Growth of β-MnO2 films on TiO2(110) by oxygen plasma assisted molecular beam epitaxy

We have used oxygen plasma assisted MBE to grow epitaxial films of pyrolusite (β-MnO₂) on TiO₂(110) for thicknesses of one to six bilayers (BL). We define a bilayer to be a layer of Mn and lattice O and an adjacent layer of bridging O within the rutile structure. The resulting surfaces have been characterized in situ by reflection high-energy electron diffraction, low-energy electron diffraction, X-ray photoelectron spectroscopy and diffraction, and atomic force microscopy. Well-ordered, pseudomorphic overlayers form for substrate temperatures between 400 and 500°C. Mn–Ti intermixing occurs over the time scale of film growth (1 BL/min) for substrate temperatures in excess of 500°C. Films grown at 400–500°C exhibit island growth, whereas intermixed films grown at temperatures of 500–600°C are more laminar. 1 BL films grown at 450°C are more laminar than multilayer films grown at the same temperature, and form a well-ordered surface cation layer of Mn on the rutile structure with at most 10% indiffusion to the second cation layer.     

Preparation of tantalum oxide thin films by photo-assisted atomic layer deposition

Tantalum oxide thin films were prepared by photo-assisted atomic layer deposition (Photo-ALD) in the substrate temperature range of 170–400 °C using Ta(OC₂H₅)₅ and H₂O as precursors. The constant growth rates of 0.42 and 0.47 Å per cycle were achieved for the films grown by normal ALD and Photo-ALD, respectively. The increased growth rate in Photo-ALD is probably due to the reactive surface by photon energy and faster surface reaction. In Photo-ALD, however, the constant growth rate started at lower temperature of 30 °C and one cycle time shortened up to 5.7 s than that of normal ALD. The films grown by normal ALD and Photo-ALD were amorphous and very smooth (0.21–0.35 nm) as examined by X-ray diffractometer and atomic force microscopy, respectively. Also, the refractive index was found to be 2.12–2.16 at the substrate temperature of 190–300 °C, similar to that of the film grown by normal ALD. However, the remarkably low leakage current density of 0.6×10⁻⁶ A/cm² to 1×10⁻⁶ A/cm² at applied field of 1 MV/cm is several order of magnitude smaller than that of normal ALD, probably due to the presence of reactive atom species.     

Defect versus nanocrystal luminescence emitted from room temperature and hot-implanted SiO2 layers

Silicon nanocrystals have been synthesized in SiO₂ matrix using Si ion implantation. Si ions were implanted into 300-nm-thick SiO₂ films grown on crystalline Si at energies of 30–55 keV, and with doses of 5×10¹⁵, 3×10¹⁶, and 1×10¹⁷ cm⁻². Implanted samples were subsequently annealed in an N₂ ambient at 500–1100°C during various periods. Photoluminescence spectra for the sample implanted with 1×10¹⁷ cm⁻² at 55 keV show that red luminescence (750 nm) related to Si-nanocrystals clearly increases with annealing temperature and time in intensity, and that weak orange luminescence (600 nm) is observed after annealing at low temperatures of 500°C and 800°C. The luminescence around 600 nm becomes very intense when a thin SiO₂ sample is implanted at a substrate temperature of 400°C with an energy of 30 keV and a low dose of 5×10¹⁵ cm⁻². It vanishes after annealing at 800°C for 30 min. We conclude that this luminescence observed around 600 nm is caused by some radiative defects formed in Si-implanted SiO₂.     

Strain effects in epitaxially grown La0.7Sr0.3MnO3 thin films

We report here on an X-ray absorption study of La_0.7Sr_0.3MnO₃ films epitaxially grown on SrTiO₃ substrate. The local organization around Mn in oriented films with 600 Å in thickness was investigated by polarized Extended X-ray Absorption Fine Structure. The angle between electric field vector and film surface was set equal to 5° and 70° to investigate almost independently the contribution of the manganese neighbors situated in and out of the film plane. The first neighboring shell oxygen is found to be the same in both geometries, but small changes in the next neighboring contribution are observed. These changes are associated with variation in the Mn–Mn bond length. A small in-plane elongation (3%) is observed in the constrained films with respect to the unconstrained case.     

