Surface hydrogen and growth mechanisms of synchrotron radiation-assisted silicon gas source molecular beam epitaxy using disilane

Surface hydrogen and growth mechanisms are investigated for synchrotron radiation (SR)-assisted gas source molecular beam epitaxy (SR-GSMBE) using Si₂H₆ on the Si(100) surface in the low-temperature region. The surface silicon hydrides (deuterides) are monitored in situ during the epitaxial growth by means of infrared reflection absorption spectroscopy with a Si(100) substrate and a CoSi₂ buried metal layer. It is concluded that the chemisorption of gas-phase reactive species such as SiH_n and H generated by SR irradiation and the subsequent hydrogen desorption are the key mechanisms of SR-GSMBE at low substrate temperatures. © 1998 John Wiley & Sons, Ltd.     

Epitaxial morphologies of polyoxymethylene. I. Electron microscopy

Epitaxial crystallization of polyoxymethylene (POM) from 0.5% iodobenzene solution has been attempted between 150 and 165°C on 11 different substrates having surface energies ranging from 136 to 1240 ergs/cm². Included in this series are several substrates such as CaF₂, SrF₂, BaF₂, graphite, mica, and silicon which had not been previously tested as substrates for POM epitaxy. The fluorite series materials are not good substrates for the epitaxial crystallization of POM from solution. In contrast, both rodlike and fold-plane epitaxial morphologies have been found on the (001) surfaces of NaCl, NaF, and mica. A possible mechanism for the formation of fold-plane epitaxy is discussed which involves solution nucleation followed by adsorption and growth of the nuclei on the substrate. It is suggested that variations observed in nucleation density of rodlike epitaxial crystals from substrate to substrate are a result of differences in degree of preferential solvent adsorption. Substrates having higher surface energies should tend to adsorb solvent more strongly and thus inhibit profuse nucleation of polymer crystals on the surface.     

Liquid‐Phase Epitaxial Growth of Two‐Dimensional Semiconductor Hetero‐nanostructures

Although many two‐dimensional (2D) hybrid nanostructures are being prepared, the engineering of epitaxial 2D semiconductor hetero‐nanostructures in the liquid phase still remains a challenge. The preparation of 2D semiconductor hetero‐nanostructures by epitaxial growth of metal sulfide nanocrystals, including CuS, ZnS and Ni₃S₂, is achieved on ultrathin TiS₂ nanosheets by a simple electrochemical approach by using the TiS₂ crystal and metal foils. Ultrathin CuS nanoplates that are 50–120 nm in size and have a triangular/hexagonal shape are epitaxially grown on TiS₂ nanosheets with perfect epitaxial alignment. ZnS and Ni₃S₂ nanoplates can be also epitaxially grown on TiS₂ nanosheets. As a proof‐of‐concept application, the obtained 2D CuS–TiS₂ composite is used as the anode in a lithium ion battery, which exhibits a high capacity and excellent cycling stability.     

Local‐Curvature‐Controlled Non‐Epitaxial Growth of Hierarchical Nanostructures

Site‐selective growth on non‐spherical seeds provides an indispensable route to hierarchical complex nanostructures that are interesting for diverse applications. However, this has only been achieved through epitaxial growth, which is restricted to crystalline materials with similar crystal structures and physicochemical properties. A non‐epitaxial growth strategy is reported for hierarchical nanostructures, where site‐selective growth is controlled by the curvature of non‐spherical seeds. This strategy is effective for site‐selective growth of silica nanorods from non‐spherical seeds of different shapes and materials, such as α‐Fe₂O₃, NaYF₄, and ZnO. This growth strategy is not limited by the stringent requirements of epitaxy and is thus a versatile general method suitable for the preparation of hierarchical nanostructures with controlled morphologies and compositions to open up a verity of applications in self‐assembly, nanorobotics, catalysis, electronics, and biotechnology.     

Temperature effect on the chemical composition of a polytetrafluoroethylene surface under the irradiation of synchrotron radiation by means of the X-ray photoelectron spectroscopy

The chemical composition and components of a polytetrafluoroethylene (PTFE) surface was investigated as a function of the temperature under the irradiation of synchrotron radiation (SR) by the X-ray photoelectron spectroscopy (XPS). When the temperature of PTFE under the SR irradiation was less than 100 °C, the C-rich surface appeared. With increasing the temperature more than 150 °C, the relative intensity of the F 1s peak to the C 1s peak increased markedly. At the temperatures of 150–180 °C, the C–C component became small and the CF₂ component was dominant. With further increasing the temperature more than 200 °C, CF₃, CF and C–CF components grew in addition to CF₂ component. Based on these XPS results, the temperature effect on the chemical composition and components is discussed.     

