2O3 thin films deposited by laser ablation on MgO

The epitaxial relationships and the microstructure of thin Y₂O₃ film, in situ grown by laser ablation at 700 °C under 0.5 mbar oxygen pressure on MgO substrate, are studied by X-ray and HRTEM investigations. X-ray φ-scanexperiments show that Y₂O₃ exhibits two different crystallographic growing directions <111> and <100> on (100) single-crystalline MgO substrate. The <111> growing direction appears with four different epitaxial relationships where the <110> Y₂O₃ in-plane direction is parallel to the <110> in-plane direction of MgO. The <100> growing direction appears with one epitaxial relationship, cube Y₂O₃ on cube MgO. The HRTEM experiments show the columnar aspect of the Y₂O₃ thin film. Both (111) and (100) Y₂O₃-oriented grains are observed in good agreement with the X-ray experiments. Received: 16 May 2000 / Accepted: 22 May 2000 / Published online: 13 September 2000     

Microscopic structure and structuring of perovskite surfaces and interfaces: SrTiO3, RBa2Cu3O7-δ

3 surfaces and bicrystal interfaces and the growth of YBa₂Cu₃O_7-δ thin films on such substrates using scanning tunneling microscopy and X-ray diffraction. Proper annealing of SrTiO₃ in oxygen and/or ultrahigh vacuum produces uniformly terminated, atomically flat and well-ordered surfaces. For vicinal SrTiO₃(001) surfaces the particular annealing sequence and miscut angle sensitively determines the resulting step structure and thus the microscopic surface morphology. Steps of SrTiO₃(001) surfaces can be adjusted to a height of one, two, or multiple times the unit-cell height (a_STO=0.3905 nm). The growth of YBa₂Cu₃O_7-δ films on these substrates by pulsed laser deposition was traced from the initial nucleation to a thickness of about 300 nm. The morphology, texture, and defect structure of the films is determined by the specific structure and morphology of the pristine substrate. Anisotropic, planar defects, originating from substrate step edges, strongly modify the electronic transport properties of the film leading to critical currents up to ≈9×10⁷ A/cm² at 4 K as well as pronounced transport anisotropies. Surfaces and interface energy terms are discussed, which also determine the observed structure of bicrystal boundaries. Received: 16 April 1998/Accepted: 21 August 1998     

Photoluminescence of Y2O3:Eu thin film phosphors by sol-gel deposition and rapid thermal annealing

Y₂O₃:Eu³⁺ phosphor films have been developed by using the sol-gel process. Comprehensive characterization methods such as Photoluminescent (PL) spectroscopy, X-ray diffraction (XRD) and Fourier Transform Infrared (FTIR) spectroscopy were used to characterize the Y₂O₃:Eu³⁺ phosphor films. In this experiment, the XRD profiles show that the Y₂O₃:Eu³⁺ phosphor films crystallization temperature and optimum annealing temperature occur at about 650 and 750 °C, respectively. The optimum dopant concentration is 12 mol% Eu³⁺ and the critical transfer distance (R_c) among Eu³⁺ ions is calculated to be about 0.84 nm. Vacuum environment is more efficient than oxygen and nitrogen to eliminate the OH content and hence yields higher luminescent phosphor films. The PL emission intensity of Y₂O₃:Eu³⁺ phosphor films is also dependent on the annealing time. It was found that the H₂O impurities were effectively eliminated after annealing time of 25 s at 750 °C in vacuum environment. From the experiment results, the schematic energy band diagram of Y₂O₃:Eu³⁺ phosphor films is constructed.     

Growth and characteristics of reactive pulsed laser deposited molybdenum trioxide thin films

Molybdenum trioxide thin films were prepared by reactive pulsed laser deposition on Corning 7059 glass substrates. The influence of oxygen partial pressure and deposition temperature on the structure, surface morphology and optical properties of these films was studied to understand the growth mechanism of MoO₃ thin films. The films formed at 473 K in an oxygen partial pressure of 100 mTorr exhibited predominantly a (0k0) orientation, corresponding to an orthorhombic layered structure of α-MoO₃. The evaluated optical band gap of the films was 3.24 eV. The crystallite size increased with increase of deposition temperature. The films formed at an oxygen partial pressure of pO₂=100 mTorr and at a deposition temperature greater than 700 K exhibited both (0k0) and (0kl) orientations, representing α-β mixed phases of MoO₃. The films formed at an oxygen partial pressure less than 100 mTorr were found to be sub-stoichiometric with α-β mixed phases. The investigation revealed the growth of polycrystalline and single-phase orthorhombic-layered-structure α-MoO₃ thin films with composition nearly approaching the nominal stoichiometry at moderate substrate temperatures in an oxygen partial pressure of 100 mTorr. Received: 9 April 2001 / Accepted: 6 August 2001 / Published online: 17 October 2001     

