Electronic structure in five-coordinate complexes of nickel(II) with heavy-donor ligands

I.

Various studies designed to elucidate the electronic structure of the arsenic donor ligand, o-phenylenebisdimethylarsine (diarsine), have been carried out. The electronic spectrum of diarsine has been measured at 300 and 77˚K. Electronic spectra of the molecular complexes of various substituted organoarsines and phosphines with tetracyanoethylene have been measured and used to estimate the relative ionization potentials of these molecules.

Uv photolysis of arsines in frozen solution (96˚K) has yielded thermally labile, paramagnetic products. These include the molecular cations of the photolyzed compounds. The species (diars)⁺ exhibits hyper-fine splitting due to two equivalent ⁷⁵As(I=3/2) nuclei. Resonances due to secondary products are reported and assignments discussed.

Evidence is presented for the involvement of d-orbitals in the bonding of arsines. In (diars)⁺ there is mixing of arsenic “lone-pair” orbitals with benzene ring π-orbitals.

II.

Detailed electronic spectral measurements at 300 and 77˚K have been carried out on five-coordinate complexes of low-spin nickel(II), including complexes of both trigonal bipyramidal (TBP) and square pyramidal (SPY) geometry. TBP complexes are of the form NiLX⁺ (X=halide or cyanide,

L = Qƭ(CH₂)₃As(CH₃)₂]₃ or

P [hexagon - Q'CH₃] , Q = P, As,

Q’=S, Se).

The electronic spectra of these compounds exhibit a novel feature at low temperature. The first ligand field band, which is asymmetric in the room temperature solution spectrum, is considerably more symmetrical at 77˚K. This effect is interpreted in terms of changes in the structure of the complex.

The SPY complexes are of the form Ni(diars)₂X^z (X=CL, Br, CNS, CN, thiourea, NO₂, As). On the basis of the spectral results, the d-level ordering is concluded to be xy ˂ xz, yz ˂ z² ˂˂ x² - y². Central to this interpretation is identification of the symmetry-allowed ¹A₁ → ¹E (xz, yz → x² - y²) transition. This assignment was facilitated by the low temperature measurements.

An assignment of the charge-transfer spectra of the five-coordinate complexes is reported, and electronic spectral criteria for distinguishing the two limiting geometries are discussed.

Reprint of: Flow filtering and the physical sources of aerodynamic sound

The physical sources of sound are expressed in terms of the non-radiating part of the flow. The non-radiating part of the flow can be obtained from convolution filtering, as we demonstrate numerically by using an axi-symmetric jet satisfying the Navier-Stokes equations. Based on the frequency spectrum of the source, we show that the sound sources exhibit more physical behaviour than sound sources based on acoustic analogies. To validate the sources of sound, one needs to let them radiate within the non-radiating flow field. However, our results suggest that the traditional Euler operator linearized about the time-averaged part of the flow should be sufficient to compute the sound field. © 2010 Published by Elsevier Ltd.

Fourier spectrum based extraction of an equivalent trap state density in indium gallium zinc oxide transistors

Segregating the dynamics of gate bias induced threshold voltage shift, and in particular, charge trapping in thin film transistors (TFTs) based on time constants provides insight into the different mechanisms underlying TFTs instability. In this Letter we develop a representation of the time constants and model the magnitude of charge trapped in the form of an equivalent density of created trap states. This representation is extracted from the Fourier spectrum of the dynamics of charge trapping. Using amorphous In-Ga-Zn-O TFTs as an example, the charge trapping was modeled within an energy range of ΔEt 0.3 eV and with a density of state distribution as Dt(Et-j)=Dt0exp(-ΔEt/ kT)with Dt0 = 5.02 × 1011 cm-2 eV-1. Such a model is useful for developing simulation tools for circuit design. © 2014 AIP Publishing LLC.

New observations on the pressure dependence of luminescence from Eu2+-doped MF2 (M = Ca, Sr, Ba) fluorides

The luminescence from Eu2+ ions in MF2 (M = Ca, Sr, Ba) fluorides has been investigated under the pressure range of 0-8 GPa. The emission band originating from the 4f(6)5d(1) -> 4f(7) transition of Eu2+ ions in CaF2 and SrF2 shows the red-shift as increasing pressure with pressure coefficients of -17 meV/GPa for CaF2 and -18 meV/GPa for SrF2. At atmospheric pressure, the emission spectrum of BaF2:Eu2+ comprises two peaks at 2.20 and 2.75 eV from the impurity trapped exciton (ITE) and the self-trapped exciton (STE), respectively. As the pressure is increased, both emission peaks shift to higher energies, and the shifting rate is slowed by the phase transition from the cubic to orthorhombic phase at 4 GPa. Due to the phase transition at 4-5 GPa pressure, the ITE emission disappears gradually, and the STE emission is gradually replaced by the 4f(6)5d(1) -> 4f(7) transition of Eu2+. Above 5 GPa, the pressure behavior of the 4f(6)5d(1) -> 4f(7) transition of EU2+ in BaF2: EU2+ is the same as the normal emission of Eu2+ in CaF2 and SrF2 phosphors.