Epitaxial growth of rhenium on intrinsic and foreign substrates

Epitaxial growth of rhenium electrodeposited from a CsCl-Cs₂ReCl₆ chloride melt onto single crystal substrates (planar and bent) of rhenium with (10 $ \overline 1 Epitaxial growth of rhenium electrodeposited from a CsCl-Cs₂ReCl₆ chloride melt onto single crystal substrates (planar and bent) of rhenium with (100), (110), and (0001) orientations and tungsten with (110), (100), (112), and (111) orientations is studied. Optimum conditions of epitaxial growth on a rhenium single crystal with (0001) and (110) orientations are found. The basic possibility is shown of the rhenium heteroepitaxial growth on the (111)-and (100)-tungsten single crystal substrates under specified conditions of electrodeposition from a melt. The rhenium epitaxial growth depends both on the electrolysis conditions and on the substrate orientation. The surface morphology of the rhenium deposits is studied. The microhardness of single crystal and polycrystalline rhenium layers with (0001) orientation is measured. Original Russian Text ? N.O. Esina, L.M. Minchenko, A.A. Pankratov, 2008, published in Elektrokhimiya, 2008, Vol. 44, No. 6, pp. 738–744.     

Preparation and Properties of Highly Oriented Sr0.3Ba0.7Nb2O6 Thin Films by a Sol-Gel Process

We succeeded in the preparation of epitaxial or highly oriented strontium-barium niobate (Sr_0.3Ba_0.7Nb₂O₆) thin film by a sol-gel process. A homogeneous coating solution was prepared with Sr and Ba acetates and Nb(OEt)₅ as raw materials, and acetic acid and diethylene glycol monomethyl ether as solvents. Sr_0.3Ba_0.7Nb₂O₆ film sintered at 900°C on MgO(1 0 0) was oriented with c-axis perpendicular to the substrate surface. Sr_0.3Ba_0.7Nb₂O₆ film sintered at 700°C on SrTiO₃(1 0 0) was an epitaxial and oriented with c-axis in parallel to the substrate surface. Transmittance of Sr_0.3Ba_0.7Nb₂O₆ film (film thickness: 144 nm) was more than 60% at the range from 400 to 800 nm. Refractive index was 2.33 at 633 nm. Dielectric constant and dielectric loss of the Sr_0.3Ba_0.7Nb₂O₆ thin films prepared on polycrystal Pt substrates were 600 and 0.06 at room temperature and 1 kHz, respectively. The curie temperature (T_c) of polycrystalline Sr_0.3Ba_0.7Nb₂O₆ thin films was about 200°C. At room temperature and 50 kHz, remanent polarization (P_r) and coercive field (E_c) of the polycrystalline thin films were 1.79 C/cm² and 2.69 kV/cm, respectively.     

Modulating fcc and hcp Ruthenium on the Surface of Palladium–Copper Alloy through Tunable Lattice Mismatch

Herein, we report an epitaxial‐growth‐mediated method to grow face‐centered cubic (fcc) Ru, which is thermodynamically unfavorable in the bulk form, on the surface of Pd–Cu alloy. Induced by the galvanic replacement between Ru and Pd–Cu alloy, a shape transformation from a Pd–Cu@Ru core–shell to a yolk–shell structure was observed during the epitaxial growth. The successful coating of the unconventional crystallographic structure is critically dependent on the moderate lattice mismatch between the fcc Ru overlayer and PdCu₃ alloy substrate. Further, both fcc and hexagonal close packed (hcp) Ru can be selectively grown through varying the lattice spacing of the Pd–Cu substrate. The presented findings provide a new synthetic pathway to control the crystallographic structure of metal nanomaterials.     

Influence des conditions experimentales du depot de SiC par RCVD sur l'infiltration de substrats de carbone poreux

The infiltration by SiC of porous substrates of carbon or graphite powders by reaction between the substrate and an SiCl₄-H₂ gaseous mixture has been studied by the reactive chemical vapor deposition (RCVD) method as a function of temperature gaseous mixture composition and total flow rate. β-SiC has been characterised using ESCA spectroscopy, X-ray diffraction and chemical analysis with MASE spectroscopy. The silicon carbide is present throughout the sample. The growth rate of the SiC layer is very slow and the activation energy of the process is evaluated at 168 kJ mol⁻¹. High temperatures (1430 °C) and flow rates (950 cm³ min⁻¹) promote the deposition on the surface of the sample and the correct orientation of the crystals. The presence of whiskers has also been detected in the pores of the substrates.     