Growth and characterization of Y2O3 thin films

Y₂O₃ thin films were grown on silicon (1 0 0) substrates by pulsed-laser deposition at different substrate temperatures and O₂ pressures. The structure and composition of films are studied by using X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The Y₂O₃ thin films deposited in vacuum strongly oriented their [1 1 1] axis of the cubic structure and the film quality depended on the substrate temperature. The magnitude of O₂ pressure obviously influences the film structure and quality. Due to the silicon diffusion and interface reaction during the deposition, yttrium silicate and SiO₂ were formed. The strong relationship between composition and growth condition was discussed.     

Growth of InN films on spinel substrates by pulsed laser deposition

We have grown InN films on MgAl₂O₄(111) substrates with atomically flat surfaces using pulsed laser deposition (PLD) and compared their structural properties with those grown on (Mn,Zn)Fe₂O₄(111) substrates. It has been revealed that InN(0001) films grow on MgAl₂O₄(111) with an in‐plane epitaxial relationship of InN[1 00] // MgAl₂O₄[1 0], achieving a lattice mismatch minimum. The InN films exhibited a clear sixfold rotational symmetry, without 30° rotational domains and with a full width at half maximum value of the InN 0002 rocking curve being 17.5 arcmin. Comparison between InN films grown on MgAl₂O₄ and those on (Mn,Zn)Fe₂O₄ led us to conclude that suppression of the interfacial reactions between the InN films and the substrate is inherently important to obtain high quality InN on substrates with a spinel structure. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structural and optical properties of Er, Yb co-doped Y2O3 thin films

Thin Er³⁺, Yb³⁺ co-doped Y₂O₃ films were grown on (1 0 0) YAG substrates by pulsed laser deposition. Ceramic targets having different active ion concentration were used for ablation. The influence of the rare-earth content and oxygen pressure applied during the deposition on the structural, morphological and optical properties of the films were investigated. The films deposited at the lower pressure, 1 Pa, and at 1/10 Er to Yb doping ratio are highly textured along the (1 1 1) direction of the Y₂O₃ cubic phase. In addition to the crystalline structure, these films possess smoother surface compared to those prepared at the higher pressure, 10 Pa. All other films are polycrystalline, consisting of cubic and monoclinic phases of Y₂O₃. The rougher surface of the films produced at the higher-pressure leads to higher scattering losses and different behavior of the reflectivity spectra. Optical anisotropy in the films of less than 0.004 was measured regardless of the monoclinic structure obtained. Waveguide losses of about 1 dB/cm at 633 nm were obtained for the films produced at the lower oxygen pressure.     

Epitaxial growth of yttria-stabilised zirconia buffer layers on X-cut LiNbO3 for superconducting electrodes

We report on the epitaxial growth of yttria-stabilised zirconia (YSZ) buffer layers on X-cut LiNbO₃ (LNO) single crystals by pulsed laser deposition. Despite the low chemical stability of the substrates at high temperature, high quality fully reproducible films were obtained over a relatively broad range of processing conditions. The films were (00h) out-of-plane single oriented and the in-plane edge of the YSZ unit cell was aligned with the polar axis of the LNO. However, the YSZ deposition also promoted the formation of the compound LiNb₃O₈. This compound is epitaxial and located at the interface. The homogeneous YSZ film presents a uniform surface, free of outgrowths and with a low roughness. These characteristics are suitable for the epitaxial growth of other oxides, as has been demonstrated with the preparation of YBa₂Cu₃O₇/CeO₂/YSZ/LNO heterostructures. The superconducting YBa₂Cu₃O₇ films were epitaxial, with the c axis perpendicular to the surface and single in-plane orientation, and presented good transport properties (critical temperatures around 86 K and critical current densities close to 10⁶ A/cm² at 77 K). Received: 5 April 2001 / Accepted: 30 July 2001 / Published online: 30 October 2001     

Photoluminescence behavior of pulsed laser deposited ZnGa<Subscript>2</Subscript>O<Subscript>4</Subscript> thin-film phosphors grown on various substrates

