Epitaxial growth of tin oxide film on TiO2(1 1 0) using molecular beam epitaxy

Growth of tin oxide thin films using molecular beam epitaxy in a pyrolyzed nitrogen dioxide atmosphere on a titanium dioxide (1 1 0) substrate was investigated using X-ray photoelectron spectroscopy (XPS), electron diffraction, and atomic force microscopy (AFM). Properties of deposited films were studied for their dependence on substrate temperature and oxidation gas pressure. Analyses using XPS data revealed that tin atoms were fully oxidized to Sn⁴⁺ and SnO₂ films were grown epitaxially in deposition conditions of substrate temperatures of 627 K or higher and NO₂ pressure greater than 3×10⁻³ Pa. At a substrate temperature of 773 K, a smooth surface with atomic steps was visible in the SnO₂ films, but above or below this temperature, fine grains with crystal facets or porous structures appeared. At pressures of 8×10⁻⁴ to 3×10⁻⁴ Pa, the randomly oriented SnO phase was dominantly grown. Further decreasing the pressure, the Sn metal phase, which was epitaxially crystallized at less than 500 K, was also grown.     

Spectrometric and ellipsometric studies of (1 − x)TiO2 · xLn2O3 (Ln = Nd, Sm, Gd, Er, Yb) thin films

Spectrometric and ellipsometric studies of (1 − x)TiO₂ · xLn₂O₃ (Ln = Nd, Sm, Gd, Er, Yb; x = 0.33, 0.5) thin films at room temperature were performed. The obtained dispersion dependences of refractive indices are successfully described by the optical-refractometric relation. The dependence of optical pseudogap and refractive indices on composition and molar mass of the films is investigated. The influence of compositional disordering on the energy width of the exponential absorption edge is studied.     

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.     

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.     

Hydride-assisted growth of GaN nanowires on Au/Si(0 0 1) via the reaction of Ga with NH3 and H2

High quality, straight GaN nanowires (NWs) with diameters of 50 nm and lengths up to 3 μm have been grown on Si(0 0 1) using Au as a catalyst and the direct reaction of Ga with NH₃ and N₂:H₂ at 900 °C. These exhibited intense, near band edge photoluminescence at 3.42 eV in comparison to GaN NWs with non-uniform diameters obtained under a flow of Ar:NH₃, which showed much weaker band edge emission due to strong non-radiative recombination. A significantly higher yield of β-Ga₂O₃ NWs with diameters of ≤50 nm and lengths up to 10 μm were obtained, however, via the reaction of Ga with residual O₂ under a flow of Ar alone. The growth of GaN NWs depends critically on the temperature, pressure and flows in decreasing order of importance but also the availability of reactive species of Ga and N. A growth mechanism is proposed whereby H₂ dissociates on the Au nanoparticles and reacts with Ga giving Ga_xH_y thereby promoting one-dimensional (1D) growth via its reaction with dissociated NH₃ near or at the top of the GaN NWs while suppressing at the same time the formation of an underlying amorphous layer. The higher yield and longer β-Ga₂O₃ NWs grow by the vapor liquid solid mechanism that occurs much more efficiently than nitridation.     

The comparative structure, properties, and ionic conductivity of LiI + Li2S + GeS2 glasses doped with Ga2S3 and La2S3

The well known and characterized fast ion conducting (FIC) LiI + Li₂S + GeS₂ glass-forming system has been further optimized for higher ionic conductivity and improved thermal and chemical stability required for next generation solid electrolyte applications by doping with Ga₂S₃ and La₂S₃. These trivalent dopants are expected to eliminate terminal and non-bridging sulfur (NBS) anions thereby increasing the network connectivity while at the same time increasing the Li⁺ ion conductivity by creating lower basicity [(Ga or La)S_4/2]⁻ anion sites. Consistent with the finding that the glass-forming range for the Ga₂S₃ doped compositions is larger than that for the La₂S₃ compositions, the addition of Ga₂S₃ is found to eliminate NBS units to create bridging sulfur (BS) units that not only gives an improvement to the thermal stability, but also maintains and in some cases increases the ionic conductivity. The compositions with the highest Ga₂S₃ content showed the highest T_gs of ∼325 °C. The addition of La₂S₃ to the base glasses, by comparison, is found to create NBS by forming high coordination octahedral LaS₆³⁻ sites, but yet still improved the chemical stability of the glass in dry air and retained its high ionic conductivity and thermal stability. Significantly, at comparable concentrations of Li₂S and Ga₂S₃ or La₂S₃, the La₂S₃-doped glasses showed the higher conductivities. The addition of the LiI to the glass compositions not only improved the glass-forming ability of the compositions, but also increased the ionic conductivity glasses. LiI concentrations from 0 to 40 mol% improved the conductivities of the Ga₂S₃ glasses from ∼10⁻⁵ to ∼10⁻³ (Ω cm)⁻¹ and of the La₂S₃ glasses from ∼10⁻⁴ to ∼10⁻³ (Ω cm)⁻¹ at room temperature. A maximum conductivity of ∼10⁻³ (Ω cm)⁻¹ at room temperature was observed for all of the glasses and this value is comparable to some of the best Li ion conductors in a sulfide glass system. Yet these new compositions are markedly more thermally and chemically stable than most Li⁺ ion conducting sulfide glasses. LiI additions decreased the T_gs and T_cs of the glasses, but increased the stability towards crystallization (T_c − T_g).     

