Dissolution of thin SiO2-coatings - Characterization and evaluation

The hydrolytic attack by liquid solutions was investigated for two different SiO₂-coatings deposited by plasma enhanced chemical vapor deposition using a pulsed microwave plasma (PICVD) on a polymer substrate. The extent of hydrolysis was determined by the thickness reduction of the SiO₂-layer. Measurements were performed before and after aqueous contact with two independent methods, scanning electron microscopy (SEM) and reflectometry. Before storage the morphology of the coatings deposited with a HMDSO-concentration of 3% tend to be columnar, whereas the coatings produced with 1.5% appear almost untextured. After hydrolytic attack the systems feature enhanced thickness reduction with increasing pH and temperature. Significant differences between the two systems were observed regarding the dissolution rate and the appearance of the corroded surface. The dissolution rates were determined after storage in aqueous buffer-systems (pH = 5.5 and pH = 7.0) at temperatures of 60 and 90 °C. Under appropriate analysis conditions it was found, that the error of these difference measurements is dominated by the thickness variation. The observed dissolution rates vary between 0.1 and >50 nm/h.     

Temperature dependence of the tribological properties of laser re-melted Al-Cu-Fe quasicrystalline plasma sprayed coatings

The aim of this study was to investigate the effect of temperature on tribological properties of plasma-sprayed Al-Cu-Fe quasicrystal (QC) coating after laser re-melting treatment. The laser treatment resulted in a more uniform, denser and harder microstructure than that of the as-sprayed coatings. Tribological experiments on the coatings were conducted under reciprocating motion at high frequency in the temperature range from 25 to 650 °C. Remarkable influence of temperature on the friction behavior of the coating was recorded and analyzed. Microstructural analysis indicated that the wear mechanisms of the re-melted QC coatings changed from abrasive wear at room temperature, to adhesive wear at 400 °C and severe adhesive wear at 650 °C owing to the material transfer of the counterpart ball. It was also observed that the ratio of the icosahedral (i)-phase to β-Al₅₀(Fe,Cu)₅₀ phase in the coating was higher after test at 400 °C than that at 650 °C. The variation of the ratio i/β of coating and of the property of the counterpart ball and coating with the temperature are the two main factors influencing the wear mechanisms and value of the friction coefficient.     

A low silica, barium borate glass-ceramic for use as seals in planar SOFCs

A low silica, barium borate glass-ceramic for use as seals in planar SOFCs containing 64 mol%BaO, 3 mol%Al₂O₃ and 3 mol%SiO₂ was studied. Coefficient of thermal expansion (CTE) between 275-550 °C, glass transition temperature (T_g), and dilatometric softening point (T_s) of the parent glass were 11.9 × 10⁻⁶ °C⁻¹, 552 °C, and 558 °C, respectively. Glass-ceramic was produced by devitrification heat treatment at 800 °C for 100 h. It was found that nucleation heat treatment, seeding by 3 wt%ZrO₂ as glass-composite and pulverization affected the amount, size and distribution of crystalline phases. SEM-EDS and XRD results revealed that crystalline phases presented in the devitrified glass-ceramic were barium aluminate (BaAl₂O₄), barium aluminosilicate (BaAl₂Si₂O₈) possibly with boron associated in its crystal structure, and barium zirconate (BaZrO₃). CTE of the devitrified glass-ceramic was in the range of (10.1-13.0) × 10⁻⁶ °C⁻¹. Good adhesion was obtained both in the cases of glass and devitrified glass-ceramic with YSZ and AISI430 stainless steel. Interfacial phenomena between these components were discussed.     

Structure of Ni/SiO2 films prepared by sol-gel dip coating

The sol-gel dip coating technique has been used to deposit composite oxide films (NiO)_x(SiO₂)_1−x with x = 0.1 on silicon wafers. Single and multilayer coatings allowed a variation of the film thickness from 70 to 400 nm. Film morphology, atomic structure and atomic composition have been investigated by transmission electron microscopy (TEM) and Rutherford backscattering spectrometry (RBS). The local environment of the Ni atoms was characterized by extended X-ray absorption fine structure (EXAFS). The samples were studied in the as-prepared state and after annealing in H₂ at 600 °C for 1 h. The structural and chemical state evolution of clusters present inside the silica matrix is discussed in terms of out-of-equilibrium reaction processes specific to low-dimensional objects and superficial effects.     

