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.     

Hydrothermal growth of single-crystal CaV6O16·3H2O nanoribbons

CaV₆O₁₆·3H₂O nanoribbons have been prepared by the hydrothermal method in the presence of sodium dodecyl sulfate (SDS) at 160°C for 10 h. X-ray diffraction pattern indicates that the sample is monoclinic phase of CaV₆O₁₆·3H₂O with the lattice contents a=12.18 Å, b=3.598 Å, c=18.39 Å, β=118.03°. Field emission scanning electron microscopy shows that the nanoribbons have widths in the range of 150–500 nm, thicknesses of 30–60 nm and lengths of 500 mm X-ray photoelectron spectrum measurements further confirm the formation of the CaV₆O₁₆·3H₂O phase. The formation of CaV₆O₁₆·3H₂O nanoribbons is a self-assembling process, in which surfactant SDS plays the role of soft template.     

The photoluminescence of ZnO thin films grown on Si (1 0 0) substrate by plasma-enhanced chemical vapor deposition

High-quality ZnO thin films have been grown on a Si(1 0 0) substrate by plasma-enhanced chemical vapor deposition (PECVD) using a zinc organic source (Zn(C₂H₅)₂) and carbon dioxide (CO₂) gas mixtures at a temperature of 180°C. A strong free exciton emission with a weak defect-band emission in the visible region is observed. The characteristics of photoluminescence (PL) of ZnO, as well as the exciton absorption peak in the absorption spectra, are closely related to the gas flow rate ratio of Zn(C₂H₅)₂ to CO₂. Full-widths at half-maximum of the free exciton emission as narrow as 93.4 meV have been achieved. Based on the temperature dependence of the PL spectra from 83 to 383 K, the exciton binding energy and the transition energy of free excitons at 0 K were estimated to be 59.4 meV and 3.36 eV, respectively.     

Densities of Li2O–B2O3 melts

The densities have been systematically measured in xLi₂O–(1−x)B₂O₃ melts of different compositions with Li₂O content varying from x=0 to 0.68 from their respective melting points up to about 1450 K with a modified Archimedean method. The density decreased with increasing temperature for all the melts measured in this work. When x<0.15, the plot of temperature versus density could be well fitted by a quadratic polynomial function, and when x0.15, density decreased linearly with increasing temperature. At a fixed temperature, the density of the melts increased rapidly with Li₂O content, went through a maximum at about x=0.333 (Li₂O–2B₂O₃), and then decreased slowly as Li₂O content was further increased. In addition, the volume expansion coefficient (β) was calculated based on the densities measured in this work, and it was found that a maximum value appeared in the dependence of β on the molar ratio of Li₂O at about x=0.333.     

Growth and optical absorption spectra of ZnO films grown by pulsed laser deposition

ZnO films on Al₂O₃ substrate were grown by using a pulsed laser deposition method. Through photoluminescence (PL) and X-ray diffraction (XRD) measurements, the optimum growth conditions for the ZnO growth were calculated. The results of the XRD measurement indicate that ZnO film was strongly oriented to the c-axis of hexagonal structure and epitaxially crystallized under constraints created by the substrate. The full-width half-maximum for a theta curve of the (0 0 0 2) peak was 0.201°. Also, from the PL measurement, the grown ZnO film was observed to be a free exciton, which indicates a high quality of epilayer. The Hall mobility and carrier density of the ZnO film at 293 K were estimated to be 299 cm²/V sec and , respectively. The absorption spectra revealed that the temperature dependence of the optical band gap on the ZnO films was − .     

