Photoluminescence enhancement and quenching in metal-semiconductor quantum dot hybrid arrays

Hybrid monolayer arrays of metal and semiconductor quantum dots have been prepared to study the exciton-plasmon interaction. We observed crossover from strong quenching to enhancement in photoluminescence of the quantum dots as a function of the emission wavelength for fixed interparticle spacings. Remarkably, the enhancement is observed even for extremely short separation at which strong quenching has been observed and predicted earlier. A significant redshift in emission maxima is also observed for quantum dots with quenched emission. The possible role of collective phenomena as well as strong interactions in such ordered hybrid arrays in controlling the emission is discussed. (C) 2011 American Institute of Physics. doi:10.1063/1.3553766]

Ab initio molecular orbital calculations on ion pair-water complexes of metal halides and oxides

Ab initio MO calculations are performed on a series of ion-molecular and ion pair-molecular complexes of H2O + MX (MX = LiF, LiCl, NaCl, BeO and MgO) systems. BSSE-corrected stabilization energies, optimized geometrical parameters, internal force constants and harmonic vibrational frequencies have been evaluated for all the structures of interest. The trends observed in the geometrical parameters and other properties calculated for the mono-hydrated contact ion pair complexes parallel those computed for the complexes of the individual ions. The bifurcated structures are found to be saddle points with an imaginary frequency corresponding to the rocking mode of water molecules. The solvent-shared ion pair complexes have high interaction energies. Trends in the internal force constant and harmonic frequency values are discussed in terms of ion-molecular and ion-pair molecular interactions.

The Zintl ion As-7](2-): an example of an electron-deficient As-x radical anion

K(2,2,2-crypt)](2)As-7]center dot THF, 1 (2,2,2-crypt = 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo8.8.8]hexacosane) is the first well characterized seven-atom radical anion of group 15. UV-Vis spectroscopy confirms the presence and electronic structure of As-7](2-). Cyclic voltammetry in DMF solution shows the As-7(3) /As-7(2) redox couple as a one-electron reversible process. Theoretical investigations explore the bonding and properties of compound 1.

Bi2W1–xCuxO6–x(0.7[less-than-or-eq]x[less-than-or-eq]0.8): a new oxide-ion conductor

Anion-deficient Aurivillius phases of the general formula, Bi2Wi-xCuxO6-2x, possessing orthorhombic/tetragonal Bi2WO6-like structures, have been synthesized by quenching the oxide melts. The tetragonal phase stabilized for the compositions 0.7 less-than-or-equal-to x less-than-or-equal-to 0.8 is a good oxide-ion conductor in the temperature range 500-900 K, the x = 0.7 composition exhibiting the highest conductivity in the series.

Effect of sodium diffusion on the structural and electrical properties of Cu2ZnSnS4 thin films

Cu2ZnSnS4 (CZTS) is a kesterite semiconductor consisting of abundantly available elements. It has a band gap of 1.5 eV and a large absorption coefficient. Hence, thin films made of this material can be used as absorber layers of a solar cell. CZTS films were deposited on soda lime and Na free borosilicate glass substrates through Ultrasonic Spray Pyrolysis. The diffusion of sodium from soda lime glass was found to have a profound effect on characteristics like grain size, crystal texture and conductivity of CZTS thin films. Copper ion concentration also varied during the deposition and it was observed that the carrier concentration was enhanced when there was a deficiency of copper in the films. The effect of sodium diffusion and copper deficiency in enhancing the structural and electrical properties of CZTS films are presented in this paper. (C) 2010 Elsevier B.V. All rights reserved.

