One-dimensional surface reconstruction as an atomic-scale template for the growth of periodically striped Ag films

The role of the In/Si(111)-(4 x 1)-In surface as an atomic-scale geometrical template for the growth of Ag thin films is clarified by scanning tunneling microscopy and low energy electron diffraction. Low-temperature grown Ag films are found to have stripe structures with a transverse periodicity equal to that of indium chains of the In/Si(111)-(4 x 1)-In. The stripes exhibit a structural transformation at the thickness of 6 monolayers (ML); this relaxation allows the stripes to persist up to a thickness as large as 30 ML (approximately = 7 nm) while maintaining their mean periodicity. We attribute this stability to a coincidental matching of the periodicity and the corrugation amplitude between the Ag film and the substrate, which is realized by periodic insertion of stacking faults into a Ag fcc crystal.     

In situ surface-enhanced infrared absorption spectroscopy for the analysis of the adsorption and desorption process of Au nanoparticles on the SiO2/Si surface

The adsorption and desorption of Au nanoparticles (AuNP) in colloidal D2O suspension on the (3-aminopropyl)triethoxysilane treated SiO2/Si surface was investigated by in situ attenuated total reflection surface enhanced infrared absorption (ATR-SEIRA) spectroscopy with a liquid flow cell. With increasing surface density of AuNP, the absorption of the vibrational modes of D2O and of the citrate molecules covering the AuNP increases due to SEIRA. Repulsive electrostatic Coulomb forces between the AuNP lead to the saturation of the AuNP surface density at submonolayer coverage. We show that the adsorption kinetics can be investigated by monitoring in situ the molecular vibrational modes of D2O and the citrate molecules. Furthermore, we clarify that the adsorption process can be described very well by a diffusion-limited first-order Langmuir kinetics model. When exposing a saturated AuNP submonolayer to 2-aminoethanethiol (AET)/D2O solution, the AuNP are removed from the surface and the IR absorption of the D2O vibrational modes become weaker again. Taking into account the time dependencies of the OD and the CH peaks, we propose a microscopic model where the AET molecules quickly adsorb on the AuNP by replacing most of the precovering citrate molecules exposed to the AET solution. As this takes place, the AuNP agglomerate-as we could detect with scanning electron microscopy-and are finally removed from the surface.     

Palladium-catalyzed formation and reactions of iodo- and bromosiloxane intermediates

Polysiloxanes are useful materials because of their functionality, such as high thermal stability, electrical resistance, and hydrophobicity. In this regard, we studied palladium-catalyzed formation of iodo- and bromopolysiloxanes from two types of hydrosiloxanes, α,ω-dihydropoly(dimethylsiloxane) (1) and cyclotetra(hydromethylsiloxane) (2), and their reactions. Treatment of 1 with mixtures of cyclic ethers or lactones and MeI or allylBr in the presence of a catalytic amount of PdCl₂ gave the corresponding α,ω-bis(haloalkoxy and haloalkanoyloxy)poly(dimethylsiloxane)s in good yields, via iodo- and bromopoly(dimethylsiloxane) intermediates. Transformation of the iodobutoxy-terminal units in the resulting poly(dimethylsiloxane) into aminoalkoxy groups was examined. The formation of α,ω-diiodo- and dibromopoly(dimethylsiloxane)s from 1 was confirmed by spectrometric analysis as well as by quenching experiments with ethanol. A reaction of α,ω-dibromopoly(dimethylsiloxane) with 2,5-dilithiothiophene gave a polydimethylsiloxane-thiophene alternating polymer. Similar palladium-catalyzed reactions of 2 with THF/MeI, THF/allylBr, and δ-valerolactone/allylBr afforded cyclo-(halobutoxy- and bromobutanoyloxymethylsiloxane)s in moderate yields. This would provide a new strategy for the introduction of various substituents to the terminal positions of linear polysiloxane and to the cyclosiloxane core.     

Finite Element Analysis Of Thermal Characteristics in Continuous Wave Long Wavelength Surface Emitting Lasers (I): Dielectric Cavity Structures

We numerically analyzed the thermal characteristic in continuous wave (cw) GalnAsP/InP surface emitting lasers with dielectric multilayer mirrors by using finite element method. From the simulation of temperature distribution in cw devices, we found that MgO/Si multilayer mirror which has a high thermal conductivity is effective for heat sinking; the thermal resistance of device using MgO/Si mirror is nearly half of that using SiO₂/Si one, almost independently of their thicknesses. It was also indicated that the optimum design for other structural parameters, especially the thickness of active region, is important to effectively suppress the temperature increase. The minimum threshold current was estimated to be 3 mA under cw condition for the active region diameter of 4 μm and thickness of 0.5 μm.     

Inclusion Compound Formation of Amylose by Sealed-Heating with Salicylic Acid Analogues

The inclusion compounds of linear amylose and salicylic acid analogues preparedby sealed-heating were evaluated by using powder X-ray diffraction and infraredspectroscopy. Sealed-heating of amylose and either salicylamide or benzoic acidinduced the amylose structural change from the 6₁- to the 7₁-helix structure, while sealed-heating with o-toluic acid, o-chlorobenzoic acid and o-nitrobenzoic acid induced the change from the 6₁- to the 8₁-helix structure. In contrast to theresults in the salicylic acid system, the amylose helix type of sealed-heated samplewas not varied by the load of the guest compound, but was fixed only by the guestspecies. No change of the helical structure of amylose depending on the amylose molecular weight was observed. From the comparison of inclusion compound formation among different guest systems, it was found that the higher vapor pressure at 100 °C of the guest resulted in faster inclusion compound formation. The vapor pressure of the guest compound would be an important factor affecting the progress of inclusion compound formation.     

The Change of the Structure of Amylose During the Inclusion of 2-Naphthol in Sealed-heating Process

When a mixture of linear amylose (AS200) and2-naphthol was heated in a glass ampoule above60 ^circC, an inclusion compound was formed. Theinclusion formation accompanied the structural changeof AS200 from a 6₁-helix to a 7₁-helix. Fromthe UV determination, one 2-naphthol molecule could beincluded per one 7₁-helical turn of amylose. It was found that the heating temperature, heating timeand water content in the physical mixture wereimportant parameters affecting the formation ofinclusion compounds during sealed-heating.     

Halogen-deuterium exchange reaction mediated by tributyltin hydride using THF-d8 as the deuterium source

A regioselective deuteration method for a wide variety of aromatic compounds using the halogen-deuterium exchange reaction initiated by Bu₃SnH using THF-d₈ as the deuterium source was developed.