The effect of oxygen pressure on the microstructures of Co-doped rutile TiO2 thin films grown by pulsed laser deposition

Comprehensive microstructures of 7% cobalt-doped rutile TiO₂ thin films grown on c-plane sapphire by pulsed laser deposition were characterized using transmission electron microscopy (TEM). The effects of oxygen pressure during growth on the Co distribution inside the films were investigated, and the detailed growth mechanism of both TiO₂ and TiO₂+Co was discussed. The similar oxygen sublattices and low mismatch between (1 0 0) rutile and c-plane sapphire favors the rutile phase. However, the three-fold symmetry of the substrate surface resulted in three rutile domain orientation variants, and they grow adjacent to each other. Cobalt was found to precipitate out as nanocrystals inside the TiO₂ matrix as the growth pressure of oxygen was decreased. At 0.05 mTorr oxygen pressure, almost all of the Co segregates into crystallographically aligned nanocrystals with a particle size of 4.4±0.15 nm. All the samples have magnetic coercivity at room temperature. The magnetic moment per Co atom increased with decreased oxygen pressure, suggesting that the Co that replaced the Ti²⁺ in the TiO₂ lattice does not have a large magnetic moment.     

Crystallization behavior and hydrophilic performances of V2O5–TiO2 films prepared by sol–gel dip-coating

Homogeneous and transparent V₂O₅–TiO₂ composite nanometer thin films were prepared on glass substrates by sol–gel processing and dip-coating technique. The films as well as the dried powder of bulk gel were characterized by different techniques like X-ray diffraction (XRD), high-resolution scanning electron microscopy (HRSEM), atomic force microscope (AFM) and thermogravimetry–differential thermal analysis (TG–DTA). The hydrophilicity of the films was determined by measuring the water contact angles on the films. The results showed that the dopant of V₂O₅ on TiO₂ thin films could produce a visible-light response to the films, and the introduction of V₂O₅ could suppress the structural phase transition and crystal growth of TiO₂ crystal. Finally, the relationship between crystalline size and hydrophilicity under sunlight was investigated in this article.     

CrO2 (1 0 0) and TiO2 (1 0 0) film heteroepitaxy on a BaF2 (1 1 1)/Si (1 0 0) substrate

Multi-domained heteroepitaxial rutile-phase TiO₂ (1 0 0)-oriented films were grown on Si (1 0 0) substrates by using a 30-nm-thick BaF₂ (1 1 1) buffer layer at the TiO₂–Si interface. The 50 nm TiO₂ films were grown by electron cyclotron resonance oxygen plasma-assisted electron beam evaporation of a titanium source, and the growth temperature was varied from 300 to 600 °C. At an optimal temperature of 500 °C, X-ray diffraction measurements show that rutile phase TiO₂ films are produced. Pole figure analysis indicates that the TiO₂ layer follows the symmetry of the BaF₂ surface mesh, and consists of six (1 0 0)-oriented domains separated by 30° in-plane rotations about the TiO₂ [1 0 0] axis. The in-plane alignment between the TiO₂ and BaF₂ films is oriented as [0 0 1] TiO₂ || BaF₂ or [0 0 1] TiO₂ || BaF₂ . Rocking curve and STM analyses suggest that the TiO₂ films are more finely grained than the BaF₂ film. STM imaging also reveals that the TiO₂ surface has morphological features consistent with the BaF₂ surface mesh symmetry. One of the optimally grown TiO₂ (1 0 0) films was used to template a CrO₂ (1 0 0) film which was grown via chemical vapor deposition. Point contact Andreev reflection measurements indicate that the CrO₂ film was approximately 70% spin polarized.     

Facile synthesis of submicron BaTiO3 crystallites by a liquid–solid reaction method

Uniform, submicron BaTiO₃ crystallites in tetragonal structure were synthesized by a novel low-temperature liquid–solid reaction method mainly via two simple steps: firstly, BaO₂·H₂O₂ submicron particles of about 130–450 nm were precipitated from the reaction of BaCl₂ and H₂O₂ in a slightly alkaline (pH 8) aqueous solution under the ambient condition; secondly, tetragonal phase BaTiO₃ submicrocrystals with the size in the range of 180 to 400 nm could be produced by subjecting the as-prepared BaO₂·H₂O₂ and commercial TiO₂ submicron particles to thermal treatment in air at 700 °C for 10 h. The as-obtained products were characterized by X-ray powder diffraction, Raman spectroscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and inductively coupled plasma-atomic emission spectroscopy, and scanning electron microscopy.     