ZnGa₂O₄ thin-film phosphors have been grown on Si(100), Al₂O₃(0001) and MgO(100) substrates using pulsed laser deposition. The structural characterization was carried out on a series of ZnGa₂O₄ films grown on various substrates under various substrate temperatures and oxygen pressures. The films grown on these substrates not only have different crystallinity and surface morphology, but also different Zn/Ga composition ratio. The crystallinity and photoluminescence (PL) of the ZnGa₂O₄ films are highly dependent on the deposition conditions, in particular the stoichiometry ratio of Zn/Ga and the kind of substrate. The variation of Zn/Ga in the films also depends on not only the oxygen pressure but also the substrate temperature during deposition. The PL properties of pulsed laser deposited ZnGa₂O₄ thin films have indicated that Al₂O₃(0001) and MgO(100) are promising substrates for the growth of high-quality ZnGa₂O₄ thin films and that the luminescence brightness depends on the substrate. The luminescence spectra show a broad band extending from 350 to 600 nm and peaking at 460 nm. Received: 11 July 2002 / Accepted: 31 July 2002 / Published online: 28 October 2002 RID="*" ID="*"Corresponding author. Fax: +82-51-6206356, E-mail: jhjeong@pknu.ac.kr     

Preparation and characterization of ferroelectric SrBi2Ta2O9 thin films on Si using Al2O3 buffer layers

SrBi₂Ta₂O₉ (SBT) thin films were prepared on p-type Si(100) substrates with Al₂O₃ buffer layers. Both the SBT films and the Al₂O₃ buffer layers were deposited by a pulsed laser deposition technique using a KrF excimer laser. An Al prelayer was used to prevent Si surface oxidization in the initial growth stage. It is shown that Al₂O₃ buffer layers effectively prevented interdiffusion between SBT and Si substrates. Furthermore, the capacitance–voltage (C-V) characteristics of the SBT/Al₂O₃/Si heterostructures show a hysteresis loop with a clockwise trace, demonstrating the ferroelectric switching properties of SBT films and showing a memory window of 1.6 V at 1 MHz. Received: 17 July 2000 / Accepted: 16 August 2000 / Published online: 30 November 2000     

Synthesis of nanocrystalline material by sputtering and laser ablation at low temperatures

Physical vapor deposition techniques such as sputtering and laser ablation – which are very commonly used in thin film technology – appear to hold much promise for the synthesis of nanocrystalline thin films as well as loosely aggregated nanoparticles. We present a systematic study of the process parameters that facilitate the growth of nanocrystalline metals and oxides. The systems studied include TiO₂, ZnO, γ-Al₂O₃, Cu₂O, Ag and Cu. The mean particle size and crystallographic orientation are influenced mainly by the sputtering power, the substrate temperature and the nature, pressure and flow rate of the sputtering gas. In general, nanocrystalline thin films were formed at or close to 300 K, while loosely adhering nanoparticles were deposited at lower temperatures. Received: 31 October 2000 / Accepted: 9 January 2001 / Published online: 26 April 2001     

The investigation of room temperature ferromagnetism in (1 0 0) oriented BaNb2O6 PLD films on LaAlO3 (1 0 0) substrate

(1 0 0) oriented BaNb₂O₆ films have been successfully grown on LaAlO₃ (1 0 0) substrate at 750 °C or 450 °C in vacuum by pulsed laser deposition. The deposited BaNb₂O₆ PLD films exhibit room-temperature ferromagnetism. Ab initio calculations demonstrate that stoichiometric BaNb₂O₆ and that with barium vacancy are nonmagnetic, while oxygen and niobium vacancy can induce magnetism due to the spin-polarization of Nb s electrons and O p electrons respectively. Moreover, ferromagnetic coupling is energetically more favorable when two Nb/O vacancies are located third-nearest-neighbored. The observed room temperature ferromagnetism in BaNb₂O₆ films should be mainly induced by oxygen vacancies introduced during vacuum deposition, with certain contribution by Nb vacancies.     