Location‐Controlled Growth of Vertically Aligned Si Nanowires using Au Nanodisks Patterned by KrF Stepper Lithography

The location‐controlled epitaxial growth of vertically aligned Si nanowire (v‐SiNW) arrays over large surface area was investigated with Au nanodisks (AuNDs) patterned by KrF stepper lithography. There are two steps for synthesizing v‐SiNWs from an AuND pattern: annealing and growth. The annealing process induces the formation of a single Au nanoparticle (AuNP) from an AuND pattern, which consists of several cracked AuNPs. Here, the oxide layer between the AuNDs and Si substrate is necessary for impeding the diffusion of Si atoms into the AuNPs. However, the oxide layer must be removed for properly aligned epitaxial SiNW growth. These SiNW arrays in large area can contribute highly to improve a nanowire‐based engineering by controlling the location of SiNWs with consistent pitch.     

Adsorption and surface diffusion of silicon growth species in silicon carbide chemical vapour deposition processes studied by quantum-chemical computations

The effect chlorine addition to the gas mixture has on the surface chemistry in the chemical vapour deposition (CVD) process for silicon carbide (SiC) epitaxial layers is studied by quantum-chemical calculations of the adsorption and diffusion of SiH₂ and SiCl₂ on the (000-1) 4H–SiC surface. SiH₂ was found to bind more strongly to the surface than SiCl₂ by approximately 100 kJ mol^?1 and to have a 50 kJ mol^?1 lower energy barrier for diffusion on the fully hydrogen-terminated surface. On a bare SiC surface, without hydrogen termination, the SiCl₂ molecule has a somewhat lower energy barrier for diffusion. SiCl₂ is found to require a higher activation energy for desorption once chemisorbed, compared to the SiH₂ molecule. Gibbs free energy calculations also indicate that the SiC surface may not be fully hydrogen terminated at CVD conditions since missing neighbouring pair of surface hydrogens is found to be a likely type of defect on a hydrogen-terminated SiC surface.     

Mathematical simulation of gas-phase deposition of epitaxial silicon films in the Si-C-H and Si-H systems

The effect of experimental conditions on the magnitude and uniformity of the deposition rate of epitaxial silicon obtained by chemical deposition from the gas phase in the SiCl₄-H₂, SiHCl₃-H₂, and SiH₄-H₂ systems (in the temperature ranges from 1300 to 1520 K for the chloride and 1270 to 1370 K for the silane systems) has been examined. Chloride and silane processes are compared.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1217–1222, July, 1995.     

Low-temperature radiation-assisted polymerization and the nature of active site in the methyl methacrylate-silica system

Differential scanning calorimetry and EPR and IR spectroscopies were used to study the low-temperature postradiation polymerization of methyl methacrylate (MMA) sorbed on a microporous glass (SiO₂). Sorbed MMA was found to exhibit an enhanced tendency to polymerize within a temperature range of 160–250 K. At a preliminary irradiation dose of 10 kGy, the degree of conversion of the monomer was 100%, with the fraction of homopolymer formed being within 18%. The radiation-chemical yield of radicals in the SiO₂-MMA system at 77 K was estimated at G = 53–55 per 100 eV. The paramagnetic centers formed during the low-temperature (77 K) radiolysis of SiO₂ and MMA were demonstrated to be of ionic and radical natures. The polymerization of sorbed MMA via the radical growth of polymer chains was largely initiated by ions. That the polymer synthesized forms a chemical bond with the support was demonstrated using IR spectroscopy.     

The study of the Cd(NH3) 4 2+ /Cd*(NH3) 4 2+ exchange reaction in hydrous oxides of zirconium(IV), silicon(IV) and tin(IV)

Kinetics of the exchange reaction of cadmium(II)-ammine complex ion using radio-active isotope¹¹⁵Cd in the same chemical form in hydrous oxides of zirconium(IV), silicon(IV) and tin(IV) has been studied. It has been found that the major contribution in the overall exchange process is from the surface of the exchanger particles. It has also been found that the rate of exchange follows the order: hydrous ZrO₂>hydrous SnO₂>hydrous SiO₂     

Molecular Beam Studies on the Laser-Enhanced Surface Reaction of GaAs(100) with Chlorine

A cw supersonic Cl₂ molecular beam coupled with an angle-resolved time-of-flight (TOF) technique has been used to investigate the laser-enhanced surface reaction of GaAs(100) with chlorine. The mass and velocity distributions of the major reaction products under 1064 nm laser irradiation have been measured as a function of laser fluence, detection angle, surface temperature and normal component of the translational energy of the incident chlorine molecules. It has been found that increasing both laser fluence and the translational energy of incident chlorine molecules markedly enhance mis surface reaction. The measured flux angular distributions of major reaction products can be fit satisfactorily with a bi-cosine function. Measurements of the mass and angular distributions of reaction products by a modulated molecular beam mass spectrometry show that the surface temperature effect is obvious for the Cl₂/GaAs(100) “dark” thermal reaction. A direct activated dissociative chemisorption is proposed for the mechanism of Cl₂ chemisorption on the GaAs(100) surface.     