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).     

Thermal dissolution of Ag(Cu) in amorphous Ge(Sx Se1 − x)2 system

Thermally induced solid state reaction of Ag(Cu) into thin Ge(S_x Se_1 − x)₂ films with x = 0, 0.1, 0.4 and 1.0 was investigated using a step by step technique in order to design films with exact Ag(Cu) concentrations for applications in integrated IR optical devices. A thin film of Ag(Cu) was deposited on top of the host Ge(S_x Se_1 − x)₂ films followed by annealing in vacuum at constant temperature, which resulted in homogeneous films of good optical quality. The variation in Ag(Cu) concentration in the films ranged between 5 and 35 at.%. The kinetics of the diffusion and dissolution of metal in the host films was measured by optically monitoring the change in thickness of doped chalcogenide during consecutive thermal annealing steps. The kinetics studies revealed that the thermal dissolution rate of the Cu is greater than that of Ag. Optical UV-VIS transmission spectra of chalcogenide glass layers, undoped and thermal doped by Ag(Cu), were measured to establish the optical properties of the films. The spectra were analyzed using the technique proposed by Swanepoel and the results show that the addition of metal increases the absorption coefficient in the power-law regime and consequently the optical gap decreases and the refractive index increases. The amorphous character of the films was checked by X-ray diffraction which confirmed the amorphous structure of all Ag(Cu)GeSSe thin films.     

Microstructure and optical properties of (Pb,Ca)TiO3 films grown on Si(1 0 0) substrates by a simple sol-gel process

Amorphous and polycrystalline (Pb_0.76Ca_0.24)TiO₃ (PCT) thin films deposited on an Si(1 0 0) substrate have been prepared by a simple sol-gel process. The microstructure and surface morphologies of the thin films have been studied by X-ray diffraction (XRD) and atomic force microscopy (AFM). The polycrystalline PCT film on the Si(1 0 0) substrate has a tetragonal perovskite structure with grain size from 60 to 110 nm. AFM reveals smooth surfaces and root mean square (rms) roughness of 0.17 and 4.4 nm for amorphous and polycrystalline films, respectively. The refractive index n and extinction coefficient k of the amorphous and polycrystalline thin films was obtained by spectroscopic ellipsometry as a function of the photon energy in the range from 2.0 to 5.4 eV. The maximum n and direct bandgap energies of amorphous and polycrystalline thin films were 2.66 and 4.11 eV, 2.64 and 3.84 eV, respectively.     

Fabrication of (1 1 1)-oriented Si layers on SiO2 substrates by an aluminum-induced crystallization method and subsequent growth of semiconducting BaSi2 layers for photovoltaic application

We have prepared (1 1 1)-oriented Si layers on SiO₂ (fused silica) substrates from amorphous-Si(a-Si)/Al or Al/a-Si stacked layers using an aluminum-induced crystallization (AIC) method. The X-ray diffraction (XRD) intensity from the (1 1 1) planes of Si was found to depend significantly on growth conditions such as the thicknesses of Si and Al, deposition order (a-Si/Al or Al/a-Si on SiO₂), deposition technique (sputtering or vacuum evaporation) and exposure time of the Al layer to air before the deposition of Si. The crystal orientation of the Si layers was confirmed by θ−2θ, 2θ XRD and electron backscatter diffraction (EBSD). The photoresponse properties of semiconducting BaSi₂ films formed on the (1 1 1)-oriented Si layers by the AIC method were measured at room temperature. Photocurrents were clearly observed for photon energies greater than 1.25 eV. The external quantum efficiencies of the BaSi₂ were also evaluated.     

