Atomistic nitriding processes of titanium thin films due to nitrogen-implantation

Nitrogen ions (N₂⁺) with 62 keV were implanted into the as-deposited Ti film composed of mainly (1 1 0)-oriented TiH_x and (0 3 · 5)-oriented hcp-Ti at room temperature, which results in the epitaxial formation of (1 1 0)-oriented and (0 0 1)-oriented TiN_y, respectively. The electron energy loss spectroscopy experiments elucidate that in the early N-implanting stage the release of hydrogen constituting TiH_x gives rise to the shift of the loss peak due to plasmon excitation to lower loss energy side. On the other hand, the energy loss peaks due to plasmon excitation for nitriding of hcp-Ti gradually shifted to higher energy side with increasing dose. Through the N-invasion into the octahedral sites of hcp-Ti with larger space and lower electron density, the hcp-fcc transformation of Ti sublattices is induced by the shift of the (0 0 · 1)-plane in the 〈0 1 ⋅ 0〉 direction of hcp-Ti promoted by the forming of the strong Ti-N bonds including the π-type covalent bonds, and by the weakening of the Ti-Ti bonds. Furthermore, the inheritance of square atomic arrangement and the movement of the N atom to other neighboring O-site in the transformed fcc-Ti sublattice are responsible for the epitaxial growth of TiN_y. The atomistic processes of the epitaxial growth of TiN_y are discussed with the aid of the molecular orbital calculations.     

Diffusion and desorption of submonolayer platinum deposited on the multi-faceted surface of a tungsten micro-crystal

Diffusion and desorption of platinum on the tungsten micro-crystal in the form of the W(1 1 1) oriented emitter tip has been studied using the field electron microscopy (FEM) technique. Diffusion of small dose of platinum (average thickness about 0.18 geometrical ML after spreading) on the thermally clean W emitter tip was studied at temperatures 648-742 K. Average activation energy for diffusion E_diff was found to lie between 1.16 ± 0.08 eVand 1.30 ± 0.16 eV. During annealing at the diffusion temperatures Pt-induced faceting of the emitter surface was visible in the neighbourhood of the {1 1 1} pole. The layer equilibrated in the diffusion process was stable at temperatures up to 1100 K where reduction of the high voltage at a fixed emission current, characteristic of alloying of Pt with W, was detected. Submonolayer of platinum (Θ_Pt = 0.18 ML) started to desorb at tip temperature ≥1780 K. The measurements of average activation energy for desorption of ‘zero coverage’ Pt (0.03 ML ≤ Θ_Pt ≤ 0.06 ML) from the entire W emitter surface were carried out at temperatures 1990-2170 K and yield the value of E_des = 5.19 ± 0.22 eV to 5.33 ± 0.19 eV. The results are compared with data for diffusion of individual Pt atoms and small clusters and with data for adsorption of Pt atoms on a planar W(1 1 0) surface. In discussion the atomic surface structure of the substrate, modified by the strong interaction of Pt with the W micro-crystal, is also taken into account.     

Formation of V2O3 nanocrystals by thermal reduction of V2O5 thin films

We report the formation of homogeneous and stable V₂O₃ nanocrystals, directly from V₂O₅ thin films, at 600 °C, as observed by using in situ electron microscopy experiments. Thermally-induced reduction of V₂O₅ thin films in vacuum is remarkably different when compared to reduction of V₂O₅ single crystals and results in the formation of nanophase V₂O₃. Thermally grown V₂O₃ nanocrystals exhibit hexagon or square shape and are stable at higher temperature as well as room temperature. The formation of stable nanocrystals through the reduction process in a non-chemical environment (vacuum) could provide a basis for understanding the complex processes of vanadium oxide phase transitions and for controlling the chemical processes to produce oxide nanocrystals.     

Effects of deposition temperature on the crystallinity of Ga-doped ZnO thin films on glass substrates prepared by sputtering method

The microstructural characterization of Ga-doped (5 at.%) ZnO thin film was conducted by a transmission electron microscopy study. The atomic arrangement of Ga-doped ZnO having an wurtzite structure was identified by the experimental HRTEM and Fourier filtered images as well as the electron diffractions. As a result, we have revealed that the orientation and defect density of Ga-doped ZnO thin films were greatly influenced by the deposition temperature, resulting in the variation of electrical property. In other words, the tendency forming a c-axis oriented texture grows up and the defects such as dislocations and stacking faults decrease, as the temperature of sputtering deposition increases. Consequently, the electrical properties of Ga-doped ZnO thin films can be controlled by the deposition temperature directly related with the defect density.     