Investigation of void formation beneath thin AlN layers by decomposition of sapphire substrates for self-separation of thick AlN layers grown by HVPE

Void formation at the interface between thick AlN layers and (0 0 0 1) sapphire substrates was investigated to form a predefined separation point of the thick AlN layers for the preparation of freestanding AlN substrates by hydride vapor phase epitaxy (HVPE). By heating 50–200 nm thick intermediate AlN layers above 1400 °C in a gas flow containing H₂ and NH₃, voids were formed beneath the AlN layers by the decomposition reaction of sapphire with hydrogen diffusing to the interface. The volume of the sapphire decomposed at the interface increased as the temperature and time of the heat treatment was increased and as the thickness of the AlN layer decreased. Thick AlN layers subsequently grown at 1450 °C after the formation of voids beneath the intermediate AlN layer with a thickness of 100 nm or above self-separated from the sapphire substrates during post-growth cooling with the aid of voids. The 79 μm thick freestanding AlN substrate obtained using a 200 nm thick intermediate AlN layer had a flat surface with no pits, high optical transparency at wavelengths above 208.1 nm, and a dislocation density of 1.5×10⁸ cm⁻².     

Structural,electrical and optical properties of SnO2 films deposited on Y-stabilized ZrO2 (1 0 0) substrates by MOCVD

SnO₂ films have been deposited on Y-stabilized ZrO₂ (YSZ) (1 0 0) substrates at different substrate temperatures (500–800 °C) by metalorganic chemical vapor deposition (MOCVD). Structural, electrical and optical properties of the films have been investigated. The films deposited at 500 and 600 °C are epitaxial SnO₂ films with orthorhombic columbite structure, and the HRTEM analysis shows a clear epitaxial relationship of columbite SnO₂(1 0 0)||YSZ(1 0 0). The films deposited at 700 and 800 °C have mixed-phase structures of rutile and columbite SnO₂. The carrier concentration of the films is in the range from 1.15×10¹⁹ to 2.68×10¹⁹ cm⁻³, and the resistivity is from 2.48×10⁻² to 1.16×10⁻² Ω cm. The absolute average transmittance of the films in the visible range exceeds 90%. The band gap of the obtained SnO₂ films is about 3.75–3.87 eV.     

Growth and characterization of epitaxial Fe0.8Ga0.2/0.69PMN-0.31PT heterostructures

Fe_0.8Ga_0.2 films were deposited on bulk single-crystal (0 0 1) 0.69PMN-0.31PT substrates by DC magnetron sputtering to make magnetoelectric bilayer composites. Films deposited at temperatures below 600 °C were X-ray amorphous. Films deposited at temperatures of 600 °C and higher exhibited a single-crystal (0 0 1) disordered BCC structure. The crystalline FeGa films demonstrate a 45° twisted cube-on-cube epitaxial relationship with the PMN–PT substrates. Heterostructures with an X-ray amorphous FeGa film exhibited zero magnetoelectric response. Heterostructures with a 990 nm epitaxial FeGa film exhibited a large inverse magnetoelectric voltage coefficient of 13.4 (G cm)/V.     

Development and characterizations of BaO-CaO-Al2O3-SiO2 glass-ceramic sealants for intermediate temperature solid oxide fuel cell application

Several compositions based on BaO-CaO-Al₂O₃-SiO₂ (BCAS) glass system have been studied in this investigation to see their applicability as sealant for solid oxide fuel cell (SOFC). The glasses as well as the corresponding glass-ceramics have been systematically characterized by differential thermal analysis, dilatometry, X-ray diffractometry, electron microscopy and impedance analysis to examine their suitability as sealant. While the glass transition temperature (T_g) determined from DTA are within 600-665 °C, the coefficient of thermal expansion (CTE) can be tailored between 9.5 and 13.0 × 10⁻⁶ K⁻¹. These glasses are found to be well adhered with metallic interconnects, such as commercial ferritic steel (Crofer22APU), at an optimum sealing temperature of 850 °C. The shrinkage behavior of the developed glasses in their pellet form has also been investigated. The resistivities of the glass-ceramics, as obtained from impedance analysis, are found to be within 10⁴-10⁶ Ω cm at 800 °C. Under sandwiched condition between two metals, some of the developed compositions are found to maintain this high resistivity even after 100 h of operation. One of the glass compositions has shown a low leak-rate of the order of ∼10⁻⁷ Pa m² s⁻¹.     

