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Cardelino, C. A.

Publications and source records attributed to Cardelino, C. A..

Theoretical Study of Indium Compounds of Interest for Organometallic Chemical Vapor Deposition

The structural. electronic and therinochemical properties of indium compounds which are of interest in halide transport and organometallic chemical vapor deposition processes have been studied by ab initio and statistical mechanics methods. The compounds reported include: indium halides and hydrides (InF, InCl, InCl3, InH, InH2, InH3); indium clusters (In2, In3); methylindium, dimethylindium, and their hydrogen derivatives [In(CH3), In(CH3)H, In(CH3)H2, In(CH3)2, In(CH3)2H]; dimethyl-indium dimer [In2(CH3)4], trimethyl-indium [In(CH3)3]; dehydrogenated methyl, dimethyl and trimethylindium [In(CH3)2CH2, In(CH3)CH2, In(CH2)], trimethylindium adducts with ammonia, trimethylamine and hydrazine [(CH3)3In:NH3, (CH3)3In:N(CH3)3, (CH3)3In:N(H2)N(H2)]; dimethylamino-indium and methylimino-indium [In(CH3)2(NH2), In(CH3)(NH)]; indium nitride and indium nitride dimer (InN, In2N2), indium phosphide, arsenide and antimonide ([InP, InAs, InSb). The predicted electronic properties are based on density functional theory calculations; the calculated thermodynamic properties are reported following the format of the JANAF (Joint Army, Navy, NASA, Air Force) Tables. Equilibrium compositions at two temperatures (298 and 1000 K) have been analyzed for groups of competing simultaneous reactions.

Cardelino, B. H.↗

Modeling and Real-Time Process Monitoring of Organometallic Chemical Vapor Deposition of III-V Phosphides and Nitrides at Low and High Pressure

The purpose of this paper is to review modeling and real-time monitoring by robust methods of reflectance spectroscopy of organometallic chemical vapor deposition (OMCVD) processes in extreme regimes of pressure. The merits of p-polarized reflectance spectroscopy under the conditions of chemical beam epitaxy (CBE) and of internal transmission spectroscopy and principal angle spectroscopy at high pressure are assessed. In order to extend OMCVD to materials that exhibit large thermal decomposition pressure at their optimum growth temperature we have designed and built a differentially-pressure-controlled (DCP) OMCVD reactor for use at pressures greater than or equal to 6 atm. We also describe a compact hard-shell (CHS) reactor for extending the pressure range to 100 atm. At such very high pressure the decomposition of source vapors occurs in the vapor phase, and is coupled to flow dynamics and transport. Rate constants for homogeneous gas phase reactions can be predicted based on a combination of first principles and semi-empirical calculations. The pressure dependence of unimolecular rate constants is described by RRKM theory, but requires variational and anharmonicity corrections not included in presently available calculations with the exception of ammonia decomposition. Commercial codes that include chemical reactions and transport exist, but do not adequately cover at present the kinetics of heteroepitaxial crystal growth.

Bachmann, K. J.↗

Natural hydrocarbons, urbanization, and urban ozone

The combined effects of emission control and urbanization, with its concomitant intensification of the urban heat island, on urban ozone concentrations are studied. The effect of temperature on ozone is considered, and attention is given to the temperature effect on ozone photochemistry. Model calculations suggest that ozone concentration enhancements are caused by the effect of temperature on the atmospheric chemistry of peroxyacetyl nitrate, as well as the temperature dependence of natural and anthropogenic hydrocarbon emissions. It is pointed out that, because of the sensitivity of urban ozone to local climatic conditions and the ability of trees to moderate summertime temperatures, the inadvertent removal of trees from urbanization can have an adverse effect on urban ozone concentration, while a temperature increase in the urban heat island caused by urbanization can essentially cancel out the ozone-reducing benefits obtained from a 50-percent reduction in anthropogenic hydrocarbon emissions.

Cardelino, C. A.↗

The atmospheric lifetime experiment. I - Introduction, instrumentation, and overview

The Atmospheric Lifetime Experiment is designed to determine accurately the atmospheric concentrations of the four halocarbons CFCl3, CF2Cl2, CCl4, and CH3CCl3, and also of N2O with emphasis on measurement of their long-term trends in the atmosphere. Comparison of these concentrations and trends for the four halocarbons with estimates of their industrial emission rates then enables calculations of their global circulation rates and globally averaged atmospheric lifetimes. The experiment utilizes automated dual-column electron-capture gas chromatographs which sample the background air about 4 times daily at the following globally distributed sites: Adrigole, Ireland, Cape Meares, Oregon; Ragged Point, Barbados; Point Matatula, American Samoa, and Cape Grim, Tasmania. The climatology of these 'clean air' sites and their ability to describe the global air mass are reviewed. The instrumentation and methods for data acquisition and processing are then described. An overview of the data obtained and the trends derived during the 3-year period from July 1978 through June 1981 for each of the five species being measured is presented.

Prinn, R. G.↗

The atmospheric lifetime experiment. III - Lifetime methodology and application to three years of CFCL3 data

Observations of the chlorofluorocarbon CFCl3 obtained several times daily over the period July 1978 to June 1981 at Adrigole, Ireland; Ragged Point, Barbados; Point Matatula, American Samoa; and Cape Grim, Tasmania are reported. In addition, observations at Cape Meares, Oregon are given for the period January 1980 to June 1981. On January 1, 1980, the average mixing ratio of CFCl3 in the lower troposphere is esimated to have been 168 pptv, and this is calculated to have been increasing 5.7 percent annually. Assuming that the only destruction of CFCl3 occurs in the stratosphere, the lifetime, on January 1, 1980, estimated by a trend technique is 83 + 73, or -27 years; the lifetime estimated from the global inventory of CFCl3 is to + 89 or -25 years. The maximum likelihood current lifetime estimate obtained by combining the estimates from both analysis techniques is 78 years.

Cunnold, D. M.↗

The Atmospheric Lifetime Experiment. IV - Results for CF2Cl2 based on three years data

Observations of dichlorodifluoromethane obtained several times daily over the period July 1978 to June 1981 at Adrigole, Ireland (52 deg N, 10 deg W), Ragged Point, Barbados (13 deg N, 59 deg W), Point Matatula, American Samoa (14 deg S, 171 deg W), and Cape Grim, Tasmania (41 deg S, 145 deg E), are reported. Observations at Cape Meares, Oregon (45 deg N, 124 deg W), are also given for the period November 1980 to June 1981. On January 1, 1980, the average mixing ratio of dichlorodifluoromethane in the lower troposphere is estimated to have been 285 pptv and to have been increasing at 6.0 percent/year. The atmospheric lifetime of this compound is estimated from this data by adjusting its destruction rate in a two-dimensional model of the atmosphere so as to provide the best fit to the observations. Assuming destruction of CF2Cl2 in the stratosphere only, the lifetime estimate for January 1, 1980, by the inventory technique is 69 + 36 or - 18 years. The trend technique principally provides a lower limit to the lifetime of 81 years. The results suggest a need for further assessment of dichlorodifluoromethane release estimates, particularly those from the USSR and eastern Europe.

Cunnold, D. M.↗