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At least 19 records

The electronic structure and second-order nonlinear optical properties of donor-acceptor acetylenes - A detailed investigation of structure-property relationships

A series of donor-acceptor acetylene compounds was synthesized in which systematic changes in both the conjugation length and the donor-acceptor strength were made. The effect of these structural changes on the spectroscopic and electronic properties of the molecules and, ultimately, on the measured second-order molecular hyperpolarizabilities (beta) was investigated. It was found that increases in the donor-acceptor strength resulted in increases in the magnitude of beta. For this class of molecules, the increase is dominated by the energy of the intramolecular charge-transfer transition, while factors such as the ground to excited-state dipole moment change and the transition-moment integral are much less important. Increasing the conjugation length from one to two acetylene linkers did not result in an increase in the value of beta; however, beta increased sharply in going from two acetylenes to three. This increase is attributed to the superposition of several nearly isoenergetic excited states.

Stiegman, A. E.↗

Experimental Demonstration of the Dependence of the First Hyperpolarizability of Donor-Acceptor Substituted Polyenes on the Ground-State Polarization and Bond Length Alternation

The dependence of the product of the first hyperpolarizability, beta, and the ground-state dipole moment, mu, for a series of donor-acceptor polyenes with a large range of ground-state polarization, was measured in a variety of solvents by electric field induced second harmonic generation. The observed behavior of mu times beta as a function of ground-state polarization agrees well with theoretical predictions. In particular, as a function of increasing polarization, mu times beta was found to first increase, peak in a positive sense, decrease, pass through zero, become large and negative, and eventually peak in a negative sense.

hyperpolarizability donor-acceptor substituted pol↗

Solvent-tuned intramolecular charge-recombination rates in a conjugated donor-acceptor molecule

The nonradiative charge-recombination rates from the charge-transfer state of a new conjugated donor-acceptor molecule (p-cyano-p-prime-methylthiodiphenylacetylene) can be tuned over almost an order of magnitude by varying the polarity of the solvent. These measurements of intramolecular recombination show a turnover of rates as a function of emission energy, consistent with the 'normal' and 'inverted' behavior of Marcus theory. Steady-state spectra and time-resolved measurements make it possible to quantitatively compare thermal and optical electron-transfer rates as a function of driving force and demonstrate their correspondence.

Khundkar, Lutfur R.↗

GaAs-oxide interface states - Gigantic photoionization via Auger-like process

Spectral and transient responses of photostimulated current in MOS structures were employed for the study of GaAs-anodic oxide interface states. Discrete deep traps at 0.7 and 0.85 eV below the conduction band were found with concentrations of 5 x 10 to the 12th/sq cm and 7 x 10 to the 11th/sq cm, respectively. These traps coincide with interface states induced on clean GaAs surfaces by oxygen and/or metal adatoms (submonolayer coverage). In contrast to surfaces with low oxygen coverage, the GaAs-thick oxide interfaces exhibited a high density (about 10 to the 14th/sq cm) of shallow donors and acceptors. Photoexcitation of these donor-acceptor pairs led to a gigantic photoionization of deep interface states with rates 1000 times greater than direct transitions into the conduction band. The gigantic photoionization is explained on the basis of energy transfer from excited donor-acceptor pairs to deep states.

Lagowski, J.↗

Defect characterization in ZnGeP2 by time-resolved photoluminescence

The native defect-related optical properties of ZnGeP2 are studied by steady-state and time-resolved photoluminescence. ZnGeP2 crystals grown from the vapor phase by high pressure physical vapor transport (HPVT) and from the melt by gradient freezing (GF) show a broad infrared emission with peak position at 1.2 eV with a decay time constant of a few micro-s and a faster recombination center peaked at 1.68 eV. The decay transient for the emission at 1.2 eV exhibits features of classical donor-acceptor recombination and is linked to close-pairs that are tentatively associated with germanium-on-zinc antisite donors and zinc vacancy acceptors. Higher energetic luminescence structures at 1.6eV and 1.7eV are revealed after annealing of the ZnGeP2 crystals and are associated with the formation zinc and phosphorous vacancies in the near surface region. ZnGeP2 crystals grown by HPVT from zinc and phosphorus supersaturated vapor compositions show additional emission structure at 1.8 eV and a sharp donor-acceptor emission at 1.778 eV that is related to the presence of additional donor states.