Growth of epitaxial TmFeCuO4 thin films by pulsed laser deposition

Epitaxial thin films of TmFeCuO₄ with a two-dimensional triangular lattice structure were successfully grown on yttria-stabilized-zirconia substrates by pulsed laser deposition and ex situ annealing in air. The films as-deposited below 500 °C showed no TmFeCuO₄ phase and the subsequent annealing resulted in the decomposition of film components. On the other hand, as-grown films deposited at 800 °C showed an amorphous nature. Thermal annealing converted the amorphous films into highly (0 0 1)-oriented epitaxial films. The results of scanning electron microscopic analysis suggest that the crystal growth process during thermal annealing is dominated by the regrowth of non-uniformly shaped islands to the distinct uniform islands of hexagonal base.     

Growth kinetics of SiGe/Si superlattices on bulk and silicon-on-insulator substrates for multi-channel devices

We have studied in reduced pressure chemical vapor deposition the growth kinetics of Si and Si_0.8Ge_0.2 on bulk Si(0 0 1) and on silicon-on-insulator (145 nm buried oxide/20 nm Si over-layer) substrates. For this, we have grown at 650 °C, 20 Torr 19 periods (Si_0.8Ge_0.2 19 nm/Si 32 nm) superlattices on both types of substrates that we have studied in secondary ion mass spectrometry, X-ray diffraction and cross-sectional transmission electron microscopy. The Si and SiGe growth rates together with the Ge content are steady on bulk Si(0 0 1), with mean values around 9.5 nm min⁻¹ and 20.2%, respectively. In contrast, growth rates decrease from ∼9.5 nm min⁻¹ down to values around 7.0 nm min⁻¹ (SiGe) and 6.3 nm min⁻¹ (Si), when the deposited thickness on SOI increases from 0 up to slightly more than 100 nm. They then go back up to values around 8.8–9.0 nm min⁻¹ as the thickness increases from 100 up to 400 nm. They then slowly decrease to values around 8.4–8.6 nm min⁻¹ as the thickness increases from 400 up to 800 nm. The Ge concentration follows on SOI exactly the opposite trend: an increase from 19.9% (0 nm) up to 20.6% (∼100 nm) followed by a decrease to values around 20.1% (400 nm) then a slow re-increase up to 20.4% (800 nm). These fluctuations are most likely due to the following SOI surface temperature variations: from 650 °C down to 638 °C (100 nm), back up to 648 °C (400 nm) followed by a slow decrease to 646 °C (800 nm). These data curves will be most useful to grow on conventional SOI substrates large number of periods, regular Si/Si_0.8Ge_0.2 superlattices that will serve as the core of multi-channel or three-dimensional nano-wires field effect transistors.     

Epitaxial NiO (1 0 0) and NiO (1 1 1) films grown by atomic layer deposition

Epitaxial NiO (1 1 1) and NiO (1 0 0) films have been grown by atomic layer deposition on both MgO (1 0 0) and α-Al₂O₃ (0 0 l) substrates at temperatures as low as 200 °C by using bis(2,2,6,6-tetramethyl-3,5-heptanedionato)Ni(II) and water as precursors. The films grown on the MgO (1 0 0) substrate show the expected cube on cube growth while the NiO (1 1 1) films grow with a twin rotated 180° on the α-Al₂O₃ (0 0 l) substrate surface. The films had columnar microstructures on both substrate types. The single grains were running throughout the whole film thickness and were significantly smaller in the direction parallel to the surface. Thin NiO (1 1 1) films can be grown with high crystal quality with a FWHM of 0.02–0.05° in the rocking curve measurements.     