Effect of the substrate temperature on the crystallization of TiO2 films prepared by DC reactive magnetron sputtering

Titanium oxide (TiO₂) films were deposited on silicon substrates at the temperature in the range 50–600 °C by DC reactive magnetron sputtering. It was found that the anatase and rutile phases co-existed in the TiO₂ films deposited at 450–500 °C, while only the anatase phase existed in those deposited at other temperatures. The mechanism of such a crystallization behavior of TiO₂ films is preliminarily explained.     

High-resolution electron microscopy of microstructure of SrTiO3/BaZrO3 bilayer thin films on MgO substrates

SrTiO₃/BaZrO₃ heterofilms as buffer layers are deposited on (0 0 1) MgO substrates by an RF-sputtering technique. The atomic structure and the defect configuration at the interfaces are investigated by means of aberration-corrected high-resolution transmission electron microscopy. At the BaZrO₃/MgO interface, two types of interfacial structures, MgO/ZrO₂-type and MgO/BaO-type, are observed. Antiphase boundaries and dislocations are found at the BaZrO₃/MgO interface. The formation of these lattice defects is discussed in terms of film growth and structural imperfections of the substrate surface. At the SrTiO₃/BaZrO₃ interface, a high density of misfit dislocations is observed with different configurations. The formation of these dislocations contributes both to the relaxation of the large misfit strain and to stopping of the further propagation of lattice defects which are formed in the BaZrO₃ layer into the SrTiO₃ layer.     

Structure and thermal stability of MOCVD ZrO2 films on Si (1 0 0)

The structure and thermal stability of ZrO₂ films grown on Si (1 0 0) substrates by metalorganic chemical vapor deposition have been studied by high-resolution transmission electron microscopy, selected area electron diffraction and X-ray energy dispersive spectroscopy. As-deposited films consist of tetragonal ZrO₂ nanocrystallites and an amorphous Zr silicate interfacial layer. After annealing at 850°C, some monoclinic phase is formed, and the grain size is increased. Annealing a 6 nm thick film at 850°C in O₂ revealed that the growth of the interfacial layer is at the expense of the ZrO₂ layer. In a 3.0 nm thick Zr silicate interfacial layer, there is a 0.9 nm Zr-free SiO₂ region right above the Si substrate. These observations suggest that oxygen reacted with the Si substrate to grow SiO₂, and SiO₂ reacted with ZrO₂ to form a Zr silicate interfacial layer during the deposition and annealing. Oxygen diffusion through the tetragonal ZrO₂ phase was found to be relatively easier than through the monoclinic phase.     

Synthesis of Y2O3:Eu phosphors by bicontinuous cubic phase process

A novel approach for preparation of red-emitting europium-doped yttrium oxide phosphor (Y₂O₃:Eu) by using the bicontinuous cubic phase (BCP) process was reported in this paper. The BCP system was composed of anionic surfactant sodium bis(2-ethylhexyl)sulfosuccinate (AOT) and aqueous yttrium nitrate/europium nitrate solution. Energy dispersive spectrometer analysis revealed the homogeneous precipitation occurred in the BCP structure. Thermogravimetric analysis measurements indicated the precursor powder was europium-doped yttrium hydroxide, Y_1−xEu_x(OH)₃. Scanning electron microscopy micrographs showed the precursor powder had a primary size about 30 nm and narrow size distribution. After heat treatment in furnace above 700 °C for 4 h, high crystallinity Y₂O₃:Eu phosphors was obtained. However, the primary size of particles grew to 50–200 nm and the dense agglomerates with a size below 1 μm were formed. X-ray diffraction patterns indicated the crystal structure of precursor powders and Y₂O₃:Eu phosphors were amorphous and body-centered cubic structure, respectively. The photoluminescence analysis showed that the obtained Y₂O₃:Eu phosphor had a strong red emitting at 612 nm and the quenching started at a Eu concentration of 10 mol%. This study indicated that the BCP process could be used to prepare the highly efficient oxide-based phosphors.     