Texturing effects in molybdenum and aluminum nitride films correlated to energetic bombardment during sputter deposition

Molybdenum films sputter-deposited at low pressure show a (110) to (211) texture turnover with increasing film thickness, which is accompanied by a transition from a fiber texture to a mosaic-like texture. The degree of (002) texturing of sputtered aluminum nitride (AlN) films strongly depends on nitrogen pressure in Ar/N₂ or in a pure N₂ atmosphere. For the understanding of these phenomena, the power density at the substrate during sputter deposition was measured by a calorimetric method and normalized to the flux of deposited atoms. For the deposition of Mo films and various other elemental films, the results of the calorimetric measurements are well described by a model. This model takes into account the contributions of plasma irradiation, the heat of condensation and the kinetic energy of sputtered atoms and reflected Ar neutrals. The latter two were calculated by TRIM.SP Monte Carlo simulations. An empirical rule is established showing that the total energy input during sputter deposition is proportional to the ratio of target atomic mass to sputtering yield. For the special case of a circular planar magnetron the radial dependence of the Mo and Ar fluxes and related momentum components at the substrate were calculated. It is concluded that mainly the lateral inhomogeneous radial momentum component of the Mo atoms is the cause of the in-plane texturing. For AlN films, maximum (002) texturing appears at about 250 eV per atom energy input. Received: 23 June 2000 / Accepted: 12 December 2000 / Published online: 3 April 2001     

Influence of deposition conditions on the optical properties of erbium-doped yttrium oxide films grown by aerosol-UV assisted MOCVD

Erbium-doped Y₂O₃ films were prepared by aerosol-UV assisted metal-organic chemical vapour deposition (MOCVD) at 410 °C. The effects of humidity of carrier gas and UV-assistance on their structure and optical properties were investigated on the as-deposited and thermal annealed films using infrared spectroscopy, X-ray diffraction and transmission electron microscopy. It was found that the as-deposited Er:Y₂O₃ films crystallise in the Y₂O₃ cubic structure and present a very low organic contamination when the deposition takes place under high air humidity and, even better, with UV-assistance. After annealing, two different structural phases are observed corresponding to the cubic and the monoclinic structures of Y₂O₃. The Er³⁺ luminescence analysed in the visible and IR regions, shows the classical green transitions. The best optical properties were obtained with as-deposited and annealed Er:Y₂O₃ films grown under high air humidity with UV-assistance. Under such deposition conditions, ⁴I_13/2 lifetimes was found to be 3.07 and 6.1 ms for films annealed at 800 and 1000 °C, respectively, and up-conversion phenomena were underlined. This indicates that the deposition conditions, in particular air humidity, play an important role in the luminescent properties even after annealing.     

Y2O3 stabilized ZrO2 thin films deposited by electron beam evaporation: Structural, morphological characterization and laser induced damage threshold

Four kinds of Y₂O₃ stabilized ZrO₂ (YSZ) thin films with different Y₂O₃ content have been prepared on BK7 substrates by electron-beam evaporation method. Structural properties and surface morphology of thin films were investigated by X-ray diffraction (XRD) spectra and scanning probe microscope. Laser induced damage threshold (LIDT) was determined. It was found that crystalline phase and microstructure of YSZ thin films was dependent on Y₂O₃ molar content. YSZ thin films changed from monoclinic phase to high temperature phase (tetragonal and cubic) with the increase of Y₂O₃ content. The LIDT of stabilized thin film is more than that of unstabilized thin films. The reason is that ZrO₂ material undergoes phase transition during the course of e-beam evaporation resulting in more numbers of defects compared to that of YSZ thin films. These defects act as absorptive center and the original breakdown points.     

Growth of thin, crystalline oxide, nitride, and oxynitride films on NiAl and CoGa surfaces

