GaN1-xPx ternary alloys with high P composition grown by metal-organic chemical vapor deposition

GaN1-xPx ternary alloys with high P compositions were deposited on sapphire substrates by means of metal-organic chemical vapor deposition. Depth profiles of the elements indicate that the maximum P/N composition ratio is about 17% and a uniform distribution of the P atoms in the alloys is achieved. 2theta/omega XRD spectra demonstrate that the (0002) peak of the GaN1-xPx alloys shifts to smaller angle with increasing P composition. From the photoluminescence (PL) spectra, the red shifts to the bandedge emission of GaN are determined to be 73, 78, 100 and 87 meV for the GaN1-xPx alloys with the P/N composition ratios of 3%, 11%, 15% and 17%, respectively. No PL peak related to GaP is observed, indicating that the phase separation between GaN and GaP is well suppressed in our GaN1-xPx samples. (C) 2003 Elsevier Science B.V. All rights reserved.

Study on the Raman spectra of GaP nanorods synthesized within carbon nanotube templates

The Raman spectra of GaP nanorods grown in carbon nanotube templates have been reported. The red shifts of the TO and LO modes were observed due to phonon confinement effect in GaP nanorods. The measured red shifts range from 2 to 10cm(-1) depending on the size of the measured nanorods. It has been found that the polarization properties, which cannot be well explained by the selection rules of single nanorod, result from the direction disorder of nanorods in the measured area. The more the disorder is, the weaker the directionality of polarization properties is. The decrease of the Raman frequency of the TO and LO mode of the nanorods with the increasing power of the exciting laser suggests that the heating effect of the nanorods is far stronger than the bulk material. In addition, the saturation and then decrease of the Raman intensity with the increasing laser power indicate the rapid increase of the defects in the nanorods exposed to a strong exciting laser.

Effect of rapid thermal annealing and hydrogen plasma treatment on the microstructure and light-emission of silicon-rich oxide film

Silicon-rich silicon oxide (SRSO) films are prepared by plasma-enhanced chemical vapor deposition method at the substrate temperature of 200degreesC. The effect of rapid thermal annealing and hydrogen plasma treatment on tire microstructure and light-emission of SRSO films are investigated in detail using micro-Raman spectroscopy, Fourier transform infrared (FTIR) spectroscopy and photoluminescence (PL) spectra. It is found that the phase-separation degree of the films decreases with increasing annealing temperature from 300 to 600degreesC, while it increases with increasing annealing temperature from 600 to 900degreesC. The light-emission of the films are enhanced with increasing annealing temperature up to 500degreesC, while it is rapidly reduced when the annealing temperature exceeds 600degreesC. The peak position of the PL spectrum blueshifts by annealing at the temperature of 300degreesC, then it red-shifts with further raising annealing temperature. The following hydrogen plasma treatment results in a disproportionate increase of the PL intensity and a blueshift or redshift of the peak positions, depending on the pristine annealing temperature. It is thought that the size of amorphous silicon clusters, surface structure of the clusters and the distribution of hydrogen in the films can be changed during the annealing procedure. The results indicate that not only cluster size but also surface state of the clusters plays an important role in the determination of electronic structure of the amorphous silicon cluster and recombination process of light-generated carriers.

Modification of emission wavelength of self-assembled In(Ga)As/GaAs quantum dots covered by InxGa1-xAs(0 <= x <= 0.3) layer

Red shifts of emission wavelength of self-organized In(Cla)As/GaAs quantum dots (QDs) covered by 3 nm thick InxGa1-xAs layer with three different In mole fractions (x = 0.1, 0.2 and 0.3, respectively) have been observed. Transmission electron microscopy images demonstrate that the stress along growth direction in the InAs dots was reduced due to introducing the InxGa1-xAs (x = 0.1, 0.2 and 0.3) covering layer instead of GaAs layer. Atomic force microscopy pictures show a smoother surface of InAs islands covered by an In0.2Ga0.8As layer. It is explained by the calculations that the redshifts of the photoluminescence (PL) spectra from the QDs covered by the InxGa1-xAs (x greater than or equal to 0.1) layers were mainly due to the reducing of the strain other than the InAs/GaAs intermixing in the InAs QDs. The temperature dependent PL spectra further confirm that the InGaAs covering layer can effectively suppress the temperature sensitivity of PL emissions. 1.3 mum emission wavelength with a very narrow linewidth of 19.2 mcV at room temperature has been obtained successfully from In,In0.5Ga0.5As/GaAs self-assembled QDs covered by a 3-nm In0.2Ga0.2As strain reducing layer. (C) 2001 Elsevier Science B.V. All rights reserved.

