Infrared reflectivity of Cox(SiO2)1−x (x∼0.85, 0.55, 0.38) granular films on SiO2 glass substrates

We report the infrared specular reflectivity of Co_x(SiO₂)_1−x (x∼0.85, 0.55, 0.38) films on SiO₂ glass spanning from a metal-like to insulating behavior. While films for x∼0.85 show carrier metallic shielding and hopping conductivity, for x∼0.65 and lower concentrations, the nanoparticles’ number and size promote a localization edge near the highest longitudinal optical frequency. Such an edge is associated with a reflectivity minimum and a higher frequency band connoting strong electron-phonon interactions, carrier phonon assisted hopping, and polaron formation. Optical conductivity fits with current polaron models provide grounds toward a microscopic understanding of transport properties in these as-prepared granular films.     

Cs nuclear magnetic resonance study in CsZnCl3 single crystals of perovskite ABX3 type

CsZnCl₃ single crystals were grown by the slow evaporation method, and the spin-lattice relaxation rates and resonance lines of the ¹³³Cs nuclei in the resulting crystals were investigated using FT NMR spectrometry. The temperature dependence of the relaxation rate of the ¹³³Cs nuclei in the CsZnCl₃ crystals was found to be continuous near T_C (=366 K), and was not affected by this phase transition. Our results for CsZnCl₃ are compared with those obtained previously for other CsBCl₃ (B=Mn, Cu, and Cd) perovskite crystals. The Cs relaxation time of CsCdCl₃ is longer than that of CsMnCl₃. The differences between the atomic weights of Mn, Cu, Zn, and Cd are responsible for the differences between the spin-lattice relaxation times of these single crystals. The influence of paramagnetic ions is also important in these crystals. The differences between the spin-lattice relaxation times of these crystals could also be due to differences between the electron structures of their metal ions, in particular the structures of the d electrons.     

Influence of temperature annealing on optical properties of SrTiO3/BaTiO3 multilayered films on indium tin oxide

We have prepared SrTiO₃/BaTiO₃ thin films with multilayered structures deposited on indium tin oxide (ITO) coated glass by a sol-gel deposition and heating at 300-650 °C. The optical properties were obtained by UV-vis spectroscopy. The films show a high transmittance (approximately 85%) in the visible region. The optical band gap of the films is tunable in the 3.64-4.19 eV range by varying the annealing temperature. An abrupt decrease towards the bulk band gap value is observed at annealing temperatures above 600 °C. The multilayered film annealed at 650 ° C exhibited the maximum refractive index of 2.09-1.91 in the 450-750 nm wavelength range. The XRD and AFM results indicate that the films annealed above 600 ° C are substantially more crystalline than the films prepared at lower temperatures which were used to change their optical band gap and complex refractive index to an extent that depended on the annealing temperature.     

Experimental and theoretical studies of polaron optical properties in KNbO3 perovskite

Time-resolved absorption and luminescence spectra have been measured in KNbO₃ perovskite crystals after pulsed band-gap excitation by 200 fs laser pulses and 10 ns electron pulses. Quantum chemical calculations using the large unit cell periodic model support the interpretation of the observed transient absorption bands at 0.8 and 1.1 eV as the self-trapped electron polarons and bound hole polarons, respectively. The activation energy for the 2.2 eV green luminescence quenching is 0.05 eV. We suggest that the short lifetime (<15 ns) of the luminescence at RT is caused by the radiative recombination of nearest electron and hole polarons.     

Crystal-field hamiltonian and spin-orbit interaction for d and d ions at low C3 symmetry sites: V:Al2O3 and Ni:LiNbO3

The experimental studies have provided evidence of the occurrence of transitions from the ³T_1g(³F) ground state to the crystal-field levels ³T_2g(³F), ³T_1g(³P) and ³A_2g(³F) for the V³⁺ centres in Al₂O₃ crystal; and from the ³A_2g(³F) ground state to the crystal-field levels ³T_2g(³F), ³T_1g(³F) and ³T_1g(³P) for the Ni²⁺ centres in LiNbO₃ crystal (levels are assigned to irreps of the O_h point symmetry group). Using the experimental spectroscopic data, theoretical calculations of the crystal-field levels of V³⁺:Al₂O₃ and Ni²⁺:LiNbO₃ are carried out based on the Racah theory. The observed crystalline-field splittings of the V³⁺ and Ni²⁺ terms were accounted for using a C₃ symmetry Hamiltonian. The spin-orbit interaction was taken into account in this work. The Racah, crystal-field and spin-orbit parameters, which fit experimental and theoretical energy levels, have been reliably obtained. A good agreement between the theoretical and experimental results for the energy levels of V³⁺:Al₂O₃ and Ni²⁺:LiNbO₃ has been obtained.     