Observation of triangular terraces and triangular craters of CaF2 film on Si(1 1 1) substrate

We have investigated the growth mode and surface morphology of CaF₂ film on Si(1 1 1)7×7 substrate by reflection high-energy electron diffraction (RHEED) using very weak electron beam and atomic force microscopy (AFM). It was found by RHEED intensity oscillation measurements and AFM observations that three-dimensional (3D) islands grow at RT; however, rather flat surface appears with two-dimensional (2D) islands around 300 °C. Especially, at high temperature of 700 °C, characteristic equilateral triangular terraces (or islands) with flat and wide shape grow with the tops directed toward [1 1 −2] of substrate Si(1 1 1). On the other hand, the desorption process of the CaF₂ film due to electron stimulated desorption (ESD) was also examined. It was found that the ESD process at 300 °C forms characteristic equilateral triangular craters on the film surface with the tops (or corners) directed toward [−1 −1 2] of substrate Si(1 1 1), provided that the film was grown at 700 °C.     

Thermal stability of the structural features in the superhydrophobic boehmite films on austenitic stainless steels

Boehmite thin film with 50–100 nm surface flake structure has been synthesized on AISI 316 type austenitic stainless steel by immersing boehmite gel film into boiling water. When further coated with hydrolyzed (heptadecafluoro-1,1,2,2-tetrahydrodecyl) trimethoxysilane (FAS), the boehmite film becomes superhydrophobic with a contact angle for water of 152°. The superhydrophobic property results from both the nanoscale surface flake structure and the low surface energy of the FAS top layer. The topography of such film was revealed by atomic force microscope (AFM) and a set of roughness parameters of such film was discussed. The degradation of superhydrophobicity of the surface was studied as a function of the heat-treatment temperatures. Below 600 °C, the surface remained to be superhydrophobic with the FAS top layer. Above 700 °C, the surface was not superhydrophobic anymore due to a gradual loss in surface roughness which was revealed by field emission scanning electron microscope (FESEM). A phase change from boehmite to γ-Al₂O₃ occurred during the heat-treatments from 700 to 900 °C which was studied by the selected area electron diffraction (SAED) patterns from the transmission electron microscope (TEM) measurement.     

Synthesis and physical behaviour of In2S3 films

In₂S₃ layers have been grown by close-spaced evaporation of pre-synthesized In₂S₃ powder from its constituent elements. The layers were deposited on glass substrates at temperatures in the range, 200–350 °C. The effect of substrate temperature on composition, structure, morphology, electrical and optical properties of the as-grown indium sulfide films has been studied. The synthesized powder exhibited cubic structure with a grain size of 63.92 nm and S/In ratio of 1.01. The films grown at 200 °C were amorphous in nature while its crystallinity increased with the increase of substrate temperature to 300 °C. The films exhibited pure tetragonal β-In₂S₃ phase at the substrate temperature of 350 °C. The surface morphological analysis revealed that the films grown at 300 °C had an average roughness of 1.43 nm. These films showed a S/In ratio of 0.98 and a lower electrical resistivity of 1.28 × 10³ Ω cm. The optical band gap was found to be direct and the layers grown at 300 °C showed a higher optical transmittance of 78% and an energy band gap of 2.49 eV.     

Structure and optical properties of sol–gel derived Gd2O3 waveguide films

Pure and rare earth doped gadolinium oxide (Gd₂O₃) waveguide films were prepared by a simple sol–gel process and dip-coating method. Gd₂O₃ was successfully synthesized by hydrolysis of gadolinium acetate. Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) were used to study the thermal chemistry properties of dried gel. Structure of Gd₂O₃ films annealed at different temperature ranging from 400 to 750 °C were investigated by Fourier transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD) and transmission electron microscopy (TEM). The results show that Gd₂O₃ starts crystallizing at about 400 °C and the crystallite size increases with annealing temperature. Oriented growth of (4 0 0) face of Gd₂O₃ has been observed when the films were deposited on (1 0 0) Si substrate and annealed at 750 °C. The laser beam (λ=632.8 nm) was coupled into the film by a prism coupler and propagation loss of the film measured by scattering-detection method is about 2 dB/cm. Luminescence properties of europium ions doped films were measured and are discussed.     