First-Principles Study of Magnetic Properties of 3d Transition Metals Doped in ZnO Nanowires

The defect formation energies of transition metals (Cr, Fe, and Ni) doped in the pseudo-H passivated ZnO nanowires and bulk are systematically investigated using first-principles methods. The general chemical trends of the nanowires are similar to those of the bulk. We also show that the formation energy increases as the diameter of the nanowire decreases, indicating that the doping of magnetic ions in the ZnO nanowire becomes more difficult with decreasing diameter. We also systematically calculate the ferromagnetic properties of transition metals doped in the ZnO nanowire and bulk, and find that Cr ions of the nanowire favor ferromagnetic state, which is consistent with the experimental results. We also find that the ferromagnetic coupling state of Cr is more stable in the nanowire than in the bulk, which may lead to a higher T (c) useful for the nano-materials design of spintronics.

Concentration effect of Mn2+ on the photoluminescence of ZnS : Mn nanocrystals

Mn-doped ZnS nanocrystals of about 3 nm diameter were synthesized by a wet chemical method. X-ray diffraction (XRD) measurements showed that the nanocrystals have the structure of cubic zinc blende. The broadening of the XRD lines is indicative of nanomaterials. Room temperature photoluminescence (PL) spectrum of the undoped sample only exhibited a defected-related blue emission band. But for the doped samples, an orange emission from the Mn2+ T-4(1)-(6)A(1) transition was also observed, apart from the blue emission. The peak position (600 nm) of the Mn2+ emission was shifted to longer wavelength compared to that (584 nm) of bulk ZnS:Mn. With the increase of the Mn2+ concentration, the PL of ZnS:Mn was significantly enhanced. The concentration quenching effect was not observed in our experiments. Such PL phenomena were attributed to the absence of Mn2+ pairs in a single ZnS:Mn nanocrystal, considering the nonradiative energy transfer between Mn2+ ions based on the Poisson approximation. (c) 2005 Elsevier B.V. All rights reserved.

Measurement of gain spectrum for Fabry-Perot semiconductor lasers by the Fourier transform method with a deconvolution process

To improve the accuracy of measured gain spectra, which is usually limited by the resolution of the optical spectrum analyzer (OSA), a deconvolution process based on the measured spectrum of a narrow linewidth semiconductor laser is applied in the Fourier transform method. The numerical simulation shows that practical gain spectra can be resumed by the Fourier transform method with the deconvolution process. Taking the OSA resolution to be 0.06, 0.1, and 0.2 nm, the gain-reflectivity product spectra with the difference of about 2% are obtained for a 1550-nm semiconductor laser with the cavity length of 720 pm. The spectra obtained by the Fourier transform method without the deconvolution process and the Hakki-Paoli method are presented and compared. The simulation also shows that the Fourier transform method has less sensitivity to noise than the Hakki-Paoli method.

Tunable optical properties of nano-Au on vanadium dioxide

The optical properties of Au nanoparticles deposited on thermochromic thin films of VO2 are investigated using spectroscopy. A localized modification on the transmittance spectrum of VO2 film is formed due to the presence of Au nanoparticles which exhibit localized surface plasmon resonance (LSPR) in the visible-near IR region. The position of the modification wavelength region shows a strong dependence on the Au mass thickness and shifts toward the red as it increases. On the other hand, it was found that the LSPR of Au nanoparticles can be thermally tunable because of the thermochromism of the supporting material of VO2. The LSPR wavelength, lambda(SPR), shifts to the blue with increasing temperature, and shifts back to the red as temperature decreases. A fine tuning is achieved when the temperature is increased in a stepwise manner.

Nano-Ag on vanadium dioxide. I. Localized spectrum tailoring

We report on the utilization of localized surface plasmon resonance (LSPR) of Ag nanoparticles to tailor the optical properties Of VO2 thin film. Interaction of nano-Ag with incident light yields a salient absorption band in the visible-near IR region and modifies the spectrum Of VO2 locally. The wavelength of modification occurs in a limited spectral region rather than affects the full spectrum. The wavelength of modification shows a strong dependence on the metal nanoparticle size and shifts toward the red as the particle size or the mass thickness of nano-Ag increases. Also, we found that the wavelength can be shifted into the IR further by introducing a thin layer of TiO2 onto the nano-Ag. Interestingly, with the help of LSPR effects the VO2 film exhibits an anomalous thermochromic behavior in the modification wavelength region, which may be useful in optical switching applications.

Spectrum broadening and reshaping via gain compensation of fiber amplifier

We report a novel technique to broaden and reshape the spectrum of picosecond laser pulse based on the seeder of gain switch laser diode and Yb(3+)-doped fiber amplifier (YDFA). From compensating the seed spectrum with the gain of YDFA, the seed pulse of 7 nm bandwidth is broadened to 20 nm, and the flat top spectral shape is obtained as well. A self-made fiber coupled tunable filter is used to realize the tunable output laser with the wavelength range from 1053 nm to 1073 nm and the line width of 1.4 nm.