Isotopic shift in angle-resolved photoemission spectra of Bi2Sr2CaCu2O8 due to quadratic electron-phonon coupling

In connection with the experiment on oxygen isotope effect of Bi₂Sr₂CaCu₂O₈ with the angle-resolved photoemission spectroscopy (ARPES), we theoretically study the isotope-induced band shift in ARPES by the Hartree-Fork and quantum Monte Carlo methods. We find that this band shift can be clarified based on a quadratically coupled electron-phonon (e-ph) model. The large ratio of band shift versus phonon energy change is connected with the softening effect of phonon, and the positive-negative sign change is due to the momentum dependence of the e-ph coupling.     

Crystal-field analysis for d ions at D4h symmetry sites: Electronic states in trans-NiCl2(H2O)4 complex

The polarized absorption spectra of trans-NiCl₂(H₂O)₄ complex were measured by Bussière et al. [Coord. Chem. Rev. 219-221 (2001) 509-543] at low-temperature. Using the experimental spectroscopic data, semiempirical calculations of the crystal-field levels of trans-NiCl₂(H₂O)₄ chromophore are carried out, based on the Racah theory. We used idealized D_4h point group symmetry to analyse the observed crystalline-field splitting of this chromophore. As a result, Racah and crystal-field parameters have been reliably obtained. A good agreement between the theoretical and experimental energy levels of trans-NiCl₂(H₂O)₄ complex has been obtained. The region of ³T_1g/¹E_g(O_h) bands is of great interest and it is useful to use the tetragonal symmetry to understand the features of this spectral region.     

Luminescence and chromaticity of alkaline earth aluminate MxSr1−xAl2O4:Eu (M: Ca,Ba)

In order to prepare fluorescent material for UV-LED used as illumination light source, two series of Eu²⁺ doped (1 mol%) alkaline earth aluminate phosphors Ca_xSr_1−xAl₂O₄ and Ba_xSr_1−xAl₂O₄ were prepared. The crystal structure, relative quantum efficiency(Qr), peak wavelength(λ_p), color tuning and chromaticity were investigated by XRD patterns and photoluminescence (PL) on samples prepared by solid solution system (s series) and powder mixing system (m series) respectively. For the s series, the synthesized Ca_xSr_1−xAl₂O₄:Eu²⁺ powders show that the structure transforms from monoclinic to hexagonal at x?0.5, and λ_p increases from 442.3 to 529.7 nm with decreasing x. For the Ba_xSr_1−xAl₂O₄:Eu²⁺ system, the structure transforms from monoclinic to hexagonal at x?0.3, and λ_p decreases from 520.5 to 502.2 nm continuously from x=0 to 1. The shift in λ_p could be explained by the crystal field effect, which is affected by different coulomb attractive forces due to the various fraction of alkaline earth cation in the host lattice. Different phosphor properties prepared by either solid solution or powder mixing methods were characterized by chromaticity measurements for both reflective and transmissive modes.     

Small polaron migration in LixMn2O4: From first principles calculations

Migration of small polarons in λ-MnO₂, Li_0.5Mn₂O₄ and LiMn₂O₄ is studied via first principles calculations. Migration energy barriers of single small polaron migrations in λ-MnO₂, Li_0.5Mn₂O₄ and LiMn₂O₄ are 0.22 eV, 0.45 eV and 0.35 eV, respectively. The energy level changes of Mn-3d states along the polaron migration path are analyzed in detail. Results indicate that the activation energy barrier of polaron migration is strongly associated with the energy level shift of Mn-3dz² orbital, which is dependent on the short range structural arrangement of Mn³⁺/Mn⁴⁺ in the crystal. The electrical conduction properties of Li_xMn₂O₄ at room temperature are then discussed.     