The effect of annealing under hydrostatic pressure on the visible photoluminescence from si-ion implanted SiO2 films

We have studied the influence of the hydrostatic pressure during annealing on the intensity of the visible photoluminescence (PL) from thermally grown SiO₂ films irradiated with Si⁺ ions. Post-implantation anneals have been carried out in an Ar ambient at temperatures T_a of 400°C and 450°C for 10 h and 1130°C for 5 h at hydrostatic pressures of 1 bar–15 kbar. It has been found that the intensity of the 360, 460 and 600 nm PL peaks increases with rising hydrostatic pressure during low-temperature annealing. The intensity of the short-wavelength PL under conditions of hydrostatic pressure continues to rise even at T_a=1130°C. Increasing T_a leads to a shift in the PL spectra towards the ultraviolet range. The results obtained have been interpreted in terms of enhanced, pressure-mediated formation of ≡Si–Si≡ centres and small Si clusters within metastable regions of the ion-implanted SiO₂.     

Soft X-ray emission study of thermally treated Ni(film)/4H–SiC(substrate) interface

Deposition of Ni as contact on 4H–SiC has been investigated. Ni/4H–SiC samples were annealed at temperatures of 600, 800 and 950 °C for 30 min and were non-destructively characterized by soft X-ray emission spectroscopy (SXES) using synchrotron radiation as excitation. Si L_2,3 SXE showed the formation of Ni₂Si for all annealing temperatures. The C K SXE indicated the formation of graphite and graphitic carbons at annealing temperatures of 950 °C and below 800 °C, respectively.     

The effect of a nitrogen-rich surface layer on the sub-surface deuterium (hydrogen) concentration distribution in titanium

Deuterium and nitrogen depth profiles in Ti with modified surfaces have been measured with Auger electron spectroscopy, secondary ion mass spectroscopy, and D(³He,p)⁴He nuclear reaction analysis. Nitrogen-rich surfaces layers of varying thicknesses were created on Ti by exposure to N₂ gas at 650°C. Deuterium loading was performed by exposure to 1 Torr of D₂ gas at 500°C. The deuterium distribution was influenced by nitrogen in the near-surface regions of all samples. Specifically, deuterium solubility was suppressed in surface regions of high (greater than 1%) nitrogen concentration. The deuterium solubility also remained low within the first few microns, well beyond the region of high nitrogen concentration. This effect is attributed to internal elastic stresses imposed by the non-deuterium absorbing nitrogen-rich layer on the Ti. These stresses prohibit the volume expansion associated with deuterium absorption. We estimate stresses on the order of 3–4 GPa are required to suppress the deuterium solubility to the values observed. The deuterium absorption kinetics were observed to depend systematically on the thickness of the nitrogen-rich layer. This is consistent with limited solubility near the surface or a surface poisoning effect influencing the overall deuterium diffusion from the gas phase into the Ti bulk.     

Superconducting Nd1.85Ce0.15CuO4 films grown by the pulsed electron deposition technique

Nd_1.85Ce_0.15CuO_4−δ superconducting thin films were prepared on (1 0 0) SrTiO₃ substrates by pulsed electron deposition technique without reducing atmosphere. Oxygen content is finely controlled by high temperature vacuum annealing, and optimal superconductivity has been obtained. The deposition conditions of the film are discussed in details. Higher deposition temperature and lower gas pressure result in the loss of copper and the appearance of the foreign phase Ce_0.5Nd_0.5O_1.75. High quality Nd_1.85Ce_0.15CuO_4−δ epitaxial films are deposited at 840–870 °C in the mixed gas with a ratio of O₂:Ar = 1:3.     

X-ray photoelectron spectroscopy investigation of the carburization of 310 stainless steel

The surface of 310 stainless steel (310SS) samples was investigated by X-ray photoelectron spectroscopy (XPS) after 500 h cyclic exposure to two carburizing atmospheres: CH₄ (2%)–H₂ (98%) at 800 °C, and CH₄ (10%)–H₂ (90%) at 1100 °C. The depth distribution of various elements in the surface region was obtained by XPS after successive cycles of argon etching. The microstructure of the alloy was observed by scanning electron microscopy (SEM) and the phases formed during the exposure were analyzed by X-ray diffraction (XRD). The results showed that the major phases that were formed within few micrometer depth during exposure at 800 °C include both iron and chromium carbides. (Mn, Cr) oxide was also formed as a result of the reaction with the residual oxygen of the atmosphere. A region of few microns width that was relatively depleted of chromium was formed under the surface as a result of the outwards diffusion of chromium. The exposure to the reducing atmosphere at 1100 °C led to the formation of various iron and chromium carbides. No oxide was formed during exposure. In all exposed samples, the surface was Cr enriched while nickel remained buried under the surface region that reacted with the atmosphere.     