Dietz, N.↗

Primary cells utilize halogen-organic charge transfer complex

Electrochemical cells with solid state components employ charge transfer complexes or donor-acceptor complexes in which the donor component is an organic compound and the acceptor component is a halogen. A minor proportion of graphite added to these composition helps reduce the resistivity.

Gutmann, F.↗

Ion-implanted epitaxially grown ZnSe

The use of ZnSe to obtain efficient, short wavelength injection luminescence was investigated. It was proposed that shorter wavelength emission and higher efficiency be achieved by employing a p-i-n diode structure rather than the normal p-n diode structure. The intervening i layer minimizes concentration quenching effects and the donor-acceptor pair states leading to long wavelength emission. The surface p layer was formed by ion implantation; implantation of the i layer rather than the n substrate permits higher, uncompensated p-type doping. An ion implanted p-n junction in ZnSe is efficiency-limited by high electron injection terminating in nonradiative recombination at the front surface, and by low hole injection resulting from the inability to obtain high conductivity p-type surface layers. While the injection ratio in p-n junctions was determined by the radio of majority carrier concentrations, the injection ratio in p-i-n structures was determined by the mobility ratios and/or space charge neutrality requirements in the i layer.

Chernow, F.↗

GaAs-oxide interface states - A gigantic photoionization effect and its implications to the origin of these states

Gigantic photoionization was discovered on GaAs-oxide interfaces leading to the discharge of deep surface states with rates exceeding 1000 times those of photoionization transitions to the conduction band. It exhibits a peak similar to acceptor-donor transitions and is explained as due to energy transfer from photo-excited donor-acceptor pairs to deep surface states. This new process indicates the presence of significant concentrations of shallow donor and acceptor levels not recognized in previous interface models.

Lagowski, J.↗

Electron tunneling through covalent and noncovalent pathways in proteins

A model is presented for electron tunneling in proteins which allows the donor-acceptor interaction to be mediated by the covalent bonds between amino acids and noncovalent contacts between amino acid chains. The important tunneling pathways are predicted to include mostly bonded groups with less favorable nonbonded interactions being important when the through bond pathway is prohibitively long. In some cases, vibrational motion of nonbonded groups along the tunneling pathway strongly influences the temperature dependence of the rate. Quantitative estimates for the sizes of these noncovalent interactions are made and their role in protein mediated electron transport is discussed.

Beratan, David N.↗

A predictive theoretical model for electron tunneling pathways in proteins

A practical method is presented for calculating the dependence of electron transfer rates on details of the protein medium intervening between donor and acceptor. The method takes proper account of the relative energetics and mutual interactions of the donor, acceptor, and peptide groups. It also provides a quantitative search scheme for determining the important tunneling pathways (specific sequences of localized bonding and antibonding orbitals of the protein which dominate the donor-acceptor electronic coupling) in native and tailored proteins, a tool for designing new proteins with prescribed electron transfer rates, and a consistent description of observed electron transfer rates in existing redox labeled metalloproteins and small molecule model compounds.

Onuchic, Jose Nelson↗

Second and third order nonlinear optical properties of conjugated molecules and polymers

Second- and third-order nonlinear optical properties of some newly synthesized organic molecules and polymers are reported. Powder second-harmonic-generation efficiencies of up to 200 times urea have been realized for asymmetric donor-acceptor acetylenes. Third harmonic generation chi(3)s have been determined for a series of small conjugated molecules in solution. THG chi(3)s have also been determined for a series of soluble conjugated copolymers prepared using ring-opening metathesis polymerization. The results are discussed in terms of relevant molecular and/or macroscopic structural features of these conjugated organic materials.

