Franck–Hertz effect in cathodo- and photoluminescence of wide-gap materials

A brief overview of previously obtained and novel data on the manifestations of an analogue of Franck–Hertz effect in photo- and cathodoluminescence of wide-gap inorganic materials is presented. On the example of NaCl:Tl⁺ and MgO:Cr³⁺ single crystals, the excitation processes of the luminescence of 6s² Tl⁺ ions and 3d³ Cr³⁺ ions by 5–15 keV electrons or 5–20 eV photons at 6–420 K have been studied. The rapid processes of the direct energy transfer to Tl⁺ by hot conduction electrons or to Cr³⁺ centers by hot electrons and/or hot valence holes have been separated from rapid excitonic and more inertial electron–hole processes.     

Low voltage red phosphorescent organic light-emitting devices with triphenylphosphine oxide and 4,4′-bis(2,2′-diphenylvinyl)-1,1′-biphenyl electron transport layers

We have developed red phosphorescent organic light-emitting devices operating at low voltages by using triphenylphosphine oxide (Ph₃PO) and 4,4′-bis(2,2′-diphenylvinyl)-1,1′-biphenyl (DPVBi) electron transport layers. 4,4′-bis(N-carbazolyl)-1,1′-biphenyl (CBP) and tris-(1-phenylisoquinolinolato-C²,N) iridium(III) [Ir(piq)₃] were used as host and guest materials, respectively. Small voltage drops across the electron transport layers and direct injection of holes from 4,4′,4″-tris[N-(2-naphthyl)-N-phenyl-amino]-triphenylamine (2-TNATA) hole transport layer into the Ir(piq)₃ guests are responsible for the high current density at low voltage, resulting in a high luminance of 1000 cd/m² at low voltages of 2.8–3.0 V in devices with a structure of ITO/2-TNATA/CBP:Ir(piq)₃/DPVBi/Ph₃PO/LiF/Al.     

Absorption,luminescence, and electron paramagnetic resonance of molybdenum ions in CdWO4

A single crystal of cadmium tungstate (CdWO₄) containing approximately 200 ppm of molybdenum was grown by the Czochralski method and then characterized in a series of optical absorption, photoluminescence (PL), photoluminescence excitation (PLE), and electron paramagnetic resonance (EPR) experiments. The Mo⁶⁺ ions substitute for W⁶⁺ ions and serve as recombination sites for electrons and holes when the crystal is exposed to ionizing radiation. A charge-transfer absorption band for the Mo⁶⁺ ions was observed near 320 nm at 10 K. The PL experiments, performed at low temperature with 325 nm excitation, showed a Mo-associated emission peaking near 680 nm. A direct correlation of the 680 nm emission and the 320 nm absorption band was established by the PLE data. When these doped CdWO₄ crystals are exposed at low temperature either to light that is near or above the band gap or to X-rays, the Mo⁶⁺ ions can trap an electron and form stable Mo⁵⁺ ions. The EPR spectrum of the Mo⁵⁺ ions was observed at temperatures near 15 K, and a complete set of parameters describing the g matrix was obtained from an angular dependence study.     

Oxygen-rich Ti1−xO2 pillar growth at a gold nanoparticle–TiO2 contact by O2 exposure

In-situ gas-injection transmission electron microscopy revealed that a pillar grew at the edge of the interface of a gold nanoparticle and a TiO₂ substrate during exposure to O₂ gas at 100 Pa. The pillar was found to have a titanium-deficient chemical composition of Ti_1 ? xO₂ (x > 0) by electron energy loss spectroscopy (EELS). The spectra showed a chemical shift of oxygen and titanium ions to have ionic states of Ti³⁺ and O^y? (y < 3/2). The formation of the Ti_1 ? xO₂ at the contact edge of gold–Ti_1 ? xO₂ interface is discussed from the perspective of an O₂ affinity, which plays an important role in CO oxidation process of supported gold particle.     

Electronic excitations and luminescence of SrAlF5 crystals doped with Ce3+ ions

This paper reports the results of a time-resolved photoluminescence and energy transfer processes study in Ce³⁺ doped SrAlF₅ single crystals. Several Ce³⁺ centers emitting near 4 eV due to 5d-4f transitions of Ce³⁺ ions substituting for Sr²⁺ in non-equivalent lattice sites were identified. The lifetime of these transitions is in the range of 25–35 ns under intra-center excitation in the energy region of 4–7 eV at T = 10 K. An effective energy transfer from lattice defects to dopant ions was revealed in the – 7–11 eV energy range. Both direct and indirect excitation channels are efficient at room temperature. Excitons bound to dopants are revealed at T = 10 K under excitation in the fundamental absorption region above 11 eV, as well as radiative decay of self-trapped excitons resulting in luminescence near 3 eV.     