Growth of nanofibrous barium carbonate on calcium carbonate seeds

Fibrous barium carbonate (BaCO₃/witherite) crystals 50–100 nm in diameter and several microns in length were grown on calcium carbonate (CaCO₃) seeds at temperatures as low as 4 °C. The BaCO₃ fibers were deposited onto calcite rhombs or CaCO₃ films using the polymer-induced liquid-precursor (PILP) process, which was induced with the sodium salt of polyacrylic acid (PAA). The structure and morphology of the resultant fibers were investigated using scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected-area electron diffraction (SAED), and polarized light microscopy (PLM). Fibers were successfully grown on calcite seeds of various morphologies, with a range of barium concentrations, and PAA molecular weight and concentration. Two categories of fibers were grown: straight and twisted. Both types of fibers displayed single-crystalline SAED diffraction patterns, but after examining high-resolution TEM lattice images, it was revealed that the fibers were in fact made up of nanocrystalline domains. We postulate that these nanocrystalline domains are well aligned due to a singular nucleation event (i.e., each fiber propagates from a single nucleation event on the seed crystal) with the nanocrystalline domains resulting from stresses caused by dehydration during crystallization of the highly hydrated precursor phase. These BaCO₃ fibers grown on calcite substrates further illustrate the robustness and non-specificity of the PILP process.     

A study of growth and morphological features of TiOxNy thin films prepared by MOCVD

The growth and morphological features of MOCVD TiO_xN_y films have been characterized to evaluate the effect of various process parameters on film growth. XRD analysis of the films deposited at 600°C on Si(1 1 1) and mica show a TiN(1 1 1) peak at 2θ=36.6°, but only anatase peaks are detected below 550°C. Above 650°C, both anatase and rutile peaks are detected. The presence of ammonia is not effective below 550°C as the deposited film is mostly TiO₂. Also, ammonia does not play any role in homogeneous nucleation in the gas phase, as evident by the deposition of anatase/rutile particles above 650°C. The following changes in the morphological features are observed by varying process parameters. By increasing the ratio of titanium-isopropoxide to ammonia flow, the cluster shape changes from angular to rounded; dilution of the flow results in larger elongated clusters; increase in flow rate at constant precursor to ammonia ratios, changes the cluster shape from rounded to elongated and the cluster size deceases. Deposition at higher temperatures results in finer clusters with a slower growth rate and eventually results in a very thin film with particle deposition at 650°C and above.     

Cracking assisted nucleation in chemical vapor deposition of silicon nanoparticles on silicon dioxide

Deposition of sub-monolayer silicon on SiO₂/Si(1 0 0) greatly facilitates nucleation in subsequent thermal chemical vapor deposition (CVD) of silicon nanoparticles. Sub-monolayer seeding is accomplished using silicon atoms generated via disilane decomposition over a hot tungsten filament. The hot-wire process is nonselective towards deposition on silicon and SiO₂, is insensitive to surface temperature below 825 K, and gives controlled coverages well below 1 ML. Thermal CVD of nanoparticles at 1×10⁻⁴ Torr disilane and temperatures ranging from 825 to 925 K was studied over SiO₂/Si(1 0 0) surfaces that had been subjected to predeposition of Si or were bare. Seeding of the SiO₂ surface with as little as 0.01 ML is shown to double the nanoparticle density at 825 K, and densities are increased twenty fold at 875 K after seeding the surface with 30% of a monolayer.     

Influence of oxygen, hydrogen, helium, argon and vacuum on the surface behavior of molten InSb, other semiconductors, and metals on silica

Sessile drop experiments were performed on molten indium antimonide on clean quartz (fused silica) surfaces. A cell was constructed through which argon, helium, oxygen, hydrogen or a mixture of these was flowed at 600 °C. Some of the InSb was doped with 0.1% Ga. The surface tension σ of oxide-free molten InSb was smaller in Ar than in He, may have increased with increasing O₂ in the gas, and was not influenced by Ga or H₂. The contact angle θ on silica was higher in the presence of Ar, was lowered by O₂, and was not influenced by H₂ or Ga. The work of adhesion W and the surface energy σ_sv of the silica were higher in He than in Ar. The surface remained free of solid oxide only in flowing gas containing 0.8 ppm O₂. This behavior is attributed to reaction of O₂ at the surface of the melt to form In₂O gas. When solid oxide formed on Ga-doped material, it was strongly enriched in Ga, with the Ga/In ratio increasing with the concentration of O₂ in the gas.