Effect of NH3 on the growth characterization of TiN films at low temperature

Titanium nitride (TiN) films were obtained by the atmospheric pressure chemical vapor deposition method of the TiCl₄–N₂–H₂ system with various flow rates of NH₃ at 600°C. The growth characteristics, morphology and microstructure of the TiN films deposited were analyzed by X-ray diffraction, scanning electron microscopy and transmission electron microscopy. Without NH₃ addition, no TiN was deposited at 600°C as shown in the X-ray diffraction curve. However, by adding NH₃ into the TiCl₄–N₂–H₂ system, the crystalline TiN was obtained. The growth rate of TiN films increased with the increase of the NH₃ flow rate. The lattice constant of TiN films decreased with the increase of the NH₃ flow rate. At a low NH₃ flow rate, the TiN (2 2 0) with the highest texture coefficient was found. At a high NH₃ flow rate, the texture coefficient of TiN (2 0 0) increased with the increase of the NH₃ flow rate. In morphology observation, thicker plate-like TiN was obtained when the NH₃ flow rate was increased. When the flow rate of NH₃ was 15 sccm, Moiré fringes were observed in the TiN film as determined by TEM analysis. The intrinsic strain was found in the TiN film as deposited with 60 sccm NH₃.     

Anisotropic vapor phase growth of Ga2O3 crystalline nanobelts

Ga₂O₃ nanobelts were synthesized by gas reaction at high temperature in the presence of oxygen in ammonia. X-ray diffraction and chemical microanalysis revealed that the nanostructures were Ga₂O₃ with the monoclinic structure. Electron microscopy study indicated the nanobelts were single crystalline with broad (0 1 0) crystallographic planes. The nanostructures grew anisotropically with the growth direction of . Statistical analysis of the anisotropic morphology of the nanobelts and electron microscopy investigation of the nanobelt tips indicated that both vapor–solid and vapor–liquid–solid mechanisms controlled the growth process. The anisotropic nature of crystallographic morphology is explained in terms of surface energy.     

Growth of single crystals of the new double perovskite Ba2HoRu1−xCuxO6 from high temperature solutions

Single crystals of Ba₂HoRu_1−xCu_xO₆ have been grown from high temperature solutions using PbO–PbF₂ as solvent in the temperature range 1150–1250 °C. Crystals with a six sided plate like morphology measuring up to 3 mm across and 0.5 mm thick and polyhedral habit measuring up to 2 and 1 mm in thick mass were obtained. Powder X-ray diffraction patterns obtained on the crystals were indexed to give a monoclinic space group P2₁/n with lattice parameters a=5.875(2), b=5.874(3), c=8.960(1) and β=89.995(2)°. The crystals with x=0 show a single anomaly at 6.5 K corresponding to an antiferromagnetic phase with . The crystals containing Cu show additional anomalies at 18 and 48 K. The SEM and EDS analysis reveals a 2116 phase.     

Growth and characterization of a new nonlinear optical material: Potassium p-nitrophenolate dihydrate (NO2–C6H4–OK·2H2O) with new bonding properties

Single crystals of potassium p-nitrophenolate dihydrate (NPK·2H₂O) have been grown successfully using the isothermal solvent evaporation technique. It is a new semiorganic nonlinear optical crystal, possessing a d_eff of about 1.5 times that of lithium niobate and in which the K⁺ ions are bonded to the nitro group instead of bonding with the phenolic O⁻. Large single crystals of dimension upto 20×6×4 mm³ are harvested within a period of 60 days. The grown crystals are subjected to single crystal X-ray, FTIR and DRS-UV visible spectral, thermal and microhardness analyses. Single crystal X-ray analysis confirms the molecular formula and the structure of the crystal. FTIR spectral studies verify the functional groups present in the crystal. The DRS-UV visible spectrum proved the optical transparency of the crystal in the entire visible and near infrared region. Thermal studies reveal that the crystals are stable upto 180 °C. Microhardness measurements on the cleaved plane (1 1 0) explain the strength and slip direction in the crystal. The SHG efficiency of the crystal is examined by performing the Kurtz powder test using Nd:YAG laser.     

Self-catalytic branch growth of SnO2 nanowire junctions

Multiple branched SnO₂ nanowire junctions have been synthesized by thermal evaporation of SnO powder. Their nanostructures were studied by transmission electron microscopy and field emission scanning electron microcopy. It was observed that Sn nanoparticles generated from decomposition of the SnO powder acted as self-catalysts to control the SnO₂ nanojunction growth. Orthorhombic SnO₂ was found as a dominate phase in nanojunction growth instead of rutile structure. The branches and stems of nanojunctions were found to be an epitaxial growth by electron diffraction analysis and high-resolution electron microscopy observation. The growth directions of the branched SnO₂ nanojunctions were along the orthorhombic [1 1 0] and . A self-catalytic vapor–liquid–solid growth mechanism is proposed to describe the growth process of the branched SnO₂ nanowire junctions.     