Theoretical study of quantum-confined band-edge shifts and radiative lifetimes in oxidized Si(001) quantum films: comparison with experiment for Si/SiO2 quantum wells

The electronic structure and radiative lifetimes of Si(001) quantum films terminated by SiO₄ tetrahedra, which simulate Si/SiO₂ quantum wells (QWs), are calculated by the extended Hückel-type non-orthogonal tight-binding method. It is found that calculated band-gap widenings and radiative lifetimes account for band-edge shifts and photoluminescence (PL) peak shifts and lifetimes measured in amorphous-Si/SiO₂ QWs, suggesting that quantum confinement effects on the extended band-edge states in the amorphous-Si layer are responsible for the observed results. However, it is shown that band-edge shifts and PL energies and lifetimes observed in crystalline-Si/SiO₂ QWs cannot be reproduced properly by the interface model proposed in this study, implying that further studies are needed on the atomic structure of the crystalline-Si/SiO₂ interface.     

Acceptor Concentration Effects on Photovoltaic Response in the La1-xSrxMnO3/SrNbyTi1-yO3 Heterojunction

Photovoltaic response in the heterojunction of La1-x SrxMnO3/SrNby Ti1-yO3 （LSMO/SNTO） is analyzed theoretically based on the drift-diffusion model. It is found that the decrease of acceptor concentration in the La1-xSrxMnO3 layer of hereto junction can increase the peak value of photovoltaic signal and the speed of photovoltaic response, whereas the changing of donor concentration in the SrNby Ti1-yO3 layer has no such evident effect. Furthermore, the result also indicates that the modulation of Sr doping in La1-xSrxMnO3 is an effective method to accommodate the sensitivity and the speed of photovoltaic response for LSMO/SNTO photoelectric devices.     

The thermoelectric power of charge-density-wave conductors Rb0.3MoO3 and Rb0.15K0.15MoO3

The thermoelectric power (TEP) of the quasi-one-dimensional charge-density-wave (CDW) conductors rubidium blue bronze Rb_0.3MoO₃ and its alloy Rb_0.15K_0.15MoO₃ were measured in the temperature range 80-280 K. The result showed a sign change from a small positive value to a great negative value where the Peierls transition temperatures (T_p) are 183 and 180 K for Rb_0.3MoO₃ and Rb_0.15K_0.15MoO₃, respectively. Above T_p, the TEP for both samples can be described with the empirical relation S=AT+B; while below T_p, the TEP fits well the relation S=AT+B/T based on the experimental data. The Fermi energies ε_F for Rb_0.3MoO₃ and Rb_0.15K_0.15MoO₃ are estimated to be 1.55 and 0.53 eV, respectively.     

Effect of temperature on polaron dynamics in poly-DNA

We investigate the effect of temperature on polaron dynamics in the framework of a tight-binding model. The dissociation of a polaron will become fast with the increase of temperature. There exists a crossover of the charge localization time from strong to weak temperature-dependence. Instead of the uniform motion at zero temperature, a polaron moves un-uniformly under a driven field at a finite temperature, which indicates a discrete hopping between base pairs. It is also found that the polaron motion is thermally activated. A high temperature will result in a fast movement of a polaron under a deriving field.     

Dielectric and optical behaviors in relaxor ferroelectric Pb(In1/2Nb1/2)1−xTixO3 crystal

Dielectric permittivities (ε′,ε″) have been measured as functions of temperature (140-535 K) and frequency (500 Hz-2.0 MHz) in a (001)-cut Pb(In_1/2Nb_1/2)_0.7Ti_0.3O₃ (PINT30%) single crystal grown by the modified Bridgman method with Pb(Mg_1/3Nb_2/3)_0.71Ti_0.29O₃ (PMNT29%) seed crystal. A diffused phase transition was observed in the temperature region of ∼430-460 K with strong frequency dispersion. Above the Burns temperature T_B≅510 K, the dielectric permittivity was found to follow the Curie-Weiss behavior, ε′=C/(T−T_C), with parameters C=3.9×10⁵ and T_C=472 K. Below T_B≅510 K, polar nanoclusters are considered to appear and are responsible for the diffused dielectric anomaly. Optical transmission, refractive indices, and the Cauchy equations were obtained as a function of wavelength at room temperature. The unpoled crystal shows almost no birefringence, indicating that the average structural symmetry is optically isotropic. The crystal exhibits a broad transparency in the wavelength range of ∼0.4-6.0 μm.     