Effect of thermal annealing on microstructural properties of Ti/Ge2Sb2Te5/Ti thin films deposited on SiO2/Si substrates by a sputtering method

Ti/Ge₂Sb₂Te₅/Ti thin films deposited by a sputtering method on SiO₂/Si substrates were annealed at 400 °C in N₂ atmosphere and characterized by using transmission electron microscopy (TEM) and Auger electron spectroscopy (AES) in order to investigate the inter-diffusion of the Ti/Ge₂Sb₂Te₅/Ti system due to annealing. The TEM and AES results showed that the interface between the Ti and the Ge₂Sb₂Te₅ layers was unstable and Ti atoms were incorporated into the Ge₂Sb₂Te₅ thin film upon annealing. The Te and Sb atoms of the Ge₂Sb₂Te₅ layer diffused into the Ti layer. The intermixing layers between the Ge₂Sb₂Te₅ layer and two Ti layers were formed. These results indicate that the microstructural properties of the Ti/Ge₂Sb₂Te₅/Ti systems can be degraded by the postgrowth thermal annealing.     

In situ transmission electron microscopy study of the nucleation and grain growth of Ge2Sb2Te5 thin films

The nucleation and grain growth of the Ge₂Sb₂Te₅ (GST) thin films were studied using high voltage electron microscope operated at 1250 kV. As a result, we have found that 2 nm-sized nucleus forms as a cluster which atoms are arranged regularly at the stage of nucleation prior to the formation of grains having crystal structure. The high-resolution transmission electron microscopy study and fast-Fourier transformations revealed that coexistence of face-centered-cubic (FCC) and hexagonal structure occurs, and formation of twin defect is found in the hexagonal structure during the grain growth as the annealing temperature is increased. GST grain having the hexagonal structure grow from the surface, and the growth proceeded perpendicular to the [0 0 0 1], namely the path parallel to the (0 0 0 1) plane. Consequently, grain growth to a large-scale result in a lengthened shape.     

Behaviour of discontinuous gold films on SrTiO3 substrates under annealing

Morphological changes of thin, discontinuous gold films on SrTiO₃ substrates, resulting from evaporation in the temperature range of 1143-1278 K, have been investigated by means of scanning electron microscopy (SEM) and atomic force microscopy (AFM). If the gold covered fraction of the surface is small, the evaporation kinetics can be related to the desorption of adatoms. Measuring the density of the gold beads and the time dependence of the effective thickness of the film as calculated from the diameter of the beads, the following parameters have been determined: the surface diffusion length of the gold adatoms, , the mass transfer surface diffusion coefficient, and the evaporation flux, .     

Heterojunction light emitting diodes fabricated with different n-layer oxide structures on p-GaN layers by magnetron sputtering

We grew heterojunction light emitting diode (LED) structures with various n-type semiconducting layers by magnetron sputtering on p-type GaN at high temperature. Because the undoped ZnO used as an active layer was grown under oxygen rich atmosphere, all LED devices showed the EL characteristics corresponding to orange-red wavelength due to high density of oxygen interstitial, which was coincident with the deep level photoluminescence emission of undoped ZnO. The use of the Ga doped layers as a top layer provided the sufficient electron carriers to active region and resulted in the intense EL emission. The LED sample with small quantity of Mg incorporated in MgZnO as an n-type top layer showed more intense emission than the LED with ZnO, in spite of the deteriorated electrical and structural properties of the MgZnO film. This might be due to the improvement of output extraction efficiency induced by rough surface.     

Effect of substrate temperature and annealing temperature on the structural, electrical and microstructural properties of thin Pt films by rf magnetron sputtering

Influence of both substrate temperature, T_s, and annealing temperature, T_a, on the structural, electrical and microstructural properties of sputtered deposited Pt thin films have been investigated. X-ray diffraction results show that as deposited Pt films (T_s = 300, 400 °C) are preferentially oriented along (1 1 1) direction. A little growth both along (2 0 0) and (3 1 1) directions are also noticed in the as deposited Pt films. After annealing in air (T_a = 500-700 °C), films become strongly oriented along (1 1 1) plane. With annealing temperature, average crystallite size, D, of the Pt films increases and micro-strain, e, and lattice constant, a₀, decreases. Residual strain observed in the as deposited Pt films is found to be compressive in nature while that in the annealed films is tensile. This change in the strain from compressive to tensile upon annealing is explained in the light of mismatch between the thermal expansion coefficients of the film material and substrate. Room temperature resistivity of Pt films is dependant on both the T_s and T_a of the films. Observed decrease in the film resistivity with T_a is discussed in terms of annihilation of film defects and grain-boundary. Scanning electron microscopic study reveals that as the annealing temperature increases film densification improves. But at an annealing temperature of ∼600 °C, pinholes appear on the film surface and the size of pinhole increases with further increase in the annealing temperature. From X-ray photoelectron spectroscopic analysis, existence of a thin layer of chemisorbed atomic oxygen is detected on the surfaces of the as deposited Pt films. Upon annealing, coverage of this surface oxygen increases.     