Growth of Na modified potassium lithium niobate crystal by the Czochralski method

Transparent Na modified potassium lithium niobate (Na_0.23K_2.60Li_1.82Nb_5.35O_15.70; NKLN) crystal was successively grown by the Czochralski method using RF induction heating from melt composition Na₂O:K₂O : Li₂O:Nb₂O₅=2:30:25:43 mol%. NKLN crystal showed a tetragonal tungsten bronze structure with lattice constants a=12.5446±0.0010 Å and c=4.0129±0.0005 Å at room temperature. The dielectric constant along the c-axis ε₃₃ showed a sharp maximum around 480 °C. Optical transmission edge was 370 nm and optical transmission spectra showed no absorption at wavelengths ranging from 380 to 800 nm. The structural and optical properties of NKLN were similar to those of the near stoichiometric KLN crystals. We believe that the growth of NKLN by the Czochralski method has an advantage for a large size and high-quality crystal.     

Fabrication of 2D ordered arrays of cobalt silicide nanodots on (0 0 1)Si substrates

Two-dimensional (2D) periodic arrays of Co metal and Co silicide nanodots were successfully fabricated on (0 0 1)Si substrate by using the polystyrene (PS) nanosphere lithography (NSL) technique and thermal annealing. The epitaxial CoSi₂ was found to start growing in samples after annealing at 500 °C. The sizes of the Co silicide nanodots were observed to shrink with annealing temperature. From the analysis of the selected-area electron diffraction (SAED) patterns, the crystallographic relationship between the epitaxial CoSi₂ nanodots and (0 0 1)Si substrates was identified to be [0 0 1]CoSi₂//[0 0 1]Si and (2 0 0)CoSi₂//(4 0 0)Si. By combining the planview and cross-sectional TEM examination, the epitaxial CoSi₂ nanodots formed on (0 0 1)Si were found to be heavily faceted and the shape of the faceted epitaxial CoSi₂ nanodot was identified to be inverse pyramidal. The observed results present the exciting prospect that with appropriate controls, the PS NSL technique promises to offer an effective and economical patterning method for the growth of a variety of large-area periodic arrays of uniform metal and silicide nanostructures on different types of silicon substrates.     

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.     

Surface and interfacial structure of epitaxial SrTiO3 thin films on (0 0 1) Si grown by molecular beam epitaxy

Effects of relaxation of interfacial misfit strain and non-stoichiometry on surface morphology and surface and interfacial structures of epitaxial SrTiO₃ (STO) thin films on (0 0 1) Si during initial growth by molecular beam epitaxy (MBE) were investigated. In situ reflection high-energy electron diffraction (RHEED) in combination with X-ray diffraction (XRD), atomic force microscopy (AFM), X-ray photoelectron spectrometry (XPS) and transmission electron microscopy (TEM) techniques were employed. Relaxation of the interfacial misfit strain between STO and Si as measured by in situ RHEED indicates initial growth is not pseudomorphic, and the interfacial misfit strain is relaxed during and immediately after the first monolayer (ML) deposition. The interfacial strain up to 15 ML results from thermal mismatch strain rather than lattice mismatch strain. Stoichiometry of STO affects not only surface morphology but interfacial structure. We have identified a nanoscale Sr₄Ti₃O₁₀ second phase at the STO/Si interface in a Sr-rich film.     

Synthesis of superparamagnetic Mn3O4 nanocrystallites by ultrasonic irradiation

Nanocrystalline Mn₃O₄ has been synthesized by ultrasonic irradiation of Mn acetate solution in water. Analysis of its X-ray diffraction data shows formation of a phase-pure compound with an average particle size of about 15 nm. DC magnetization measurements as a function of temperature and field show a reduced ferrimagnetic transition temperature as compared to those reported for the bulk , and a subsequent observation of superparamagnetic behavior at 40 K. The observed magnetic properties are suggestive of formation of a single domain magnetically ordered Mn₃O₄ nanoparticles below their ferrimagnetic transition temperature.     