A new in-situ surface treatment during MBE-grown PbSe on CaF2/Si(1 1 1) heterostructure

The continual improvement of IV-VI materials grown by molecular beam epitaxy (MBE) is a key step in the development of IV-VI infrared semiconductor devices on silicon substrates. This study presents a novel surface-treatment method which is carried out during MBE growth of monocrystalline PbSe on Si(1 1 1)-oriented substrates. Details of the experimental procedures are described and supported by reflection high-energy electron diffraction (RHEED) patterns. The effect of the in-situ surface-treatment method is exhibited in the forms of improved electrical and morphological properties of PbSe thin films. Specially, the carrier mobility increases almost three-fold at 77 K and nearly two-fold at 300 K. The density of the growth pits undergoes almost three-fold reduction, whereas the density of the threading dislocations decreases around four-fold.     

Crystallization behavior of (GeS2)0.1(Sb2S3)0.9 glass

The crystal growth kinetics of antimony trisulfide in (GeS₂)_0.1(Sb₂S₃)_0.9 glass has been studied by microscopy and DSC. The linear crystal growth kinetics has been confirmed in the temperature range 492 ? T ? 515 K (E_G = 405 ± 7 kJ mol⁻¹). The applicability of standard growth models has been assessed. From the crystal growth rate corrected for viscosity plotted as a function of undercooling it has been found that the most probable mechanism is interface controlled 2D nucleated growth. The non-isothermal DSC data, corresponding to the bulk sample, can be described by the Johnson-Mehl-Avrami equation.     

Study on the growth and interfacial strain of CoFe2O4/BaTiO3 bilayer films

CoFe₂O₄/BaTiO₃ bilayer films were epitaxially deposited on SrTiO₃ substrates by laser molecular beam epitaxy (LMBE). The growth process of the bilayer films was in-situ monitored by reflection high-energy electron diffraction (RHEED). Sixty nanometer thick-BTO layer was firstly fabricated in a layer-by-layer growth mode with an atomic smooth surface. CFO films with a varying thickness ranging from 5 to 60 nm were subsequently deposited on BTO-coated STO substrates. The different growth behaviors of CFO films were observed due to the lattice mismatch strain. Between two short stages of the growth mode transforming, a long duration with Stransky and Krastonov growth mode was maintained. Strainfully relaxed CFO film in the island growth mode was finally formed. High-resolution X-ray diffraction (HRXRD) was used to further analyze the strain effect. It was found that the tensile stress imposed on BTO by CFO was strengthened with increasing the thickness of CFO films, which could lessen the distortion of BTO by counteracting the compressive stress caused by STO substrates. The strengthened tensile stress weakened the ferroelectric property of BTO films by reducing structural tetragonality, which was demonstrated by polarization-electric (P-E) measurement.     

Crystallization kinetics of Fe73.5−xMnxCu1Nb3Si13.5B9 (x = 0, 1, 3, 5, 7) amorphous alloys

In this study, we have investigated the effect of substituting Mn for Fe on the crystallization kinetics of amorphous Fe_73.5−xMn_xCu₁Nb₃Si_13.5B₉ (x = 1, 3, 5, 7) alloys. The samples were annealed at 550 °C and 600 °C for 1 h under an argon atmosphere. The X-ray diffraction analyses showed only a crystalline peak belonging to the α-Fe(Si) phase, with the grain size ranging from 12.2 nm for x = 0 to 16.7 nm for x = 7. The activation energies of the alloys were calculated using Kissinger, Ozawa and Augis-Bennett models based on differential thermal analysis data. The Avrami exponent n was calculated from the Johnson-Mehl-Avrami equation. The activation energy increased up to x = 3, then decreased with increasing Mn content. The values of the Avrami exponent showed that the crystallization is typical diffusion-controlled three-dimensional growth at a constant nucleation rate.     

Three-dimensional structure of fast ion conducting 0.5Li2S + 0.5[(1 − x)GeS2 + xGeO2] glasses from high-energy X-ray diffraction and reverse Monte Carlo simulations

A high-energy X-ray diffraction study has been carried out on a series of 0.5Li₂S + 0.5[(1 − x)GeS₂ + xGeO₂] glasses with x = 0.0, 0.1, 0.2, 0.4, 0.6 and 0.8. Structure factors were measured to wave vectors as high as 30 Å⁻¹ resulting in atomic pair distribution functions with high real space resolution. The three dimensional atomic-scale structure of the glasses was modeled by reverse Monte Carlo simulations based on the diffraction data. Results from the simulations show that at the atomic-scale 0.5Li₂S + 0.5[(1 − x)GeS₂ + xGeO₂] glasses may be viewed as an assembly of independent chains of (Li^+-S)₂GeS_2/2 and (Li^+-O)₂GeO_2/2 tetrahedra as repeat units, where the Li ions occupy the open space between the chains. The new structure data may help understand the reasons for the sharp maximum in the Li⁺ ion conductivity at x ∼ 0.2.     

