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NASA NTRS2004

Advanced Computational Modeling of Vapor Deposition in a High-Pressure Reactor

In search of novel approaches to produce new materials for electro-optic technologies, advances have been achieved in the development of computer models for vapor deposition reactors in space. Numerical simulations are invaluable tools for costly and difficult processes, such as those experiments designed for high pressures and microgravity conditions. Indium nitride is a candidate compound for high-speed laser and photo diodes for optical communication system, as well as for semiconductor lasers operating into the blue and ultraviolet regions. But InN and other nitride compounds exhibit large thermal decomposition at its optimum growth temperature. In addition, epitaxy at lower temperatures and subatmospheric pressures incorporates indium droplets into the InN films. However, surface stabilization data indicate that InN could be grown at 900 K in high nitrogen pressures, and microgravity could provide laminar flow conditions. Numerical models for chemical vapor deposition have been developed, coupling complex chemical kinetics with fluid dynamic properties.

Cardelino, Beatriz H.↗

NASA NTRS2004

Thermally Stable Heterocyclic Imines as New Potential Nonlinear Optical Materials

In the course of a search for new thermostable acentric nonlinear optical crystalline materials, several heterocyclic imine derivatives were designed, with the general structure D-pi-A(D'). Introduction of a donor amino group (D') into the acceptor moiety was expected to bring H-bonds into their crystal structures, and so to elevate their melting points and assist in an acentric molecular packing. Six heterocycle-containing compounds of this type were prepared, single crystals were grown for five of them, and these crystals were characterized by X-ray analysis. A significant melting temperature elevation was found for all of the synthesized compounds. Three of the compounds were also found to crystallize in acentric space groups. One of the acentric compounds is built as a three-dimensional H-bonded molecular network. In the other two compounds, with very similar molecular structure, the molecules form one-dimensional H-bonded head-to-head associates (chains). These chains are parallel in two different crystallographic directions and form very unusual interpenetrating chain patterns in an acentric crystal. Two of the compounds crystallized with centrosymmetric molecular packing.

Nesterov, Volodymyr V.↗

NASA NTRS2004

Advanced Computational Modeling of Vapor Deposition in a High-pressure Reactor

In search of novel approaches to produce new materials for electro-optic technologies, advances have been achieved in the development of computer models for vapor deposition reactors in space. Numerical simulations are invaluable tools for costly and difficult processes, such as those experiments designed for high pressures and microgravity conditions. Indium nitride is a candidate compound for high-speed laser and photo diodes for optical communication system, as well as for semiconductor lasers operating into the blue and ultraviolet regions. But InN and other nitride compounds exhibit large thermal decomposition at its optimum growth temperature. In addition, epitaxy at lower temperatures and subatmospheric pressures incorporates indium droplets into the InN films. However, surface stabilization data indicate that InN could be grown at 900 K in high nitrogen pressures, and microgravity could provide laminar flow conditions. Numerical models for chemical vapor deposition have been developed, coupling complex chemical kinetics with fluid dynamic properties.

Cardelino, Beatriz H.↗

NASA NTRS1999

Development of an Advanced Computational Model for OMCVD of Indium Nitride

An advanced computational model is being developed to predict the formation of indium nitride (InN) film from the reaction of trimethylindium (In(CH3)3) with ammonia (NH3). The components are introduced into the reactor in the gas phase within a background of molecular nitrogen (N2). Organometallic chemical vapor deposition occurs on a heated sapphire surface. The model simulates heat and mass transport with gas and surface chemistry under steady state and pulsed conditions. The development and validation of an accurate model for the interactions between the diffusion of gas phase species and surface kinetics is essential to enable the regulation of the process in order to produce a low defect material. The validation of the model will be performed in concert with a NASA-North Carolina State University project.