Perry, Joseph W.↗

Optical Characterization of Bulk ZnSeTe Solid Solutions

Optical characterization was performed on wafers sliced from crystals of ZnSe, ZnTe and ZnSe (sub 1-x) Te (sub x) (0 less than x less than 0.4) grown by physical vapor transport technique. The energy band gaps at room temperature were determined from optical transmission measurements on 11 wafers. The best fit to the band gap vs. composition, x, data gives a bowing parameter of 1.336 which is between the value of 1.23 determined previously on ZnSeTe bulk crystals by reflectivity and the value of 1.621 reported on epilayers by photoconductivity. Low-temperature photoluminescence (PL) spectra were measured on 6 samples. The spectra of ZnSe and ZnTe were dominated by near band edge emissions and no deep donor-acceptor pairs were observed. The PL spectrum exhibited a broad emission for each of the ZnSe (sub 1-x) Te (sub x) samples, 0.09 less than x less than 0.39. For x = 0.09, this emission energy is about 0.2eV lower than the band gap energy measured at low temperature. As x increases the energy discrepancy gradually decreases and reduces to almost zero at x = 0.4. The single broad PL emission spectra and the spectra measured as a function of temperature were interpreted to be associated with the exciton bound to Te clusters because of the high Te content in these samples.

Su, Ching-Hua↗

The Effect of the Wall Contact and Post-Growth, Cool-Down on Defects in CdTe Crystals Grown By 'Contactless' PVT

To take a maximum advantage of materials processing in microgravity for understanding the effects of gravity, gravity-independent effects should be minimized. In crystal growth, the quality of the grown crystals may depend, among other factors, on their interaction with the walls of the processing container during and after growth, and on the rate of the crystal cool-down at the end of the process. To investigate the above phenomena, a series of CdTe crystal growth processes was carried out. The crystals were grown by physical vapor transport without contact with the side walls of the silica glass ampoules. To eliminate the effect of the seed quality, and to reduce the number of nuclei and related crystal grains, the Low Supersaturation Nucleation technique was applied. The source temperature was 930 C, the undercooling was a few degrees. The crystals, having the diameter of 25 mm, grew at the rate of a few mm per day. The post-growth cool-down to the room temperature was conducted at different rates, and lasted from a few minutes to four days. The crystals were characterized using chemical etching, low temperature luminescence, and Synchrotron White Beam X-ray Topography techniques. The dislocation (etch pit) density was measured and its distribution was analyzed by comparison with Poisson curves and with the Normalized Radial Distribution Correlation Function. In the regions where the crystal is in contact with silica, the materials show a considerable strain field which extends for a few mm or more from the silica-crystal interface. In the reference crystal grown with contact with the ampoule walls, and when the crystals are cooled at the highest rates, the etch pit/dislocation density is in the high 10(exp 5) per square centimeter region. Typical EPD values for lower cool-down rates are in the lower 10(exp 4) per square centimeter region. In some areas the actual dislocation density was about 10(exp 3) per square centimeter or even less. No apparent effect of the cool-down rate on polygonization was observed. Low temperature PL spectra show, that the dominant peak is (D(sup 0), h) and (A(sup 0), e) for samples with low and high dislocation densities, respectively. For low EPD crystals a peak at 1.45 eV with 21 meV phonon replicas was observed and attributed to donor-acceptor pair to neutral copper-acceptor transition. In high EPD crystals this PL structure was not observed, apparently due to the masking effect of the strong contribution from the dislocation band.