PHOTOLUMINESCENCE SPECTRUM STUDY OF THE GAAS/SI EPILAYER GROWN BY USING A THIN AMORPHOUS SI FILM AS BUFFER LAYER

Recently, we reported successful growth of high-quality GaAs/Si epilayers by using a very thin amorphous Si film as buffer layer. In this paper, the impurity properties of this kind of GaAs/Si epilayers have been studied by using PL spectrum, SIMS and Hall measurement. Compared to a typical PL spectrum of the GaAs/Si epilayers grown by conventional two-step method, a new peak was observed in our PL spectrum at the energy of 1.462 eV, which is assigned to the band-to-silicon acceptor recombination. The SIMS analysis indicates that the silicon concentration in this kind of GaAs/Si epilayers is about 10(18) cm(-3). But its carrier concentration (about 4 x 10(17) cm(-3)) is lower than the silicon concentration. The lower carrier concentration in this kind of GaAs/Si epilayer can be interpreted both as the result of higher compensation and as the result of the formation of the donor-defect complex. We also found that the high-quality and low-Si-concentration GaAs/Si epilayers can be regrown by using this kind of GaAs/Si epilayer as substrate. The FWHM of the X-ray (004) rocking curve from this regrowth GaAs epilayer is 118 '', it is much less than that of the first growth GaAs epilayer (160 '') and other reports for the GaAs/Si epilayer grown by using conventional two-step method (similar to 200 '').

Influence of a tilted cavity on quantum-dot optoelectronic active devices

Quantum-dot laser diodes (QD-LDs) with a Fabry-Perot cavity and quantum-dot semiconductor optical amplifiers (QD-SOAs) with 7° tilted cavity were fabricated. The influence of a tilted cavity on optoelectronic active devices was also investigated. For the QD-LD, high performance was observed at room temperature. The threshold current was below 30 mA and the slope efficiency was 0.36 W/A. In contrast, the threshold current of the QD-SOA approached 1000 mA, which indicated that low facet reflectivity was obtained due to the tilted cavity design.A much more inverted carrier population was found in the QD-SOA active region at high operating current, thus offering a large optical gain and preserving the advantages of quantum dots in optical amplification and processing applications. Due to the inhomogeneity and excited state transition of quantum dots, the full width at half maximum of the electroluminescence spectrum of the QD-SOA was 81.6 nm at the injection current of 120 mA, which was ideal for broad bandwidth application in a wavelength division multiplexing system. In addition, there was more than one lasing peak in the lasing spectra of both devices and the separation of these peak positions was 6-8 nm,which is approximately equal to the homogeneous broadening of quantum dots.

Transition to Film Boiling in Microgravity: Influence of Subcooling

The transition process to film pool boiling in microgravity is studied experimentally aboard the Chinese recoverable satellite SJ-8. A quasi-steady heating method is adopted, in which the heating voltage is controlled to increase exponentially with time. Small, primary bubbles are formed and slid on the surface, which coalesce with each other to form a large coalesced bubble. Two ways are observed for the transition from nucleate to film boiling at different subcoolings. At high subcooling, the coalesced bubble with a smooth surface grows slowly. It is then difficult for the coalesced bubble to cover the whole heater surface, resulting in a special region of transition boiling in which nucleate boiling and local dry areas can coexist. In contrast, strong oscillation of the coalesced bubble surface at low subcooling may cause rewetting of local dry areas and activation of more nucleate sites, resulting in an abrupt transition to film boiling.

Synthesis, structure, photoluminescence, and electroluminescence properties of a new dysprosium complex

A new dysprosium complex Dy(PM)(3)(TP)(2) [where PM = 1-phenyl-3-methyl-4-isobutyryl-5-pyrazolone and TP = triphenyl phosphine oxide] was synthesized, and its single-crystal structure was also studied. Its photophysical properties were studied by absorption spectra, emission spectra, fluorescence quantum efficiency, and decay time of the f-f transition of the Dy3+ ion. In addition, the antenna effect was introduced to discuss the energy transfer mechanism between the ligand and the central Dy3+ ion. Finally, a series of devices with various structures was fabricated to investigate the electroluminescence (EL) performances of Dy(PM)(3)(TP)(2). The best device with the structure ITO/CuPc 15 nm/Dy complex 70 nm/BCP 20 nm/AlQ 30 nm/LiF 1 nm/Al 100 nm exhibits a maximum brightness of 524 cd/m(2), a current efficiency of 0.73 cd/A, and a power efficiency of 0.16 lm/W, which means that a great improvement in the performances of the device was obtained as compared to the results reported in published literature. Being identical to the PL spectrum, the EL spectrum of the complex also shows characteristic emissions of the Dy3+ ion, which consist of a yellow band at 572 nm and a blue emission band at 480 nm corresponding to the F-4(9/2)-H-6(13/2) and F-4(9/2)-H-6(15/2) transition of the Dy3+ ion, respectively. Consequently, an appropriate tuning of the blue/yellow intensity ratio can be presumed to accomplish a white luminescent emission.