Diffusion of Zn in stoichiometric LiTaO3

As stoichiometric LiTaO₃ (LT) draws a considerable attention for integrated optical waveguide devices, we have investigated Zn diffusion into this material by diffusing 70- nm-thick ZnO films deposited on y-cut LT substrates at 700–900 °C under various atmospheres. It was observed that the surface quality was very sensitive to pressure, but weakly affected by other diffusion conditions such as temperature and atmosphere. While the surface degraded, being covered with some residuals after heat treatment at the atmospheric pressure, it was very smooth and clear when the pressure was lowered below about 10 Torr. Another feature of Zn-diffused stoichiometric LT is that the crystal maintains its transparency even after diffusion at a pressure as low as 0.1 Torr, thus without a post-annealing step required. The diffusion coefficient varied from D=1.1×10^-2 to 5.5×10⁻¹ μm²/h in the given temperature range, with an activation energy of .     

Enhanced two-dimensional growth of MOVPE InN films on sapphire (0 0 0 1) substrates

MOVPE growth of InN on sapphire substrates is compared using two different designs of horizontal reactor. The major difference between the two designs is a variation in the reactant-gas flow-spacing between the substrate and the ceiling of the quartz chamber: 33 mm for the Type A reactor and 14 mm for Type B. Compared with the Type A reactor, the Type B reactor brings about InN films with a larger grain size. This is especially true when InN is grown at 600°C using the Type B reactor, in which case the two-dimensional (2D) growth of InN is found to be extremely enhanced. An investigation of the NH₃/TMIn molar ratio dependence of the surface morphology of grown InN films using the two reactors suggests that the enhanced 2D growth is attributed to the decrease in the effective NH₃/TMIn ratio in the growth atmosphere. Even using the Type A reactor, a film with enhanced 2D growth can be obtained when the NH₃/TMIn ratio is considerably low (1.8×10⁴). The enhanced 2D growth results in a smaller XRC-FWHM (full-width at half maximum of the X-ray rocking curve) (1500 arcsec), than that for a 3D-grown film (5000 arcsec).     

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.     

Epitaxial growth of the CoFe2O4 film on SrTiO3 and its characterization

Cobalt ferrite (CoFe₂O₄) thin film is epitaxially grown on (0 0 1) SrTiO₃ (STO) by laser molecular beam epitaxy (LMBE). The growth modes of CoFe₂O₄ (CFO) film are found to be sensitive to laser repetition, the transitions from layer-by-layer mode to Stranski–Krastanov (SK) mode and then to island mode occur at the laser repetition of 3 and 5 Hz at 700 °C, respectively. The X-ray diffraction (XRD) results show that the CFO film on (0 0 1) SrTiO₃ is compressively strained by the underlying substrate and exhibits high crystallinity with a full-width at half-maximum of 0.86°. Microstructural studies indicate that the as-deposited CFO film is c-oriented island structure with rough surface morphology and the magnetic measurements reveal that the compressive strained CoFe₂O₄ film exhibits an enhanced out-of-plane magnetization (190 emu/cm³) with a large coercivity (3.8 kOe).     

ZnO hexagonal prisms grown onto p-Si (1 1 1) substrate from poly (vinylpyrrolidone) assisted electrochemical assembly

Nonionic polymer poly (vinylpyrrolidone) (PVP) was firstly mixed into oxygenated zinc chloride electrolyte to modulate the crystal growth and morphology of ZnO from electrodeposition. Arrays of ZnO hexagonal prisms with well-defined (0 0 0 1) end facets and side facets were grown perpendicularly onto p-type Si substrates using the simple and economic route. It was observed that the concentration of PVP played an important role in the final morphology and size of ZnO crystals. The optical studies indicated that the addition of PVT not only influenced crystal growth habit but also improved the optical properties of ZnO.