Influence of InxGa1-xAs (0 <= x <= 0.3) cap layer on structural and optical properties of self-assembled InAs/GaAs quantum dots

Optical and structural properties of self-organized InAs/GaAs quantum dots (QDs) with InxGa1-xAs or GaAs cover layers grown by molecular beam epitaxy (MBE) have been characterized by transmission electron microscopy (TEM), atomic force microscopy (AFM) and photoluminescence (PL) measurements. The TEM and AFM images show that the surface stress of the InAs QDs was suppressed by overgrowth of a InxGa1-xAs covering layer on the top of the QDs and the uniformity of the QDs preserved. PL measurements reveal that red shifts of the PL emission due to the reduction of the surface strain of the InAs islands was observed and the temperature sensitivity of the PL emission energy was suppressed by overgrowth of InxGa1-xAs layers compared to that by overgrowth of GaAs layers.

Microstructure of SiOx : H films prepared by plasma enhanced chemical vapor deposition

The micro-Raman spectroscopy and infrared (IR) spectroscopy have been performed for the study of the microstructure of amorphous hydrogenated oxidized silicon (alpha-SiOx,:H) films prepared by Plasma Enhanced Chemical Vapor Deposition technique. It is found that a-SiOx:H consists of two phases: an amorphous silicon-rich phase and an oxygen-rich phase mainly comprised of HSi-SiO2 and HSi-O-3. The Raman scattering; results exhibit that the frequency of TO-like mode of amorphous silicon red-shifts with decreasing size of silicon-rich region. This is related to the quantum confinement effects, similar to the nanocrystalline silicon.

STUDY OF RAMAN-SPECTRA OF ZNSE-ZNTE STRAINED LAYER SUPERLATTICES

The Raman spectra of the II-VI wide band-gap compound ZnSe-ZnTe semiconductor strained-layer superlattices have been studied. The relations between the Raman shifts of the longitudinal optical phonon modes and the superlattice-structure parameters have been determined. When the layer thickness exceeds 40 angstrom, the change of the LO phonon-mode frequency shifts with the layer thickness is minimal, whereas when the layer thickness is smaller than 40 angstrom, great shifts have been observed. We estimate that the critical thickness of ZnSe-ZnTe SLS is about 40 angstrom. We have also found that the shifts induced by strain are much larger than the red shifts due to confinement.

Modification of emission wavelength of self-assembled In(Ga)As/GaAs quantum dots covered by InxGa1-xAs(0 <= x <= 0.3) layer

Red shifts of emission wavelength of self-organized In(Cla)As/GaAs quantum dots (QDs) covered by 3 nm thick InxGa1-xAs layer with three different In mole fractions (x = 0.1, 0.2 and 0.3, respectively) have been observed. Transmission electron microscopy images demonstrate that the stress along growth direction in the InAs dots was reduced due to introducing the InxGa1-xAs (x = 0.1, 0.2 and 0.3) covering layer instead of GaAs layer. Atomic force microscopy pictures show a smoother surface of InAs islands covered by an In0.2Ga0.8As layer. It is explained by the calculations that the redshifts of the photoluminescence (PL) spectra from the QDs covered by the InxGa1-xAs (x greater than or equal to 0.1) layers were mainly due to the reducing of the strain other than the InAs/GaAs intermixing in the InAs QDs. The temperature dependent PL spectra further confirm that the InGaAs covering layer can effectively suppress the temperature sensitivity of PL emissions. 1.3 mum emission wavelength with a very narrow linewidth of 19.2 mcV at room temperature has been obtained successfully from In,In0.5Ga0.5As/GaAs self-assembled QDs covered by a 3-nm In0.2Ga0.2As strain reducing layer. (C) 2001 Elsevier Science B.V. All rights reserved.