The effect of thickness and annealing condition on the microstructure and magnetic properties of Fe/Pt multilayer thin films

[Fe(0.5 nm)/Pt(0.5 nm)]₄₀, [Fe(1 nm)/Pt(1.5 nm)]₂₀ and [Fe(3 nm)/Pt(3 nm)]₁₀ multilayer were prepared by DC magnetron sputtering. By conventional furnace annealing (CA) at 270–600 °C for various time, all of the films still remained the disordered structure with the soft magnetic phase. By rapid thermal annealing (RTA) at 500 °C for various time, we obtained the [Fe(1 nm)/Pt(1.5 nm)]₂₀ and [Fe(3 nm)/Pt(3 nm)]₁₀ films with L1₂ ordered FePt₃ phase which was almost ferromagnetic at room temperature. However, the [Fe(0.5 nm)/Pt(0.5 nm)]₄₀ films was still disordered state even under RTA. Compared with CA, RTA exposed an outstanding effect on accelerating the phase transition when the film thickness is over [Fe(0.5 nm)/Pt(0.5 nm)]₄₀.     

In situ X-ray photoelectron spectroscopy study of the oxidation of CuGaSe2

The thermal and native oxidation of CuGaSe₂ thin films was studied by in situ X-ray photoelectron spectroscopy (XPS). The special design of the XPS chamber allowed to measure XP-spectra under oxidizing gas atmospheres at pressures of up to 5 mbar (in situ) or in ultra high vacuum (UHV). During thermal oxidation, the formation of predominantly Ga₂O₃ and some amount of SeO₂ were observed, but no copper oxides could be detected in the near surface region of the thin films. The same oxides were found after native oxidation in air under ambient conditions. Only after long term native oxidation for longer than 4 months Cu(OH)₂ was detected. An additional sodium oxide compound formed at the thin film surface, Na_xO and Na₂CO₃ after thermal and native oxidation, respectively. The amount of these sodium oxide compounds depends on the Na content on the as prepared surface. The formation of SeO₂ under humid conditions at 100 °C was found to depend on the surface composition of the thin film.     

Oxidation of heated diamond C(100):H surfaces

This paper extends a previous study (Pehrsson and Mercer, submitted to Surf. Sci.) on unheated, hydrogenated, natural diamond (100) surfaces oxidized with thermally activated oxygen (O^*₂). In this paper, the oxidation is performed at substrate temperatures from T_sub=24 to 670°C. The diamond surface composition and structure were then investigated with high resolution electron energy loss spectroscopy (HREELS), Auger electron spectroscopy (AES), electron loss spectroscopy (ELS) and low energy electron diffraction (LEED).

The oxygen coverage (θ) increased in two stages, as it did during oxidation at T<80°C. However, there are fundamental differences between the oxidation of nominally unheated and heated diamond surfaces. This difference is attributed to simultaneous adsorption and rapid desorption of oxygen species at higher temperatures; the desorption step is much slower without heating. The initial oxidation rates were similar regardless of the substrate temperatures, but the peak coverage (θ) was lower at higher temperatures. For example, θ plateaued at 0.4±0.1 ML at 600°C. The lower saturation coverage is again attributed to oxygen desorption during oxidation. Consistent results were obtained on fully oxidized surfaces, which when heated in vacuum to T_sub=600°C, lost 60% of their adsorbed oxygen. ELS revealed few C=C dimers on the oxidized surfaces, and more graphitization than on unheated surfaces. Oxidation at elevated temperatures also increased the carbonyl to ether ratio, reflecting etching-induced changes in the types of surface sites. The carbonyl and C–H stretch frequencies increased with oxygen dose due to formation of higher oxidation states and/or hydrogen bonding between adjacent groups. The oxygen types did not interconvert when the oxidized surfaces were heated in vacuum. Oxygen desorption generated a much more reactive surface than heating-induced dehydrogenation of the smooth, hydrogenated surface.     