Morphology of sol-gel produced composite films for optical oxygen sensors

The results reported concern the characterization of thin layer SiO₂-based matrices with an oxygen sensing component Ru(II)-tris(4,7-diphenyl-1,10-phenanthroline) immobilized, when a sol-gel process along with dip- and spin-coating deposition methods are used.SEM, TEM and AFM study, assisted by X-ray energy dispersive microanalysis reveals the influence of the precursors used, sol treatment and the coating conditions on the films morphology and Ru distribution in the matrices. Uniform and smooth surface is produced from tetraethoxysilane (TEOS). The presence of ormosils (methyltriethoxysilane, MtEOS and octyltriethoxysilane, OtEOS) significantly increases the surface roughness exhibited as dots on the SEM image. Their surface concentration and size depend on the number of immersions and withdrawal speed at the dip coating. Spin deposition leads to rather different morphology of the films, based on TEOS/OtEOS. Following commonly used sol preparation procedure (with 1.25-2.5 g Ru-complex/dm³ sol) microcrystallization of the complex occurs with formation of randomly distributed crystals 100-400 nm in size. The ultrasound treatment of the sol by means of ultrasound disintegrator leads to homogeneous distribution of the complex without observable crystallization and significant improvement of the film sensing properties (increase of Stern-Volmer constant and better linearity of the Stern-Volmer plots both in gaseous and aqueous media).     

Surfactant effect of Sb on the growth of MnSi1.7 layers on Si(0 0 1)

Deposition of one monolayer of Sb prior to the deposition of Mn at 600 °C is observed to increase the MnSi_1.7 island density by about two orders of magnitude as well as to change the crystalline orientation of the silicide grains. The preferential epitaxial orientation of MnSi_1.7 grains grown by this process is determined to be MnSi_1.7(1 0 0)[0 1 0]||Si(0 0 1)[1 0 0]. This growth procedure results in the silicide growth into the Si matrix. For comparison, the same deposition process carried out without Sb leads to silicide formation on top of the substrate surface. The observed morphological changes of the MnSi_1.7 layers can be explained by a reduced surface diffusion of the Mn atoms on Si(0 0 1) in presence of the Sb monolayer. Additionally, lateral Si diffusion is considered to be nearly suppressed, which is responsible for the observed silicide growth into the substrate.     

Atomic force microscopy study of thermal stability of silver selenide thin films grown on silicon

Silver selenide thin films were grown on silicon substrates by the solid-state reaction of sequentially deposited Se and Ag films of suitable thickness. Transmission electron microscopy and particle-induced X-ray emission studies of the as-deposited films showed the formation of single phase polycrystalline silver selenide from the reaction of Ag and Se films. Atomic force microscopy images of the as-deposited and films annealed at different temperatures in argon showed the film morphology to evolve into an agglomerated state with annealing temperature. The results indicate that when annealed above 473 K, silver selenide films on silicon become unstable and agglomerate through holes generated at grain boundaries.     

Surface characterization and microstructure of ITO thin films at different annealing temperatures

In this study, the electron beam evaporation method is used to generate an indium tin oxide (ITO) thin film on a glass substrate at room temperature. The surface characteristics of this ITO thin film are then investigated by means of an AFM (atomic force microscopy) method. The influence of postgrowth thermal annealing on the microstructure and surface morphology of ITO thin films are also examined. The results demonstrate that the film annealed at higher annealing temperature (300 °C) has higher surface roughness, which is due to the aggregation of the native grains into larger clusters upon annealing. The fractal analysis reveals that the value of fractal dimension D_f falls within the range 2.16-2.20 depending upon the annealing temperatures and is calculated by the height-height correlation function.     

Structural characterization of nc-Si films grown by low-energy PECVD on different substrates

The knowledge and control of the structural details (texture, crystallite environment and size) of nanocrystalline silicon films is a prerequisite for their proper application in various technological fields. To this purpose, nanocrystalline silicon films grown by low energy plasma enhanced chemical vapour deposition (LEPECVD) on different kinds of substrates were submitted to a systematic characterization using Raman spectroscopy, X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM). The results showed how the difference in substrate morphology is responsible for a deep difference in the film structural properties, particularly in the case of high silane dilutions.     

