OVERVIEW ON SURFACE MICROSTRUCTURING BY PHOTODESORPTION ETCHING OF CHLORINATED SILICON

Developing a mechanistic interpretation of complex dynamical chemical systems such as halogen photoetching requires correlated microscopic data on the kinetics, dynamics, surface composition and microstructure of prototypical and real surfaces. This overview is concerned especially with two important variables which significantly influence the microetching mechanisms and structures; (I) the role of electronic point defects induced by substitutional doping in producing site-specific reactions and, (II) the quantum mechanical enhancement of chemical reaction induced by uv-radiation at low fluences and temperatures.

From uv-photoetching and photodesorption studies of heavily doped Si(100) and Si(111) with chlorine beams at low laser fluences, the mechanisms of photostimulated desorption is analyzed based primarily on the kinetics of chemisorption and surface layer microanalysis obtained from core-level photoemission. These results are coupled with time-of-flight dynamical measurements on the energetics of the photodesorption process to provide a more unified understanding of anisotropic photon-stimulated microetching.

Substantial alterations of the etching mechanisms occur when selective surface molecular processes are driven quantum mechanically by low level photon radiation rather than thermally. This is clearly reflected in the dynamical mechanisms for photodesorption which become strongly site- and atomic process-selective illustrated by the energetics of the processes. Creation and transport of charged carriers, especially at high doping levels by photoionization coupled with field-induced charge transport, introduces new reaction channels into the surface chemistry leading to resultant changes in the microstructure on an atomic scale. The results from the kinetics, velocity dynamics and film composition measurements are combined in terms of the dependency of chlorine adsorption on doping at high carrier levels and low laser fluences, to provide an improved interpretation of the anisotropic microetching in terms of field-promoted electron-hole activation.     

Graphitized carbon black in quartz tubes for the sampling of indoor air nicotine and analysis by microwave thermal desorption-capillary gas chromatography

Nicotine in a smoky indoor air environment can be determined using graphitized carbon black as a solid sorbent in quartz tubes. The temperature stability, high purity, and heat absorption characteristics of the sorbent, as well as the permeability of the quartz tubes to microwaves, enable the thermal desorption by means of microwaves after active sampling. Permeation and dynamic dilution procedures for the generation of nicotine in the vapor phase at low and high concentrations are used to evaluate the performances of the sampler. Tube preparation is described and the microwave desorption temperature is measured. Breakthrough volume is determined to allow sampling at 0.1-1 L/min for definite periods of time. The procedure is tested for the determination of gas and paticulate phase nicotine in sidestream smoke produced in an experimental chamber.     

Catalytic conversion of 2-propanol on La2MnZnO6

The perovskite La₂MnZnO₆ has been synthesized by a ceramic technique and its catalytic activity has been tested for 2-propanol decomposition. The catalyst is totally selective to dehydrogenation of the alcohol. A possible mechanism for the reaction is proposed.

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La₂MnZnO₆ 2-. . .

     

Miscibility in systems containing aqueous solutions of various alkylbenzenesulfonates, toluene and, n-butanol

Miscibility relationships in four-component systems containing sodium alkylbenzenesulfonates, toluene, n-butanol, and water were studied at 25°C in the hope of clarifying the complex systems used in the “micellar flood” enhanced oil recovery process. Phase boundary curves for the pseudo three-component systems (constant sulfonate/water ratios, 2.5 moles sulfonate per kg water) were determined. The sulfonates included those of benzene, toluene, xylene, ethylbenzene, isopropylbenzene, mesitylene, cymene, methyl-t-butylbenzene, and diisopropylbenzene, in all of which the alkyl substituents are smaller than in the usual surfactants. The phase boundary curves have similar and fairly symmetrical shapes. The amount of n-butanol (cosolvent) required to produce miscibility decreases with increasing number of alkyl carbons on the benzene ring of the sulfonates and seems relatively independent of the isomeric structure. The sodium salt of diisopropylbenzenesulfonate gives the lowest phase boundary curve (least n-butanol required for miscibility) among the nine sulfonates studied.     

Asymmetric Diels-Alder reactions with 5-menthyloxy-2-(5H)-furanone

A new class of chiral dienophiles, 5-alkoxy-2(5H)-furanones, has been developed. Both enantiomers of 5-menthyloxy-2(5H)-ftiranone are readily available in enantiomerically pure form, starting from furfural and d- or l-menthol. Excellent diastereoselectivities (d.e. β99%) are obtained in thermal Diels-Alder reactions with several cyclic and acyclic dienes. The use of silyl dienol ethers has resulted in new routes to enantiomerically pure cyclohexanones in a highly regioselective manner.