Examination of published sessile-drop results for liquid metals and semiconductors on silica revealed that W and σ_sv were highest for reactive melts, in which SiO₂ dissolves. For non-reactive melts, W and σ_sv were lower and θ higher in a gas than in a vacuum, regardless of whether the experiments had been carried out in sealed ampoules, a flowing gas, or dynamic vacuum. The implication is that the surface of silica was different in a vacuum than in a gas at 1 bar.     

Synthesis of calcium carbonate polymorphs in the presence of polyacrylic acid

Calcium carbonate precipitates are prepared from a solution of CaCl₂ and K₂CO₃ in the presence of polyacrilic acid. The effect of polyacrilic acid incorporation in the [25–80 °C] temperature range on crystal morphologies and CaCO₃ precipitated polymorph concentrations are investigated using scanning electron microscopy and X-ray diffraction quantitative microstructural and phase analysis. Large changes in morphology and phase proportions are observed in the presence of polyacrylic acid, which strongly depend on the solution temperature. While crystallization of vaterite is favoured in the presence of polyacrilic acid up to 50 °C, it is largely destabilized at higher temperatures. Our process also enables the elaboration of particles in the range 10–20 nm.     

Surface crystallization of rare-earth aluminosilicate glasses

Surface crystallization in a rare-earth aluminosilicate glass (Nd₂O₃–Al₂O₃–SiO₂–TiO₂) was studied using an isothermal method and the crystal growth rate of the glasses was evaluated as a function of the composition. For measuring the surface crystal growth rate, two different methods: measurement of the crystal layer in the longitudinal and lateral growth direction. It was found that crystallization proceeded by surface crystallization only and TiO₂ did not act as a nucleating agent. The growth rate was strongly dependent on the viscosity of glass and agreed with prediction from the Preston model using the known viscosity and melting temperature. As the Si/Nd and Si/Al ratios decreased, the crystal growth rate increased. TiO₂ and Nd₂O₃ played the role of network modifier, which decreased the viscosity of the glass, facilitating crystallization of the rare-earth aluminosilicate glass.     

Material characteristics of metalorganic chemical vapor deposition of Bi2Te3 films on GaAs substrates

Metal organic chemical vapor deposition has been investigated for growth of Bi₂Te₃ films on (0 0 1) GaAs substrates using trimethylbismuth and diisopropyltelluride as metal organic sources. The results of surface morphology, electrical and thermoelectric properties as a function of growth parameters are given. The surface morphologies of Bi₂Te₃ films were strongly dependent on the deposition temperatures. Surface morphologies varied from step-flow growth mode to island coalescence structures depending on deposition temperature. In-plane carrier concentration and electrical Hall mobility were highly dependent on precursor's ratio of VI/V and deposition temperature. By optimizing growth parameters, we could clearly observe an electrically intrinsic region of the carrier concentration at the temperature higher than 240 K. The high Seebeck coefficient (of −160 μVK⁻¹) and good surface morphology of this material is promising for Bi₂Te₃-based thermoelectric thin film and two-dimensional supperlattice device applications.     

Growth and properties of (Pb0.90La0.10)TiO3 thick films prepared by RF magnetron sputtering with a PbO buffer layer

The (Pb_0.90La_0.10)TiO₃ [PLT] thick films (3.0 μm) with a PbO buffer layer were deposited on the Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrates by RF magnetron sputtering method. The PLT thick films comprise five periodicities, the layer thicknesses of (Pb_0.90La_0.10)TiO₃ and PbO in one periodicity are fixed. The PbO buffer layer improves the phase purity and electrical properties of the PLT thick films. The microstructure and electrical properties of the PLT thick films with a PbO buffer layer were studied. The PLT thick films with a PbO buffer layer possess good electrical properties with the remnant polarization (P_r=2.40 μC cm⁻²), coercive field (E_c=18.2 kV cm⁻¹), dielectric constant (ε_r=139) and dielectric loss (tan δ=0.0206) at 1 kHz, and pyroelectric coefficient (9.20×10⁻⁹ C cm⁻² K⁻¹). The result shows the PLT thick film with a PbO buffer layer is a good candidate for pyroelectric detector.     