Structure and growth morphology of Gd2O3-doped CeO2 thin films

Gd₂O₃-doped CeO₂ (Gd_0.1Ce_0.9O_1.95, GDC) thin films were synthesized on (1 0 0) Si single crystal substrates by a reactive radio frequency magnetron sputtering technique. Structures and surface morphologies were characterized by X-ray diffraction (XRD), Atomic Force Microscopy (AFM) and one-dimensional power spectral density (1DPSD) analysis. The XRD patterns indicated that, in the temperature range of 200–700 °C, f.c.c. structured GDC thin films were formed with growth orientations varying with temperature—random growth at 200 °C, (2 2 0) textures at 300–600 °C and (1 1 1) texture at 700 °C. GDC film synthesized at 200 °C had the smoothest surface with roughness of R_rms=0.973 nm. Its 1DPSD plot was characterized with a constant part at the low frequencies and a part at the high frequencies that could be fitted by the f^−2.4 power law decay. Such surface feature and scaling behavior were probably caused by the high deposition rate and random growth in the GDC film at this temperature. At higher temperatures (300–700 °C), however, an intermediate frequency slope (−γ₂≈−2) appeared in the 1DPSD plots between the low frequency constant part and the high frequency part fitted by f⁻⁴ power law decay, which indicated a roughing mechanism dominated by crystallographic orientation growth that caused much rougher surfaces in GDC films (R_rms>4 nm).     

Epitaxial growth of InN films on lattice-matched EuN buffer layers

Indium nitride (InN) films have been grown on lattice matched europium nitride (EuN) buffer layers by pulsed laser deposition (PLD) and their structural properties have been investigated. It has been revealed that the growth of EuN films on Al₂O₃ (0 0 0 1) substrates leads to the formation of polycrystalline EuN films, whereas epitaxial EuN (1 1 1) films grow on MgO (1 1 1) substrates at 860 °C. By using the EuN (1 1 1) films as buffer layers for InN growth, we have succeeded in the epitaxial growth of InN (0 0 0 1) films at 490 °C with an in-plane epitaxial relationship of [1 1 2¯ 0]_InN∥[1 1¯ 0]_EuN∥[1 1¯ 0]_MgO, which minimized the lattice mismatch between InN and EuN.     

Spectroscopic and dielectric properties of a lithia-containing glass

Glass of the composition 65SiO₂-20CaO-15Li₂O (mol %) was prepared and subjected to heat treatment. The obtained samples were characterized before and after heat treatment by DTA, TG, XRD, SEM, IR and dielectric spectroscopy. DTA showed an endothermic peak at 954 °C, accompanied by a pronounced change in the microstructure, as revealed by SEM. XRD showed that metasilicate predominates on heat treatment at 726 °C, while on heat treatment at 726 °C, then at 954 °C, disilicate crystallizes as the main phase. The IR spectra of the heat-treated glasses revealed that the vibrations of O-H groups are drastically decreased, while those due to non-bridging oxygens Si-O⁻ are increased. The dielectric constant (ε′), the loss tangent (tan δ) and the ac conductivity (σ_ac) for the prepared glasses were investigated before and after heat treatment over a moderately wide range of frequency and temperature. The activation energy of the dielectric relaxation process was found to depend on the techniques of sample preparation. A drop of dielectric constant values was observed for the heat-treated sample, which can be attributed to the ordering of the induced crystalline phases. The conductivity behavior suggests a hopping mechanism responsible for conduction.     

UV-visible and infrared absorption spectra of gamma irradiated V2O5-doped in sodium phosphate, lead phosphate, zinc phosphate glasses: A comparative study

Radiation-induced defects generated by successive gamma irradiation have been investigated in V₂O₅-doped phosphate glasses of three basic compositions, namely, sodium metaphosphate, lead metaphosphate and zinc metaphosphate. Glasses were prepared from chemically pure materials. Melting was carried at 900°-1100 °C for 1 h and with several stirrings of the melt to achieve homogeneity. The glassy samples were annealed at 200°-250 °C and left to cool to room temperature at a rate of 20 °C/h. Polished samples from undoped and V-doped samples of equal thickness. ~ 2 mm were measured in a double beam UV-visible spectrophotometer at 200-1000 nm before and after gamma irradiation. Induced defects were analyzed for these three phosphate glass systems. Infrared absorption spectra were measured for the prepared undoped and V-doped samples by the KBr technique before irradiation and after being subjected to a high dose of 7 M Rads (7 × 10⁴ Gy). The cumulative effects of gamma irradiation on the UV-visible spectra are correlated with the intrinsic and extrinsic defects within the various three glasses. Some shielding behavior for the various glasses towards successive gamma irradiation are observed and realized in relation to the different partner anions studied. The effect of gamma irradiation on IR spectra indicates the persistence of the main characteristic bands due to phosphate network and the minor changes are correlated with the possible changes in the bond lengths and/or bond angles of the building units during the irradiation process. The effect of V₂O₅ on the IR spectra is correlated with the depolymerization effect of the glass network.     