Starburst substituted hexaazatriphenylene compounds: synthesis, photophysical and electrochemical properties

Starburst-substituted hexaazatriphenylene Compounds have been designed and synthesized by introducing various peripheral aryl substituents to the central heterocyclic core. The effects of various substituent groups on the photophysical and electrochemical properties of the substituted hexaazatriphenylene have been investigated. Significant red-shifts of the absorption peak (from 413 nm to 530 nm) and emission peak (from 432 nm to 700 nm) were observed when the electron-donating ability of the aryl substituents was increased, corresponding to a decrease in the band gap from 2.90 eV to 2.05 eV. Introducing bulky substituents with weak electron-donating ability enhances the fluorescence quantum yield from 23% to 87%. In contrast, incorporating aryl substituents with strong electron-donating ability decreases the fluorescence quantum yield.

Luminescent properties of divalent samarium-doped strontium hexaborate

The valence change of samarium from trivalent to divalent in strontium hexaborate (SrB6O10) prepared in air is observed. The temperature dependence of the luminescence and vibronic transitions of Sm2+ are studied. The Sm2+ ions occupy three crystallographic sites. With increasing temperature, the D-5(0)-->F-7(0) transition line exhibits red shifts, and the half-width increases. At room temperature, due to the thermal population through the 4f(5)5d channel, the D-5(1)-->F-7(J) transitions are observed even though the vibrational energy is very close to the energy gap between the D-5(1) and D-5(0) levels in the host. A coupled phonon energy of about 108 cm(-1) is determined from the vibronic transitions of Sm2+ in the host.

Dibenzodioxin adsorption on inorganic materials

Dibenzodioxin adsorption/desorption on solid surfaces is an important issue associated with the formation, adsorption, and emission of dioxins. Dibenzodioxin adsorption/desorption behaviors on inorganic materials (amorphous/mesoporous silica, metal oxides, and zeolites) were investigated using in situ FT-IR spectroscopy and thermogravimetric (TG) analysis. Desorption temperatures of adsorbed dibenzodioxin are very different for different kinds of inorganic materials: similar to 200 degrees C for amorphous/mesoporous silica, similar to 230 degrees C for metal oxides, and similar to 450 degrees C for NaY and mordenite zeolites. The adsorption of dibenzodioxin can be grouped into three categories according to the red shifts of the IR band at 1496 cm(-1) of the aromatic ring for the adsorbed dibenzodioxin: a shift of 6 cm-1 for amorphous/mesoporous silica, a shift of 10 cm(-1) for metal oxides, and a shift of 14 cm(-1) for NaY and mordenite, suggesting that the IR shifts are proposed to associated with the strength of the interaction between adsorbed dibenzodioxin and the inorganic materials. It is proposed that the dibenzodioxin adsorption is mainly via the following three interactions: hydrogen bonding with the surface hydroxyl groups on amorphous/mesoporous silica, complexation with Lewis acid sites on metal oxides, and confinement effect of pores of mordenite and NaY with pore size close to the molecular size of dibenzodioxin.

Consequences of N,C,N '- and C,N,N '-coordination modes on electronic and photophysical properties of cyclometalated aryl ruthenium(II) complexes