Optical and electrical properties of SnS semiconductor crystals grown by physical vapor deposition technique

Tin sulfide (SnS) is a material of interest for use as an absorber in low cost solar cells. Single crystals of SnS were grown by the physical vapor deposition technique. The grown crystals were characterized to evaluate the composition, structure, morphology, electrical and optical properties using appropriate techniques. The composition analysis indicated that the crystals were nearly stoichiometric with Sn-to-S atomic percent ratio of 1.02. Study of their morphology revealed the layered type growth mechanism with low surface roughness. The grown crystals had orthorhombic structure with (0 4 0) orientation. They exhibited an indirect optical band gap of 1.06 eV and direct band gap of 1.21 eV with high absorption coefficient (up to 10(3) cm(-1)) above the fundamental absorption edge. The grown crystals were of p-type with an electrical resistivity of 120 Omega cm and carrier concentration 1.52 x 10(15) cm(-3). Analysis of optical absorption and diffuse reflectance spectra showed the presence of a wide absorption band in the wavelength range 300-1200 nm, which closely matches with a significant part of solar radiation spectrum. The obtained results were discussed to assess the suitability of the SnS crystal for the fabrication of optoelectronic devices. (C) 2011 Elsevier B.V. All rights reserved.

Dielectric Relaxation Spectroscopy for Evaluation of the Influence of Solvent Dynamics on Ion Transport in Succinonitrile-Salt Plastic Crystalline Electrolytes

Influence of succinonitrile (SN) dynamics on ion transport in SN-lithium perchlorate (LiClO4) electrolytes is discussed here via dielectric relaxation spectroscopy. Dielectric relaxation spectroscopy (similar to 2 x 10(-3) Hz to 3 MHz) of SN and SN-LiClO4 was studied as a function of salt content (up to 7 mol % or 1 M) and temperature (-20 to +60 degrees C). Analyses of real and imaginary parts of permittivity convincingly reveal the influence Of trans gauche isomerism and solvent-salt association (solvation) effects on ion transport. The relaxation processes are highly dependent on the salt concentration and temperature. While pristine SN display only intrinsic dynamics (i.e., trans-gauche isomerism) which enhances with an increase in temperature, SN-LiClO4 electrolytes especially at high salt concentrations (similar to 0.04-1 M) show salt-induced relaxation processes. In the concentrated electrolytes, the intrinsic dynamics was observed to be a function of salt content, becoming faster with an increase in salt concentration. Deconvolution of the imaginary part of the permittivity spectra using Havriliak-Negami (HN) function show a relaxation process corresponding to the above phenomena. The permittivity data analyzed using HN and Kohlrausch-Williams-Watta (KWW) functions show non-Debye relaxation processes and enhancement in the trans phase (enhanced solvent dynamics) as a function of salt concentration and temperature.

Effect of Li+-ion on enhancement of photoluminescence in Gd2O3:Eu3+ nanophosphors prepared by combustion technique

Gd2O3:Eu3+ (4 mol%) nanophosphor co-doped with Li+ ions have been synthesized by low-temperature solution combustion technique in a short time. Powder X-ray diffractometer (PXRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), UV-VIS and photoluminescence (PL) techniques have been employed to characterize the synthesized nanoparticles. It is found that the lattice of Gd2O3:Eu3+ phosphor transforms from monoclinic to cubic as the Li+-ions are doped. Upon 254 nm excitation, the phosphor showed characteristic luminescence D-5(0) -> F-7(J) (J= 0-4) of the Eu3+ ions. The electronic transition located at 626 nm (D-5(0) -> F-7(2)) of Eu3+ ions was stronger than the magnetic dipole transition located at 595 nm (D-5(0) -> F-7(1)). Furthermore, the effects of the Li+ co-doping as well as calcinations temperature on the PL properties have been studied. The results show that incorporation of Li+ ions in Gd2O3:Eu3+ lattice could induce a remarkable improvement of their PL intensity. The emission intensity was observed to be enhanced four times than that of with out Li+-doped Gd2O3:Eu3+. (C) 2010 Elsevier B.V. All rights reserved,