At 300 K, an amorphous Al-oxide film is formed on NiAl(001) upon oxygen adsorption. Annealing of the oxygen-saturated NiAl(001) surface to 1200 K leads to the formation of thin well-ordered θ-Al₂O₃ films. At 300 K, and low-exposure oxygen atoms are chemisorbed on CoGa(001) on defects and on step edges of the terraces. For higher exposure up to saturation, the adsorption of oxygen leads to the formation of an amorphous Ga-oxide film. The EEL spectrum of the amorphous film exhibits two losses at ≈400 and 690 cm^-1. After annealing the amorphous Ga-oxide films to 550 K thin, well-ordered β-Ga₂O₃ films are formed on top of the CoGa(001) surface. The EEL spectrum of the β-Ga₂O₃ films show strong Fuchs-Kliewer (FK) modes at 305, 455, 645, and 785 cm^-1. The β-Ga₂O₃ films are well ordered and show (2×1) LEED pattern with two domains, oriented perpendicular to each other. The STM study confirms the two domains structure and allows the determination of the two-dimensional lattice parameters of β-Ga₂O₃. The vibrational properties and the structure of β-Ga₂O₃ on CoGa(001) and θ-Al₂O₃ on NiAl(001) are very similar. Ammonia adsorption at 80 K on NiAl(111) and NiAl(001) and subsequent thermal decomposition at elevated temperatures leads to the formation of AlN. Well-ordered and homogeneous AlN thin films can be prepared by several cycles of ammonia adsorption and annealing to 1250 K. The films render a distinct LEED pattern with hexagonal [AlN/NiAl(111)] or pseudo-twelve-fold [AlN/NiAl(001)] symmetry. The lattice constant of the grown AlN film is determined to be a_AlN= 3.11 Å. EEL spectra of AlN films show a FK phonon at 865 cm^-1. The electronic gap is determined to be E_g= 6.1±0.2 eV. GaN films are prepared by using the same procedure on the (001) and (111) surfaces of CoGa. The films are characterized by a FK phonon at 695 cm^-1 and an electronic band gap E_g= 3.5±0.2 eV. NO adsorption at 75 K on NiAl(001) and subsequent annealing to 1200 K leads to the formation of aluminium oxynitride (AlON). An oxygen to nitrogen atomic ratio of ≈2:1 was estimated from the analysis of AES spectra. The AlON films shows a distinct (2×1) LEED pattern and the EEL spectrum exhibits characteristic Fuchs-Kliewer modes. The energy gap is determined to be E_g= 6.6±0.2 eV. The structure of the AlON film is derived from that of θ-Al₂O₃ formed on NiAl(001). Received: 21 March 1997/Accepted: 12 August 1997     

Yttrium oxide thin films prepared under different oxygen-content atmospheres: microstructure and optical properties

Yttrium oxide films were prepared on silicon wafers by reactive magnetron sputtering at different oxygen flow rates to investigate the microstructure and optical properties for desirable planar optical waveguiding applications. Under the different conditions of target surface, the deposition rate, structure, and optical properties have great changes. The deposition rate increases to the maximum, and then monotonically decreases. Oxygen content in films increases and the composition of films transforms from stoichiometry to an oxygen-rich state. Y₂O₃ films grow with the (222) preferred growth orientation at low oxygen flow rate, and then turn into the (622) orientation; the microstructure evolves from crystal structure to amorphous state as oxygen flow rate increases from 2 to 12 sccm. Sufficient oxygen makes films low-order structure and oxygen-rich films have poor crystallinity. Very smooth film has been obtained at oxygen flow rate of 12 sccm. The refractive index can be greatly modulated by the oxygen-content factor. It is convincing that the controllable structure and optical properties of Y₂O₃ films can be achieved by adjustment the oxygen flow rate for desired optical design and applications.     

Thin film solid oxide fuel cells

We have investigated the deposition of 91% ZrO₂ − 9% Y₂O₃ thin films by a variety of sputtering techniques for the application as electrolytes in thin film solid oxide fuel cells. The deposition by RF sputtering was accomplished by using an oxide target of the desired composition. The deposition rate in these initial tests was limited to 0.5 μm/hr and the morphology of the film was substantially modified by deposition rate and substrate temperature. Using DC magnetron sputtering we deposited metallic films from a metallic target with the desired chemical composition. We introduced oxygen into the sputtering chamber to reactively deposit the desired 91% ZrO₂ − 9% Y₂O₃ thin films; however, we encountered problems with target oxidation and growth rate reproducibility. We subsequently demonstrated that controlled oxidation of the metallic films could result in adhering, non porous yttria stabilized zirconia films. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy, Sept. 15–22, 1996     

Microstructure, hardness, and electrical behavior of Y-doped CaZrO3 films prepared by chemical solution deposition

CaZr_0.9Y_0.1O_3???δ films were fabricated by chemical solution deposition on single-crystalline YSZ (ZrO₂ doped by 10 mol% of Y₂O₃) substrates. Mechanical hardness and morphology of the films were studied using nano-indentation and atomic force microscopy techniques. Grain microstructure of the films has been shown to depend upon thermal treatment duration and film thickness. Thin films with grains a few times greater than the film thickness have been obtained. It has been shown that thickness of films can be evaluated by comparing of the indentation curves for the clean and coated by the film substrates. Mechanical hardness of the film has been found to be sensitive to the film grain microstructure. Electrical behavior of CaZr_0.9Y_0.1O_3???δ films studied by impedance spectroscopy strongly depends on the film microstructure.