Molecular beam epitaxy of highly mismatched N-rich GaNSb and InNAs alloys

GaN materials alloyed with group V anions form the so-called highly mismatched alloys (HMAs). Recently, the authors succeeded in growing N-rich GaNAs and GaNBi alloys over a large composition range by plasma-assisted molecular beam epitaxy (PA-MBE). Here, they present first results on PA-MBE growth and properties of N-rich GaNSb and InNAs alloys and compare these with GaNAs and GaNBi alloys. The enhanced incorporation of As and Sb was achieved by growing the layers at extremely low growth temperatures. Although layers become amorphous for high As, Sb, and Bi content, optical absorption measurements show a progressive shift of the optical absorption edge to lower energy. The large band gap range and controllable conduction and valence band positions of these HMAs make them promising materials for efficient solar energy conversion devices

Highly mismatched GaN1−xSbxalloys: synthesis, structure and electronic properties

Highly mismatched alloys (HMAs) is a class of semiconductor alloys whose constituents are distinctly different in terms of size, ionicity and/or electronegativity. Electronic properties of the alloys deviate significantly from an interpolation scheme based on small deviations from the virtual crystal approximation. Most of the HMAs were only studied in a dilute composition limit. Recent advances in understanding of the semiconductor synthesis processes allowed growth of thin films of HMAs under non-equilibrium conditions. Thus reducing the growth temperature allowed synthesis of group III-N–V HMAs over almost the entire composition range. This paper focuses on the GaNxSb1−x HMA which has been suggested as a potential material for solar water dissociation devices. Here we review our recent work on the synthesis, structural and optical characterization of GaN1−xSbx HMA. Theoretical modeling studies on its electronic structure based on the band anticrossing (BAC) model are also reviewed. In particular we discuss the effects of growth temperature, Ga flux and Sb flux on the incorporation of Sb, film microstructure and optical properties of the alloys. Results obtained from two separate MBE growths are directly compared. Our work demonstrates that a large range of direct bandgap energies from 3.4 eV to below 1.0 eV can be achieved for this alloy grown at low temperature. We show that the electronic band structure of GaN1−xSbx HMA over the entire composition range is well described by a modified BAC model which includes the dependence of the host matrix band edges as well as the BAC model coupling parameters on composition. We emphasize that the modified BAC model of the electronic band structure developed for the full composition of GaNxSb1−x is general and is applicable to any HMA

Making the right link to theranostics : the photophysical and biological properties of dinuclear Ru^II-Re^I dppz complexes depend on their tether

The synthesis of new dinuclear complexes containing linked RuII(dppz) and ReI(dppz) moieties is reported. The photophysical and biological properties of the new complex, which incorporates a N,N′-bis(4-pyridylmethyl)-1,6-hexanediamine tether ligand, are compared to a previously reported RuII/ReI complex linked by a simple dipyridyl alkane ligand. Although both complexes bind to DNA with similar affinities, steady-state and time-resolved photophysical studies reveal that the nature of the linker affects the excited state dynamics of the complexes and their DNA photocleavage properties. Quantum-based DFT calculations on these systems offer insights into these effects. While both complexes are live cells permeant, their intracellular localizations are significantly affected by the nature of the linker. Notably, one of the complexes displayed concentration-dependent localization and possesses photophysical properties that are compatible with SIM and STED nanoscopy. This allowed the dynamics of its intracellular localization to be tracked at super resolutions

Syntheses and structures of M(L)(X)BPh4 complexes {M = Co(II), Zn(II); L = cis-1,3,5-tris[3-(2-furyl)prop-2- enylideneamino]cyclohexane, X = OAc, NO3}: structural models of the active site of carbonic anhydrase

The metal coordination geometries in the structures of the zinc(II) and cobalt(II) complexes of the ligand cis-1,3,5-tris[3-(2-furyl)prop-2-enylideneamino]cyclohexane (fr-protach) and with the anions nitrate and acetate are structural models for the active site of carbonic anhydrase. The acetate structures show a striking structural correlation with the metal coordination environments in the known bicarbonate forms of the enzyme. Such structures provide a basis for understanding the marked effect of different metal substitution on the catalytic rate of the enzyme

Growth and characterization of highly mismatched GaN1-xSbx alloys

A systematic investigation on the effects of growth temperature, Ga flux, and Sb flux on the incorporation of Sb, film structure, and optical properties of the GaN1-xSbx highly mismatched alloys (HMAs) was carried out. We found that the direct bandgap ranging from 3.4 eV to below 1.0 eV for the alloys grown at low temperature. At the growth temperature of 80 degrees C, GaN1-xSbx with x>6% losses crystallinity and becomes primarily amorphous with small crystallites of 2-5 nm. Despite the range of microstructures found for GaN1-xSbx alloys with different composition, a well-developed absorption edge shifts from 3.4 eV (GaN) to close to 2 eV for samples with a small amount, less than 10% of Sb. Luminescence from dilute GaN1-xSbx alloys grown at high temperature and the bandgap energy for alloys with higher Sb content are consistent with a localized substitutional Sb level E-Sb at similar to 1.1 eV above the valence band of GaN. The decrease in the bandgap of GaN1-xSbx HMAs is consistent with the formation of a Sb-derived band due to the anticrossing interaction of the Sb states with the valence band of GaN

Tellurium n-type doping of highly mismatched amorphous GaN1-xAsx alloys in plasma-assisted molecular beam epitaxy

In this paper we report our study on n-type Te doping of amorphous GaNi1-xAsx layers grown by plasma assisted molecular beam epitaxy. We have used a low temperature PbTe source as a source of tellurium. Reproducible and uniform tellurium incorporation in amorphous GaNi1-xAsx layers has been successfully achieved with a maximum Te concentration of 9 x 10(20) cm(-3). Tellurium incorporation resulted in n-doping of GaN1-xAsx layers with Hall carrier concentrations up to 3 x 10(19) cm(-3) and mobilities of similar to 1 cm(2)/V s. The optimal growth temperature window for efficient Te doping of the amorphous GaNi1-xAsx layers has been determined

Highly mismatched GaN1−xSbxalloys: synthesis, structure and electronic properties

Highly mismatched alloys (HMAs) is a class of semiconductor alloys whose constituents are distinctly different in terms of size, ionicity and/or electronegativity. Electronic properties of the alloys deviate significantly from an interpolation scheme based on small deviations from the virtual crystal approximation. Most of the HMAs were only studied in a dilute composition limit. Recent advances in understanding of the semiconductor synthesis processes allowed growth of thin films of HMAs under non-equilibrium conditions. Thus reducing the growth temperature allowed synthesis of group III-N–V HMAs over almost the entire composition range. This paper focuses on the GaNxSb1−x HMA which has been suggested as a potential material for solar water dissociation devices. Here we review our recent work on the synthesis, structural and optical characterization of GaN1−xSbx HMA. Theoretical modeling studies on its electronic structure based on the band anticrossing (BAC) model are also reviewed. In particular we discuss the effects of growth temperature, Ga flux and Sb flux on the incorporation of Sb, film microstructure and optical properties of the alloys. Results obtained from two separate MBE growths are directly compared. Our work demonstrates that a large range of direct bandgap energies from 3.4 eV to below 1.0 eV can be achieved for this alloy grown at low temperature. We show that the electronic band structure of GaN1−xSbx HMA over the entire composition range is well described by a modified BAC model which includes the dependence of the host matrix band edges as well as the BAC model coupling parameters on composition. We emphasize that the modified BAC model of the electronic band structure developed for the full composition of GaNxSb1−x is general and is applicable to any HMA