Palosz, W.↗

Optical Characterization of Bulk ZnSeTe Solid Solutions

Optical characterization was performed on wafers sliced from crystals of ZnSe, ZnTe, and ZnSe(1-x)Te(x)(0 less than x less than 0.4) grown by physical vapor transport. Energy band gaps at room temperature were determined from optical transmission measurements on 11 wafers. A best fit curve to the band gap versus composition x data gives a bowing parameter of 1.45. This number lies between the value of 1.23 determined previously on ZnSeTe bulk crystals and the value of 1.621 reported on ZnSeTe epilayers. Low-temperature photoluminescence (PL) spectra were measured on six samples. The spectra of ZnSe and ZnTe were dominated by near band edge emissions and no deep donor-acceptor pairs were observed. The PL spectrum exhibited a broad emission for each of the ZnSe(1-x)Te(x) samples, 0.09 less than x less than 0.39. For x=0.09, this emission energy is about 0.2 eV lower than the band gap energy measured at low temperature. As x increases the energy discrepancy gradually decreases and reduces to almost zero at x=0.4. The single broad PL emission spectra and the spectra measured as a function of temperature were interpreted as being associated with the exciton bound to Te clusters because of the high Te content in these samples.

Su, Ching-Hua↗

Crystal Growth of ZnSe and Related Ternary Compound Semiconductors by Vapor Transport

The objective of the project is to determine the relative contributions of gravity-driven fluid flows to the compositional distribution, incorporation of impurities and defects, and deviation from stoichiometry observed in the crystals grown by vapor transport as results of buoyance-driven convection and growth interface fluctuations caused by irregular fluid-flows. ZnSe and related ternary compounds, such as ZnSeS and ZnSeTe, were grown by vapor transport technique with real time in-situ non-invasive monitoring techniques. The grown crystals were characterized extensively to correlate the grown crystal properties with the growth conditions. The following are the research progress in the past two years. In-situ monitoring of partial pressure by optical absorption technique and visual observation of the growing crystal were performed during vapor growth of ZnSe. Low-temperature photoluminescence (PL) spectra and glow discharge mass spectroscopy (GDMS) were measured on ZnSe starting materials provided by various vendors and on bulk crystals grown from these starting materials by physical vapor transport (PVT) to study the effects of purification and contamination during crystal growth process. Optical characterization was performed on wafers sliced from the grown crystals of ZnSe, ZnTe and ZnSe(1-x),Te(x), (0<x<0.4). Energy band gaps at room temperature were determined from optical transmission measurements and a best fit curve to the band gap vs. composition, x, data gives a bowing parameter of 1.45. Low-temperature photoluminescence (PL) spectra of ZnSe and ZnTe were dominated by near band edge emissions and no deep donor-acceptor pairs were observed. The PL spectrum exhibited a broad emission for the ZnSe(1-x),Te(x), samples, 0.09<x<0.39. The single broad PL emission spectra and the spectra measured as a function of temperature were interpreted as being associated with the exciton bound to Te clusters because of the high Te content in these samples. To validate numerical codes, in-situ monitoring during the PVT of HgI2 was designed. Optical absorption spectra of the vapor phase over HgI2 were measured for wavelengths between 200 and 600nm at sample temperatures between 349 and 610K. The Beer's Law constants for 15 wavelengths between 200 and 440 nm were determined. From these constants the vapor pressure of HgI2 was established as a function of temperature for the liquid and the solid Beta-phases To characterize the growth conditions during the PVT growth of In-doped ZnSe the optical absorbance of the vapor phase over the In-Se system were measured and were used to obtain the partial pressures of Se2(g) and In2Se(g).

Su, Ching-Hua↗

The Effect of the Wall Contact and Post-Growth Cool-Down on Defects in CdTe Crystals Grown by 'Contactless' Physical Vapour Transport

A series of cadmium telluride crystals grown by physical vapor transport without contact with the ampoule walls and cooled at different rates were characterized using synchrotron X-ray topography, photoluminescence, and chemical etching. Strain from sticking to silica glass and its effect on the dislocation density is shown. It was found that very fast cool-down increases dislocation density by at least one order of magnitude. None of the samples had random dislocation distributions but coarse clumping of dislocations on the scale of more than 100 microns was more prevalent in slowly cooled crystals. Photoluminescence revealed that slow cooling favored the donor-acceptor luminescence involving complex A centers. This was diminished in fast cooled material; and effect presumed to be due to dislocation gettering. Fast cooling also enhanced the formation of shallow acceptors. Implications for Bridgman growth of CdTe and the vapor growth of CdZnTe are discussed briefly.

Palosz, W.↗