Solvothermal growth of ZnO

The growth of ZnO single crystals and crystalline films by solvothermal techniques is reviewed. Largest ZnO crystals of 3 inch in diameter are grown by a high-pressure medium-temperature hydrothermal process employing alkaline-metal mineralizer for solubility enhancement. Structural, thermal, optical and electrical properties, impurities and annealing effects as well as machining are discussed. Poly- and single-crystalline ZnO films are fabricated from aqueous and non-aqueous solutions on a variety of substrates like glass, (100) silicon, -Al₂O₃, Mg₂AlO₄, ScAlMgO₄, ZnO and even some plastics at temperatures as low as 50 °C and ambient air conditions. Film thickness from a few nanometers up to some tens of micrometers is achieved. Lateral epitaxial overgrowth of thick ZnO films on Mg₂AlO₄ from aqueous solution at 90 °C was recently developed. The best crystallinity with a full-width half-maximum from the (0002) reflection of 26 arcsec has been obtained by liquid phase epitaxy employing alkaline-metal chlorides as solvent. Doping behavior (Cu, Ga, In, Ge) and the formation of solid solutions with MgO and CdO are reported. Photoluminescence and radioluminescence are discussed.     

Synthesis of AlN from Li3N and Al: Application to vapor phase epitaxy

We performed synthesis of AlN using Al and Li₃N. In this method, there are two problems that must be solved for obtaining single-phase AlN. One of them is suppression of Li₃AlN₂ formation and the other is precipitation of LiAl from the residual source materials during the cooling process. In the present work, we analyzed phase stability of products and found that AlN was stable at high temperatures and low Li–N/Al molar ratios. However, the products still contained LiAl and Al. Therefore, we examined the effectiveness of vapor phase epitaxy for separating AlN from the extra phase (LiAl and Al formed from residual source materials). From the experimental results, feasibility of vapor phase epitaxy was confirmed. That is, we can deposit only an AlN layer on a sapphire substrate by optimizing the growth conditions, i.e., temperature range above 1150 °C and Li–N/Al molar ratio less than 1.     

Textural properties of synthetic nano-calcite produced by hydrothermal carbonation of calcium hydroxide

The hydrothermal carbonation of calcium hydroxide (Ca(OH)₂) at high pressure of CO₂ (initial P_CO2=55 bar) and moderate to high temperature (30 and 90 °C) was used to synthesize fine particles of calcite. This method allows a high carbonation efficiency (about 95% of Ca(OH)₂–CaCO₃ conversion), a significant production rate (48 kg/m³ h) and high purity of product (about 96%). However, the various initial physicochemical conditions have a strong influence on the crystal size and surface area of the synthesized calcite crystals. The present study is focused on the estimation of the textural properties of synthesized calcite (morphology, specific surface area, average particle size, particle size distribution and particle size evolution with reaction time), using Rietveld refinements of X-ray diffraction (XRD) spectra, Brunauer–Emmett–Teller (BET) measurements, and scanning electron microscope (SEM) and transmission electron microscope (TEM) observations. This study demonstrate that the pressure, the temperature and the dissolved quantity of CO₂ have a significant effect on the average particle size, specific surface area, initial rate of precipitation, and on the morphology of calcium carbonate crystals. In contrast, these PTx conditions used herein have an insignificant effect on the carbonation efficiency of Ca(OH)₂.

Finally, the results presented here demonstrate that nano-calcite crystals with high specific surface area (S_BET=6–10 m²/g) can be produced, with a high potential for industrial applications such as adsorbents and/or filler in papermaking industry.     

Investigation of Ni/Au-contacts on p-GaN annealed in different atmospheres

We investigated the effect of different annealing atmospheres on contact behaviour of Ni/Au contacts on moderately doped p-GaN layers. We used the annealing gases N₂, O₂, Ar, and forming gas (N₂/H₂) at varying annealing temperatures from 350°C to 650°C in steps of 50°C. The p-GaN samples were either metalorganic chemical vapor deposition or molecular beam epitaxy grown. Contact characterization was done after each annealing step by using the circular transmission line model. Specific contact resistances were determined to be in the low 10⁻⁴ Ω cm² range for oxidized contacts. Accompanying chemical analysis using depth resolved Auger electron spectroscopy revealed that NiO was formed and Au diffused towards the interface, whereas annealing in forming gas prevented oxidation and did not lead to Ohmic behaviour.