The thermopower of transition-metal double-perovskites: A sensitive probe of their electronic structures around the Fermi level

We report on a comparative study of S(T) for a series of transition-metal double-perovskites A₂BB′O₆ (A – Ca, Sr, Ba, and B, B′ = transition metal ions), some of them known to have half-metallic ground states. For Sr₂BB′O₆ with BB′ = CrMo, CrW, CrRe, FeMo, and FeRe (ferrimagnetic with high Curie temperatures), S(T) is metallic, for B′ = Mo and W it is n-type and for B′ =  Re, p-type. For A₂FeMoO₆ (A = Ca, Sr, Ba), the crystallographic differences (monoclinic, tetragonal and cubic space-groups, respectively) are accompanied by prominent differences in their (metallic) S(T). For the insulating Sr₂MnReO₆ and Ba₂MnReO₆, the onset of ferromagnetic order below T_c ∼ 120 K is marked by a steep drop of S(T) accompanied by only a slight change in the slope of ln ρ versus 1/T^1/2. Significant conclusions were drawn from the experimental results without the need for elaborate models.     

Modifications in physical,optical and electrical properties of tin oxide by swift heavy Au8+ ion bombardment

Tin oxide thin films were deposited by a novel technique called as modified-SILAR. The preparative parameters were optimized to obtain good quality thin films. As-deposited films were annealed in O₂ atmosphere for 1 h at 500 °C. The annealed films were irradiated using Au⁸⁺ ions with energy of 100 MeV at different fluencies of 1 × 10¹¹, 1 × 10¹², 5 × 10¹² and 1 × 10¹³ ions/cm² using tandem pelletron accelerator. The irradiation-induced modifications in tin oxide thin films were studied using XRD, AFM, optical band gap, photoluminescence and I–V measurements. XRD studies showed formation of tin oxide with tetragonal structure. AFM revealed uniform deposition of the material with increase in grain size after irradiation. Decrease in band gap from 3.51 eV to 2.82 eV was seen with increases in fluency. A decrease in PL intensity, and an additional peak was observed after irradiation. I–V measurements showed a decrease in resistance with fluency.     

Electrical characteristics and efficiency of organic light-emitting diodes depending on hole-injection layer

In a device structure of ITO/hole-injection layer/N,N′-biphenyl-N,N′-bis-(1-naphenyl)-[1,1′-biphthyl]4,4′-diamine(NPB)/tris(8-hydroxyquinoline)aluminum(Alq₃)/Al, we investigated the effect of the hole-injection layer on the electrical characteristics and external quantum efficiency of organic light-emitting diodes. Thermal evaporation was performed to make a thickness of NPB layer with a rate of 0.5–1.0 Å/s at a base pressure of 5 × 10⁻⁶ Torr. We measured current–voltage characteristics and external quantum efficiency with a thickness variation of the hole-injection layer. CuPc and PVK buffer layers improve the performance of the device in several aspects, such as good mechanical junction, reducing the operating voltage, and energy band adjustment. Compared with devices without a hole-injection layer, we found that the optimal thickness of NPB was 20 nm in the device structure of ITO/NPB/Alq₃/Al. By using a CuPc or PVK buffer layer, the external quantum efficiencies of the devices were improved by 28.9% and 51.3%, respectively.     

Ionic conductivity and phase transition in Pb4.8Bi1.6Na3.6(PO4)6, an apatite-type compound

Bismuth sodium lead phosphate, Pb_4.8Bi_1.6Na_3.6(PO₄)₆, a compound having an apatite structure, was obtained via a solid-state reaction. Determination of the structure by X-ray diffraction on a single crystal gave the following results: hexagonal, P6₃/m, a = 9.6545(11) Å, c = 7.1457(5) Å, R = 0.03 and R_w = 0.09. The presence of Bi³⁺ and Pb²⁺ ions, carrying a lone electron pair, at (6h) sites helped to stabilize the apatite structure in spite of the anionic vacancies in the center of the tunnel. The compound was characterized by chemical analysis, differential thermal analysis, thermal expansion of the cell, and infrared, impedance and ²³Na NMR spectroscopy. The thermal behavior revealed two breaks attributed to order–disorder transitions. One of them was ascribed to a reordering of cations from the (6h) site to the center of the tunnel. Conductivity was dominated by hopping mechanisms.     