The effects of isoelectronic replacement of a neutral nitrogen donor atom by an anionic carbon atom in terpyridine ruthenium(II) complexes on the electronic and photophysical properties of the resulting N,C,N'- and C,N,N'-cyclometalated aryl ruthenium(II) complexes were investigated. To this end, a series of complexes was prepared either with ligands containing exclusively nitrogen donor atoms, that is, [Ru(R-1-tpy)(R-2-tpy)](2+) (R-1, R-2 = H, CO2Et), or bearing either one N,C,N'- or C,N,N'-cyclometalated ligand and one tpy ligand, that is, [Ru(R-1-(NCN)-C-Lambda-N-Lambda)(R-2-tpy)](+) and [Ru(R-1-(CNN)-N-Lambda-N-Lambda)(R-2-tpy)](+), respectively. Single-crystal X-ray structure determinations showed that cyclometalation does not significantly alter the overall geometry of the complexes but does change the bond lengths around the ruthenium(II) center, especially the nitrogen-to-ruthenium bond length trans to the carbanion. Substitution of either of the ligands with electron-withdrawing ester functionalities fine-tuned the electronic properties and resulted in the presence of an IR probe. Using trends obtained from redox potentials, emission energies, IR spectroelectrochemical responses, and the character of the lowest unoccupied molecular orbitals from DFT studies, it is shown that the first reduction process and luminescence are associated with the ester-substituted C,N,N'-cyclometalated ligand in [Ru(EtO2C-(CNN)-N-Lambda-N-Lambda)(tpy)](+). Cyclometalation in an N,C,N'-bonding motif changed the energetic order of the ruthenium d(zx), d(yz), and d(xy) orbitals. The red-shifted absorption in the N,C,N'-cyclometalated complexes is assigned to MLCT transitions to the tpy ligand. The red shift observed upon introduction of the ester moiety is associated with an increase in intensity of low-energy transitions, rather than a red shift of the main transition. Cyclometalation in the C,N,N'-binding motif also red-shifts the absorption, but the corresponding transition is associated with both ligand types. Luminescence of the cyclometalated complexes is relatively independent of the mode of cyclometalation, obeying the energy gap law within each individual series.

Ligand dynamics in myoglobin: calculation of infrared spectra for photodissociated NO

We present molecular dynamics simulations of the photodissociated state of MbNO performed at 300 K using a fluctuating charge model for the nitric oxide (NO) ligand. After dissociation, NO is observed to remain mainly in the centre of the distal haem pocket, although some movement towards the primary docking site and the xenon-4 pocket can be seen. We calculate the NO infrared spectrum for the photodissociated ligand within the haem pocket and find a narrow peak in the range 1915-1922 cm(-1). The resulting blue shift of 1 to 8 cm(-1) compared to gas-phase NO is much smaller than the red shifts calculated and observed for carbon monoxide (CO) in Mb. A small splitting, due to NO in the xenon-4 pocket, is also observed. At lower temperatures, the spectra and conformational space explored by the ligand remain largely unchanged, but the electrostatic interactions with residue His64 become increasingly significant in determining the details of the ligand orientation within the distal haem pocket. The investigation of the effect of the L29F mutation reveals significant differences between the behaviour of NO and that of CO, and suggests a coupling between the ligand and the protein dynamics due to the different ligand dipole moments.

Binding of pentagalloyl glucose to two globular proteins occurs via multiple surface sites

The interaction between pentagalloyl glucose (PGG) and two globular proteins, bovine serum albumin (BSA) and ribulose-1,5-bisphosphate carboxylase oxygenase (rubisco), was investigated by isothermal titration calorimetry (ITC). ITC data fit to a binding model consisting of two sets of multiple binding sites, which reveal similarities in the mode of binding of PGG to BSA and rubisco. In both cases, the interaction is characterized by a high number of binding sites, which suggests that binding occurs by a surface adsorption mechanism that leads to coating of the protein surface, which promotes aggregation and precipitation of the PGG-protein complex. This model was confirmed by turbidimetry analysis of the PGG-BSA interaction. Analysis of tryptophan fluorescence quenching during the interaction of PGG with BSA suggests that binding of PGG leads to some conformational changes that are energetically closer to the unfolded state of the BSA structure, because small red shifts in the resulting emission spectra were observed.

Calculations of vibrational frequencies, Raman activities and degrees of depolarization for complexes involving water, methanol and ethanol

Raman activities and degrees of depolarization are reported for 14 complexes involving methanol, ethanol and water using the MP2/aug-cc-pVDZ model. For ethanol both trans and gauche isomers are considered. The red-shifts of the OH stretching and the blue shifts of the bending tau(CO-OH) mode were analyzed for the proton-donor molecules upon hydrogen bond. The shift of the nu(CO) stretching mode of the alcohol molecules are also analyzed and found to be specific giving characterization of the amphoteric relation, being positive for the proton-acceptor and negative for the proton-donor molecule. (c) 2008 Elsevier B.V. All rights reserved.