The glass transition temperature and infrared absorption spectra of: (70−x)TeO2 + 15B2O3 + 15P2O5 + xLi2O glasses

Glasses of the system: (70−x) TeO₂ + 15B₂O₃ + 15P₂O₅ + xLi₂O, where x = 5, 10, 15, 20, 25 and 30 mol% were prepared by melt quench technique. Dependencies of their glass transition temperatures (T_g) and infrared (IR) absorption spectra on composition were investigated. It is found that the gradual replacement of oxides, TeO₂ by Li₂O, decreases the glass transition temperature and increases the fragility of the glasses. Also, IR spectra revealed broad weak and strong absorption bands in the investigated range of wave numbers from 4000 to 400 cm⁻¹. These bands were assigned to their corresponding bond modes of vibration with relation to the glass structure.     

Maskless selective growth of semi-polar (1 12¯ 2) GaN on Si (3 1 1) substrate by metal organic vapor phase epitaxy

Semi-polar (1 1 2¯ 2) GaN layers were selectively grown by metal organic chemical vapor phase epitaxy on patterned Si (3 1 1) substrates without SiO₂ amorphous mask. The (1 1 2¯ 2) GaN layers could be selectively grown only on Si (1 1 1) facets when the stripe mask width was narrower than 1 μm even without SiO₂. Inhomogeneous spatial distribution of donor bound exciton (DBE) peak in low-temperature cathodoluminescence (CL) spectra was explained by the difference of growth mode before and after the coalescence of stripes. It was found that the emission intensity related crystal defects is drastically decreased in case of selective growth without SiO₂ masks as compared to that obtained with SiO₂ masks.     

Formation of Ge nanoislands before the completion of a wetting layer in the Ge/Si(1 1 1) system

The formation of Ge nanoislands directly on Si(1 1 1) surface before the completion of a wetting layer was studied by scanning tunneling microscopy and Raman scattering spectroscopy. The mechanism of the wetting layer formation in the Ge/Si(1 1 1) system depends on the rate of Ge deposition. Within the temperature range 350–500 °C, with Ge deposition rates of the order of 10⁻³ bilayers/min, the Ge wetting layer is formed by the multilayer growth mechanism. Therefore, the arrays of Ge islands with the densities of 10⁹–10¹² cm⁻², depending on the rate of Ge deposition, appear directly on the Si surface during the evolution of the wetting layer. The height of Ge islands is limited by 3 bilayers. The lateral dimensions depend on the coverage of Ge and on the growth temperature. A series of lines related to the quantization of the phonon spectrum along the growth direction [1 1 1] was observed in the spectra of Raman scattering by optical phonons of Ge nanoislands.     

Optical properties of Cr ion in lithium metasilicate Li2O · SiO2 transparent glass-ceramics

The optical properties of Cr³⁺ ions in lithium metasilicate (Li₂O · SiO₂) transparent glass-ceramics were investigated. The main crystalline phase precipitated was the lithium metasilicate (Li₂O · SiO₂) crystal. The percent crystallinity and crystalline size were ranging 65-75% and 20-35 nm, respectively. The color changes drastically to deep pink from emerald green upon crystallization. New and strong absorption bands appeared and the absorption intensity increases by about 10 times that in glass. These new absorption bands are found to be derived from Cr³⁺ ions in octahedral sites in the lithium metasilicate crystal lattice. Cr³⁺ ions substitute for three Li⁺ ions and occupy the distorted octahedral site between single [SiO₄]_n chains of lithium metasilicate crystal. The ligand field parameters can be estimated: 10Dq = 13 088 cm⁻¹, B = 453 cm⁻¹, Dq/B = 2.89 and C = 2036 cm⁻¹. The near-infrared luminescence centered at 1250 nm was not detected in the deep pink glass-ceramics unlike emerald green glass.     

Concentration quenching of fluorescence from the (P0 + P1) manifold in heavily-doped Pr: ZBAN glasses

Fluorescence waveforms from the (³P₀ + ³P₁) manifold in Pr³⁺ doped ZBAN glass at wavelengths of 520, 635 and 695 nm were measured for Pr³⁺ concentrations from 4 to 12 mol%. The waveforms were found to be non-exponential with decay rates rapidly increasing with Pr³⁺ concentration and independent of whether the ³P₀ or the ³P₁ level was excited. The multipolar energy transfer model was used to analyse the waveforms and this showed that concentration quenching was due to cross-relaxation by dipole-dipole interaction. The critical concentration, at which the cross-relaxation rate equals the intrinsic decay rate, was found to be of 2.06 × 10²⁶ m⁻³ (1.20 mol%). There was no evidence of excitation diffusion for Pr³⁺ concentrations of up to 12 mol%.