Unraveling Epitaxial Habits in the NaLnF4 System for Color Multiplexing at the Single‐Particle Level

We report an epitaxial growth technique for scalable production of hybrid sodium rare‐earth fluoride (NaLnF₄) microcrystals, including NaYF₄, NaYbF₄, and NaLuF₄ material systems. The single crystalline nature of the as‐synthesized products makes them strong upconversion emission. The freedom of combining a lanthanide activator (Er³⁺ or Tm³⁺) with a sensitizer (Yb³⁺) at various doping concentrations readily gives access to color multiplexing at the single‐particle level. Our kinetic and thermodynamic investigations on the epitaxial growth of core–shell microcrystals using NaLnF₄ particle seeds suggest that within a certain size regime it is plausible to exert precise control over shell thickness and growth orientation under hydrothermal conditions.     

Specificity of mono- and disilane decomposition at silicon surface under conditions of epitaxial growth

Basic kinetic parameters of surface hydrogen desorption and of adsorbed silicon hydrides decomposition has been evaluated by kinetic simulation based on data of the technological experiments on silicon layer growth at 450–700°C. For the molecular epitaxial growth, the silicon surface population with silicon hydrides fragments has been estimated. The relationship between the surface hydrides pyrolysis frequency and the rate of silicon atoms incorporation into the growing crystal has been found.     

Hierarchical Surface Atomic Structure of a Manganese‐Based Spinel Cathode for Lithium‐Ion Batteries

The increasing use of lithium‐ion batteries (LIBs) in high‐power applications requires improvement of their high‐temperature electrochemical performance, including their cyclability and rate capability. Spinel lithium manganese oxide (LiMn₂O₄) is a promising cathode material because of its high stability and abundance. However, it exhibits poor cycling performance at high temperatures owing to Mn dissolution. Herein we show that when stoichiometric lithium manganese oxide is coated with highly doped spinels, the resulting epitaxial coating has a hierarchical atomic structure consisting of cubic‐spinel, tetragonal‐spinel, and layered structures, and no interfacial phase is formed. In a practical application of the coating to doped spinel, the material retained 90 % of its capacity after 800 cycles at 60 °C. Thus, the formation of an epitaxial coating with a hierarchical atomic structure could enhance the electrochemical performance of LIB cathode materials while preventing large losses in capacity.     

A Facile Synthesis of New L‐Proline‐Based Trifluoromethyl Oxazole Derivatives Using Microwave Irradiation and Conventional Method

Cyclization reaction of l ‐proline with trifluoroacetimidoyl chlorides has been developed as an efficient strategy for the synthesis of trifluoromethyl oxazole derivatives by two methods: (a) in the presence of K₂CO₃ as a base in acetonitrile at room temperature and (b) in the presence of K₂CO₃ as a base in acetonitrile using microwave irradiation, in one pot reaction. The microwave irradiation has been found to be the most efficient method. High yields and short reaction times were obtained for both electron‐releasing and electron‐withdrawing substituted N‐aryltrifluoroacetimidoyl chloride derivatives by microwave irradiation.     

Synthesis and Properties of Highly Conductive Thin Films as Buffer Layer from Sol-Gel Process

We prepared epitaxial growth SrRuO₃ thin film on LaAlO₃ (001) (LAO) single crystal substrate and highly oriented BaTiO₃ ferroelectric thin film on the epitaxial SrRuO₃ thin film. A homogeneous precursor solution for preparing SrRuO₃ thin film was prepared with Sr(O—i—C₃H₇)₂ and Ru(NO)(NO₃)₃ as starting materials, and 2-methoxy ethanol as solvents. The as-coated thin films were heat treated at temperatures from 723 to 1273 K for 1 h in air. SrRuO₃ grew epitaxially on LAO(001) substrate, which were confirmed by XRD theta-2theta method and XRD pole figure analysis. The crystallographic relationship of the film and substrate was SrRuO₃(001) parallel to LAO(001) and SrRuO₃[110] parallel to LAO[100]. A homogeneous precursor solution for preparing BaTiO₃ thin film was prepared with Ti[O—n—(CH₂)₃CH₃]₄ and Ba(OCOCH₃)₂ as starting materials, and acetic acid, 2-methoxy ethanol. SrRuO₃ coated LAO substrates were coated by spin-coating method with the coating solution. The as-coated thin films were heat treated at temperatures from 973 to 1173 K in air. It was confirmed that the thin films were growing orientated for c-axis by measurement of XRD theta-2theta method.