Cardelino, Carlos A.↗

NASA NTRS1999

Molecular Modeling and Experimental Investigations of Nonlinear Optical Compounds Monosubstituted Derivatives of Dicyanovinylbenzene

A search for potential nonlinear optical compounds was performed using the Cambridge Structure Database and molecular modeling. We investigated a series of monosubstituted derivatives of dicyanovinylbenzene, since the nonlinear optical (NLO) properties of such derivatives (o-methoxy-dicyanovinylbenzene, DIVA) were studied earlier. The molecular geometry of these compounds was investigated with x-ray analysis and discussed along with the results of molecular mechanics and ab initio quantum chemical calculations. The influence of crystal packing on the planarity of the molecules of this series has been revealed. Two new compounds from the series studied, ortho-F and para-Cl-dicyanovinylbenzene, according to powder measurements, were found to be NLO compounds in the crystal state about 10 times more active than urea. The peculiarities of crystal structure formation in the framework of balance between van der Waals and electrostatic interactions have been discussed. The crystal shape of DIVA and two new NLO compounds have been calculated on the basis of the known crystal structure.

Timofeeva, Tatiana V.↗

NASA NTRS1998

Effect of halogenation on the nonlinear optical properties of porthyrin and substituted porphyrins

The effect that fluorine and chlorine substitution has on the nonlinear optical properties of porphyrin, tetramethylporphyrin and tetraphenylporphyrin has been theoretically studied. The calculations of nonlinear optical properties have been obtained by performing finite-field calculations on structures determined by semiempirical methods. In addition, tetra(p-chlorophenyl)porphyrin and tetra(p-bromophenyl)porphyrin were synthesized by the condensation of pyrrol and the appropriate aldehyde. Thin films of polymethylmethacrylate were obtained containing these materials, by spin coating onto glass substrates. The films were characterized by third-harmonic generation. It was determined that the experimental conditions enhance the third-order polarizability of the tetraphenylporphyrins by a factor of about 1.6.

Cardelino, Beatriz H.↗

NASA NTRS1997

Molecular Static Third-Order Polarizabilities of Carbon-Cage Fullerenes and their Correlation with Three Geometric Parameters: Group Order, Aromaticity, and Size

Calculations were performed on the valence contribution to the static molecular third-order polarizabilities (gamma) of thirty carbon-cage fullerenes (C60, C70, five isomers of C78, and twenty-three isomers of C84). The molecular structures were obtained from B3LYP/STO-3G calculations. The values of the tensor elements and an associated numerical uncertainty were obtained using the finite-field approach and polynomial expansions of orders four to eighteen of polarization versus static electric field data. The latter information was obtained from semiempirical calculations using the AM1 hamiltonian.

Moore, Craig E.↗

NASA NTRS1991

Static second-order polarizability calculations for large molecular systems

A procedure to calculate all second-order polarizability tensor elements in static fields has been developed. The calculations are based on semiempirical Hamiltonians (MNDO) that include shaped electric fields. The technique has been applied to mono-, di-, and trisubstituted benzenes incorporating nitro, methyl, and primary and secondary amino groups.

Cardelino, Beatriz H.↗

NASA NTRS1991

Growth of bulk single crystals of organic materials for nonlinear optical devices - An overview

Highly perfect single crystals of nonlinear optical organic materials are required for use in optical devices. An overview of the bulk crystal growth of these materials by melt, vapor, and solution processes is presented. Additionally, methods that may be used to purify starting materials, detect impurities at low levels, screen materials for crystal growth, and process grown crystals are discussed.

Penn, Benjamin G.↗

NASA NTRS1991

Static second-order polarizabilities of aminobenzophenones and nitrobenzophenones

Static-field theoretical studies on molecular second-order polarizabilities (beta) of benzophenone derivatives were performed. Calculations were based on the use of shaped electric fields and semiempirical Hamiltonians. Either an electron-donating (amine) or an electron-withdrawing (nitro) substituent was incorporated into a phenyl ring of benzophenone; the phenyl rings of benzophenone were oriented either coplanar or perpendicular to the carbonyl. The change in charge transfer with respect to the electrophilic character of the carbonyl group was monitored to determine its effect on the molecular second-order polarizability. Calculations were performed for all constitutional isomers of the two benzophenone derivatives.

Moore, Craig E.↗