Room temperature chemical synthesis of lead selenide thin films with preferred orientation

Room temperature chemical synthesis of PbSe thin films was carried out from aqueous ammoniacal solution using Pb(CH₃COO)₂ as Pb²⁺ and Na₂SeSO₃ as Se²⁻ ion sources. The films were characterized by a various techniques including, X-ray diffraction (XRD), energy dispersive X-ray analysis (EDAX), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HR-TEM), selected area electron diffraction (SAED), Fast Fourier transform (FFT) and UV-vis-NIR techniques. The study revealed that the PbSe thin film consists of preferentially oriented nanocubes with energy band gap of 0.5 eV.     

The impact of twinning on the local texture of chalcopyrite‐type thin films

Twinning in a CuInS₂ layer in a completed thin‐film solar cell was analyzed by means of electron backscatter diffraction. This technique revealed the microstructure of the CuInS₂ thin films and local orientation relationships between the grains. At various locations within the layer it was possible to retrace how twinning occurred comparing the local orientations with the theoretically possible changes in orientation by twinning. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)

     

Ordered thin films of alkyloxy-substituted benzaldehydes on a graphite surface studied by scanning tunneling microscopy

The molecular assembly of three different trialkyloxy-substituted benzaldehydes on graphite has been studied using scanning tunneling microscopy (STM). It is found that these benzaldehydes, which do not have intermolecular hydrogen bonding, could form a lamella arrangement in which the headgroups are aligned side by side. The effect due to the alkyl chain length on the lamella structure is also presented. Received: 21 January 2002 / Accepted: 22 March 2002 / Published online: 10 September 2002 RID="*" ID="*"Corresponding author. Fax: +86-10/6255-7908     

Highly oriented (1 0 0) ZnO thin films by spray pyrolysis

Undoped ZnO thin films have been deposited onto glass substrates by spray pyrolysis. The structural, electrical and optical properties were studied on thin films, prepared from precursor solutions with varying the ethanol concentrations. X-ray diffraction studies have shown polycrystalline nature of the films with a hexagonal wurtzite-type structure. The preferential orientation plane (1 0 0) of the ZnO thin film is found to be sensitive to ethanol concentration. The texture coefficient (TC) and grain size value have been calculated. Also ethanol concentration was found to have significant effect on sheet resistivity of the films.     

Thickness influence on surface morphology and ozone sensing properties of nanostructured ZnO transparent thin films grown by PLD

Transparent zinc oxide (ZnO) thin films with a thickness from 10 to 200 nm were prepared by the PLD technique onto silicon and Corning glass substrates at 350 °C, using an Excimer Laser XeCl (308 nm). Surface investigations carried out by atomic force microscopy (AFM) and X-ray diffraction (XRD) revealed a strong influence of thickness on film surface topography. Film roughness (RMS), grain shape and dimensions correlate with film thickness. For the 200 nm thick film, the RMS shows a maximum (13.9 nm) due to the presence of hexagonal shaped nanorods on the surface. XRD measurements proved that the films grown by PLD are c-axis textured. It was demonstrated that the gas sensing characteristics of ZnO films are strongly influenced and may be enhanced significantly by the control of film deposition parameters and surface characteristics, i.e. thickness and RMS, grain shape and dimension.     

Influence of substrate temperature on the chemical and microstructural properties of MO-CVD ZrTiO<Subscript>4</Subscript> thin films

In the last few years, intensive research activity has been focused on the development of suitable synthesis methods for high-permittivity materials, used for the realization of next-generation microdevices able to fulfil the previsions of the Technology Roadmap of Semiconductors. The use of high-permittivity materials can overcome the difficulties concerning the production of SiO₂-based ultra-thin dielectrics, such as the generation of pinholes and the non-uniformity of the film, which may result in a malfunction in high-density systems. Recently, zirconium titanate thin films were discovered to have very interesting dielectric properties, which suggests a use for them in microwave integrated systems, such as receivers or DRAMs, since they are monophasic, have little dissipation and show a good thermal stability and a high value for the dielectric constant, independent of frequency in the range from kilohertz to a few gigahertz. Real application is possible only in strict connection with the development of a suitable preparation method which allows production with controlled and reproducible characteristics. In this work, the synthesis and characterization of Zr_xTi_1-xO₄ (ZT) thin films grown via MO-CVD is described, studying the influence of growth parameters on their structural, chemical and physical properties. Received: 17 June 2002 / Accepted: 24 June 2002 / Published online: 4 November 2002 RID="*" ID="*"Corresponding author. Fax: +39-06/9067-2445, E-mail: Pad@mlib.cnr.it