MOVPE growth of InN films using 1,1-dimethylhydrazine as a nitrogen precursor

InN films have been successfully grown on sapphire substrates by MOVPE using trimethylindium (TMIn) and 1,1-dimethylhydrazine (DMHy) with N₂ carrier. DMHy is an advantageous precursor of N as it decomposes efficiently at relatively low temperature (T₅₀=420 °C) compatible with the InN growth. The reactor is specially designed so as to avoid parasitic reaction between TMIn and DMHy occurring at room temperature. The growth feature was studied by varying growth temperature, V/III ratio, TMIn flow and reactor pressure. The InN films were obtained at 500–570 °C and 60–200 Torr with a V/III ratio optimized to 100–200. The In droplets are seen on the grown surfaces, indicating an excess supply of TMIn. It is demonstrated that the InN films grows on the sapphire substrate in a single domain with an epitaxial relationship, [1 01¯ 0]_InN//[1 1 2¯ 0]_sapphire.     

The effect of thermal annealing on the structural and mechanical properties of a-C:H thin films prepared by the CFUBM magnetron sputtering method

a-C:H films were prepared by closed-field unbalanced magnetron (CFUBM) sputtering on silicon substrates using argon (Ar) and acetylene (C₂H₂) gases, and the effects of post-annealing temperature on structural and mechanical properties were investigated. Films were annealed at temperatures ranging from 300 °C to 700 °C in increments of 200 °C using rapid thermal annealing equipment in vacuum ambient. Variations in microstructure were examined using Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). Surface and mechanical properties were investigated by atomic force microscopy (AFM), nano-indentation, residual stress tester, and nano-scratch tester. We found that the mechanical properties of a-C:H films deteriorated with increased annealing temperature.     

Characterization of nanocluster formation in Cu-implanted silica: Influence of the annealing atmosphere and the ion fluence

High-purity silica plates were implanted with 2 MeV Cu⁺ ions at various ion fluences: 0.7 × 10¹⁶, 3 × 10¹⁶ and 6 × 10¹⁶ ions/cm². After implantation, thermal treatments were performed at 400 °C and 900 °C in either an oxidizing (air) or a reducing (50% H₂ + 50% N₂) atmosphere for 1 h. All the samples were studied by electron paramagnetic resonance, X-ray photoelectron spectroscopy, high-resolution transmission electron microscopy (HRTEM), Rutherford backscattering spectrometry and optical absorption. The advantages of the reducing atmosphere (RA) over the oxidizing atmosphere (OA) are clearly observed. When annealed in a RA, the surface plasmon resonance is more intense and a narrower size distribution of the Cu nanoparticles is obtained. The existence of CuO nanoparticles was confirmed by HRTEM, and while both annealing atmospheres favor the formation of CuO nanoparticles, this process is strengthened when the sample is annealed in an OA.     

The study on various wet chemistry techniques on YBa2Cu3O7−δ superconducting oxides powder preparation

This paper reports on the results of four different wet chemical techniques used for the synthesis of superconducting oxides, YBa₂Cu₃O₇ (YBCO). YBCO samples were prepared by complexion citric gel route (CT), acetate-tartrate sol-gel (ASG), oxalate/ethanol coprecipitation (COP), and acetate-tartrate sol-gel solid-state reaction (ASG-SSR) techniques. Each of the YBCO powders was annealed for 4 h at 880 °C, 900 °C, 920 °C, and 950 °C to find the optimum temperature. The optimum sintering temperature for the formation of Y-123 phase is very much dependent on the type of wet chemical technique used to prepare the powders.     

Thermal stability of a low Tg phosphate glass investigated by DSC, XRD and solid state NMR

The thermal stability of a low Tg phosphate glass (Tg = 339 °C), formulated in the ZnO-Na₂O-P₂O₅ system, is investigated in this contribution by Differential Scanning Calorimetry (DSC), X-Ray diffraction (XRD) and solid state Nuclear Magnetic Resonance (NMR). DSC measurement indicates a very important T_x − T_g value (197 °C) for the investigated composition compared to other low Tg phosphate glasses found in literature. XRD and 1D ³¹P solid state NMR were used to monitor the isothermal crystallization process occurring at 60 °C above Tg (400 °C). The mixture of phases formed after crystallization cannot be identified by XRD but 2D MAS-NMR experiment provides valuable information about the composition and the structure of the unknown sample.