Slowing down of the relaxational dynamics at the ferroelectric phase transition in one-dimensional (TMTTF)2AsF6

We present measurements of the dielectric response of quasi one-dimensional system (TMTTF)₂AsF₆ in a wide temperature and frequency range. We provide a thorough characterization of the relaxational dynamics observed close to the ferroelectric-like transition at T_c=100 K. Our measurements, extending up to 100 MHz, reveal a continuous slowing down of the mean relaxation time when approaching T_c from high as well as from low temperatures. The simultaneous critical rise of the dielectric constant and relaxation time point to an explanation of the transition in terms of a classic ferroelectric scenario.     

Chemical-bond analysis of the nonlinear optical properties of the borate crystals LiB3O5, CsLiB6O10, and CsB3O5

The second-order nonlinear optical properties of practical borate crystals, LiB₃O₅, CsLiB₆O₁₀, and CsB₃O₅, which all contain the identical basic structural unit [the (B₃O₇)^5- group], have been quantitatively studied from the chemical-bond viewpoint. Differences in the nonlinear optical properties among these three borate crystals arise from the contributions of the different cations, i.e., the different interaction between the cation and the (B₃O₇)^5- anionic group. The chemical-bond method quantitatively expresses this important difference. At the same time, the current calculation also shows that the B₃O₇ group is a very important crystallographic frame in the crystalline borate solids; it offers different cations an excellent coordination environment. Received: 20 February 2001 / Accepted: 14 June 2001 / Published online: 30 August 2001     

Spectroscopic properties of Tm -doped Ba3Gd2(BO3)4 crystal

crystal with the size up to Φ 13 mm×44 mm was grown successfully by the Czochralski technique and its optical properties were presented. The absorption cross-section and emission cross-section were presented. Also, the potential laser gain near 1.9 μm was investigated. In the framework of the Judd-Ofelt (J-O) theory, the intensity parameters were calculated to be: Ω₂=11.375×10⁻²⁰ cm², Ω₄=5.077×10⁻²⁰ cm² and Ω₆=6.524×10⁻²⁰ cm². The spectroscopic parameters of this crystal such as the oscillator strengths, radiative transition probabilities, radiative lifetime as well as the branching ratios were calculated, too. This crystal is promising as a tunable infrared laser crystal.     

Optical properties of lattice/magnetic small polarons from DMFT

We calculate the optical conductivity of small polarons in the Holstein and Holstein-t-J models, by applying the dynamical mean field theory. We show that the antiferromagnetic correlations tend to increase the region of the parameters where polaronic signatures are found in the optical spectra, and shift the polaronic absorption band to higher frequencies compared to the case of purely lattice polarons. On the other hand, the electron-lattice interaction is essential in order to have polaronic features in the optical absorption.     

Effect of helix angles on polaron motion in poly-DNA

We investigate the effect of helix angles on polaron motion in poly-DNA in the framework of a tight binding model. A DNA molecule is supposed to have a uniform or a random distribution of the helix angles. It is found that a polaron moves faster along a DNA molecule with an overwinding helix than that with an unwinding one. In DNA molecule with randomly distributed helix angles, charge transport is suggested to be field-facilitated tunneling between spatial disordered potential wells.     

Assessment of electronic properties of InNxSb1−x for long-wavelength infrared detector applications

This work assesses theoretically the potential of dilute nitride alloys of InN_xSb_1−x for long-wavelength IR applications. A 10-band k.p approximation modified to account for conduction/valence band coupling is implemented to extract the bandgap as a function of the nitrogen concentration in the alloy and the temperature. The calculations show the possibility to obtain a band closure at ∼2% of nitrogen for InSbN at 300 K. The absorption coefficient, and its temperature dependence, is then determined using an Elliot-like formalism, predicting stronger absorption properties associated with the enhancement of conduction band effective masses. This enhancement yields over an order of magnitude increase in the non-radiative Auger recombination lifetimes suggesting the potential of InNSb for significantly enhancing detectivity limits and operation temperatures of long-wavelength IR detectors.