Solvation dynamics, energy distribution and trapping of a light solute ion

In the theoretical treatments of the dynamics of solvation of a newly created ion in a dipolar solvent, the self-motion of the solute is usually ignored. Recently, it has been shown that for a light ion the translational motion of the ion can significantly enhance its own rate of solvation. Therefore, solvation itself may not be the rate determining step in the equilibration. Instead, the rate determining step is the search of the low energy configuration which serves to localize the light ion. In this article a microscopic calculation of the probability distribution of the interaction energy of the nascent charge with the dipolar solvent molecules is presented in order to address this problem of solute trapping. It is found that to a good approximation, this distribution is Gaussian and the second moment of this distribution is exactly equal to the half of its own solvation energy. It is shown that this is in excellent agreement with the simulation results that are available for the model Brownian dipolar lattice and for liquid acetonitrile. If the distortion of the solvent by the ion is negligible then the same relation gives the energy distribution for the solvated ion, with the average centered at the final equilibrium solvation energy. These results are expected to be useful in understanding various chemical processes in dipolar liquids. Another interesting outcome of the present study is a simple dynamic argument that supports Onsager's ''inverse snow-ball'' conjecture of solvation of a light ion. A simple derivation of the semi-phenomenological relation between the solvation time correlation function and the single particle orientation, reported recently by Maroncelli et al. (J. Phys. Chem. 97 (1993) 13), is also presented.

ChemInform Abstract: Synthesis of Anion-Deficient Layered Perovskites, ACa2Nb3-xMxO10-x (A: Rb, Cs; M: Al, Fe), Exhibiting Ion-Exchange and Intercalation. Evidence for the Formation of Layered Brownmillerites, ACa2Nb2AlO9 (A: Cs, H)

Anion-deficient layered perovskite oxides of the formula, ACa2Nb3-xMxO10-x (A = Rb, Cs; M = Al, Fe) for 0 < x less-than-or-equal-to 1.0, possessing tetragonal structures similar to the parent ACa2Nb3O10, have been synthesized. The interlayer A cations in these materials are readily exchanged with protons in aqueous HNO3 to give the protonated derivatives, HCa2Nb3-xMxO10-x; the latter are solid Bronsted acids intercalating a number of organic amines including aniline (pK(a) = 4.63). The distribution of acid sites in the interlayer region of HCa2Nb2MO9 inferred from n-alkylamine intercalation suggests that oxygen vacancies and Nb/M atoms are disordered in the ACa2Nb2MO9 samples prepared at 1100-1200-degrees-C. Annealing a disordered sample of CsCa2Nb2AlO9 for a long time at lower temperatures tends to order the Nb/Al atoms and oxygen vacancies to produce octahedral (NbO6/2)-tetrahedral (AlO4/2)-octahedral (NbO6/2) layer sequence reminiscent of the brownmillerite structure.

Ionic conductivity, mechanical strength and Li-ion battery performance of mono-functional and bi-functional (''Janus'') ``soggy sand'' electrolytes

Influence of dispersion of uniformly sized mono-functional and bi-functional (''Janus'') particles on ionic conductivity of novel ``soggy sand'' electrolytes and its implications on mechanical strength and lithium-ion battery performance are discussed here.

AM(1-x)Al(x)O(3-x) (A=Na or K; M=Nb or Ta): New anion-deficient Perovskite oxides exhibiting oxide ion conduction

Anion-deficient perovskite oxides of the formula AM(1-x)Al(x)O(3-x) (A = Na or K; M = Nb or Ta) have been prepared for 0 < x less than or equal to 0.5. Diffraction experiments reveal that while the potassium compounds adopt orthorhombic/cubic perovskite structures similar to the parent KNbO3/KTaO3, the sodium compound, NaNb0.5Al0.5O2.5, possesses a brownmillerite/LaSr-CuAlO5-like superstructure. Al-27 NMR spectra show an exclusive tetrahedral oxygen coordination for AI(III) in Na-Nb0.5Al0.5O2.5 (I) and both tetrahedral and octahedral coordination for Al(III) in KNb0.5Al0.5O2.5 (II). The results suggest a long-range and short-range ordering of oxide ion vacancies in I and II respectively. Electrical conductivity measurements show a significant oxide ion conduction for KNb1-xAlxO3-x, with the conductivity increasing with x up to x = 0.5. The differences in the Arrhenius plots of the ionic conductivity of I and II have been rationalized in terms of the long-range and short-range ordering of oxide ion vacancies in the anion-deficient perovskite oxides.