A comparison of FePt thin films with HfO2 or MnO additive

The influence of oxide additives on the magnetic and structural properties of FePt L1₀ thin films has been studied. FePt films with HfO₂ additive grown on a 5 nm MgO buffer showed a primarily random texture for both as-deposited and annealed samples. The average grain size was limited to 10 nm and the perpendicular coercivity was 1.3 kOe for a 10 nm thick FePt +20% HfO₂ film annealed at 650°C for 10 min. In direct contrast, MnO additive neither limited grain size nor L1₀ ordering in annealed FePt films. A 10 nm thick FePt+20% MnO film grown on a 5 nm MgO buffer showed a unique discontinuous microstructure composed of clusters of (0 0 1) textured L1₀ grains after being annealed at 650°C for 10 min. The average size of the grains making up these clusters was 50 nm and the perpendicular coercivity of the film exceeded 7 kOe.     

Solid-phase epitaxy of CaSi2 on Si(1 1 1) and the Schottky-barrier height of CaSi2/Si(1 1 1)

Thin Ca films were evaporated on Si(1 1 1) under UHV conditions and subsequently annealed in the temperature range 200–650 °C. The interdiffusion of Ca and Si was examined by ex situ Auger depth profiling. In situ monitoring of the Si 2p core-level shift by X-ray photoemission spectroscopy (XPS) was employed to study the silicide formation process. The formation temperature of CaSi₂ films on Si(1 1 1) was found to be about 350 °C. Epitaxial growth takes place at T≥400 °C. The morphology of the films, measured by atomic force microscopy (AFM), was correlated with their crystallinity as analyzed by X-ray diffraction (XRD). According to measurements of temperature-dependent I–V characteristics and internal photoemission the Schottky-barrier height of CaSi₂ on Si(1 1 1) amounts to qΦ_Bn=0.25 eV on n-type and to qΦ_Bp=0.82 eV on p-type silicon.     

Growth behavior of high k LaAlO3 films on Si by metalorganic chemical vapor deposition for alternative gate dielectric application

LaAlO₃ (LAO) is explored in this work to replace SiO₂ as the gate dielectric material in metal–oxide–semiconductor field effect transistor. Amorphous LAO gate dielectric films were deposited on Si (0 0 1) substrates by low pressure metalorganic chemical vapor deposition using La(dpm)₃ and Al(acac)₃ sources. The effect of processing parameters such as deposition temperature and precursor vapor flux on growth, structure, morphology, and composition of LAO films has been investigated by various analytical methods deeply. The film growth mechanism on Si is reaction limiting instead of mass transport control. The reaction is thermally activated with activation energy of 37 kJ/mol. In the initial growth stage, Al element is deficient due to higher nucleation barrier on Si. The LAO films show a smooth surface and good thermal stability and remain amorphous up to a high temperature of 850 °C. The electrical properties of amorphous LAO ultrathin films on Si have also been evaluated, indicating LAO is suitable for high k gate dielectric applications.     

Synthesis of YBa2Cu3O7−x superconducting thin films on LaAlO3 by means of PAMOCVD

High-T_c superconducting thin films have been deposited in situ by means of a plasma assisted metal-organic chemical vapour deposition (PAMOCVD) process on LaAlO₃. An EMCORE high-speed rotating disc reactor was used to deposit the films at a substrate temperature of 600°C to 800°C. The system is equipped with a (remote) 120 W microwave plasma generator. The oxidising plasma gas is N₂O and/or O₂ while Ar was used as the inert carrier gas for the different metal-organics. The influence of different process parameters (such as the temperatures of the metal-organics, substrate temperature, and plasma gas composition) on the superconductive properties and on the morphology of the films was investigated. Surface morphology and composition were studied by SEM/EDX or EPMA, and AC susceptibility measurements were used to investigate the superconductive properties (T_c and J_c). X-ray diffraction measurements indicated that single-phase YBa₂Cu₃O_7−x films were epitaxially grown with the 00l orientation perpendicular to the substrate surface. The critical temperature (T_c) of the films is about 90 K and the critical current density (J_c) is higher than 10⁶ A/cm² at 77 K and zero field.