Resonant energy transfer and cross relaxation between Sm3+ ions in LiYF4 crystals

Luminescence decay curves of Sm³⁺ ions in LiYF₄ crystals doped with 1, 5 and 10 mol% Sm³⁺ are multi-exponential, whereas that in a LiYF₄ crystal doped with 0.1 mol% Sm³⁺ is well approximated by a single exponential function with a decay time of 4.8 ms. The average luminescence decay times decrease from 4.8 to 0.60 ms with the increasing Sm³⁺ concentrations between 1 and 10 mol%. The decay curves for all crystals are found to be almost independent of the temperature between 15 and 300 K. The decrease of the decay times for the higher Sm³⁺ concentrations indicates energy transfer between two Sm³⁺ ions. Taking the crystal structure of LiYF₄ into account, it is deduced that a single-step energy transfer process for the 1 and 5 mol% Sm³⁺ concentrations occurs from a Sm³⁺ ion at the origin of (0 0 0) to one of the Sm³⁺ ions substituting for the first nearest neighbor Y³⁺ sites and beyond within a sphere with an approximate radius of less than 0.7 nm. On the other hand, a multi-step energy transfer process dominates for the highest concentration (10 mol%) because the calculated average distance between two Sm³⁺ ions in the 10 mol% Sm³⁺ sample is comparable with the migration length of the single-step energy transfer process estimated from the 1 and 5 mol% Sm³⁺ samples.     

Thermal cis–trans isomerization of triazo-benzene

1,3,5-Hydroxy-triazo-benzene (H-TAB) was synthesized through a coupling-oxidation protocol. Temperature-controlled UV, IR, and ab initio calculation were carried out to investigate the cis–trans thermal isomerization of H-TAB. In temperature-controlled UV experiments, λ_max of the π–π¹ band and for the trans conformation at 335 nm and that for the cis form at 282 nm are shifted by increased temperature; band intensities of the π–π¹ transition decrease and λ_max of the π–π¹ band is shifted toward the high-energy region. The maximum peak at 2922 cm⁻¹ is shifted to 2926 cm⁻¹, and that at 2852 cm⁻¹ is shifted to 2856 cm⁻¹ at increased temperature in the temperature-controlled IR experiment. Ab initio calculation reveals that the cis conformation of H-TAB is more stable than the trans form because the cis form has less spatial repulsion. Therefore, the ground-state energy difference induced by steric repulsion of the benzene unit is the driving force of the blue shift in the thermal IR and UV spectra for the triazo-benzene.     

Universal dynamics behavior in superionic conducting glasses

The inelastic neutron scattering experiment on superionic glass system AgI-AgPO₃ have been performed in the energy and momentum transfer range from ? 5 to 15 meV and 0 to 8 Å^? 1, respectively by using a time of flight MARI instrument at Rutherford Appleton Laboratory, ISIS, UK. The E-dependence of the inelastic data show an excess intensity at low energy around 3 meV, the so-called Boson peak, which increased with the dopant salt. The Q-dependence of the elastic scattering reveals a prepeak at anomalously low Q value around 0.8 Å^? 1, which is not observed in the undoped AgPO₃ glass. The Q-dependence in the energy region from 1 to 3 meV shows clearly an excess intensity at Q ~ 2.2 Å ^? 1compared with the undoped AgPO₃. All these features correlate with the increasing mobility of Ag⁺ ions due to the expansion of the network structure caused by salt doping, which leads to the increase of ionic conductivity. Similar results have also been observed in the corresponding superionic glass system AgI-Ag₂S-AgPO₃ that was observed by both MARI and NEAT instrument at HMI, Berlin. The results show a universal dynamic behavior in silver phosphate glasses.     

Influences of Al doping concentration on structural,electrical and optical properties of Zn0.95Ni0.05O powders

Nanocrystalline Zn_0.95−xNi_0.05Al_xO (x = 0.01, 0.02, 0.05 and 0.10) diluted magnetic semiconductors have been synthesized by an auto-combustion method. X-ray diffraction measurements indicate that all Al-doped Zn_0.95Ni_0.05O samples have the pure wurtzite structure. Transmission electron microscope analyses show that the as-synthesized powders are of the size 40–45 nm. High-resolution transmission electron microscope, energy dispersive spectrometer and X-ray photoemission spectroscope analyses indicate that Ni²⁺ and Al³⁺ uniformly substitute Zn²⁺ in the wurtzite structure without forming any secondary phases. The Al doping concentration dependences of cell parameters (a and c), resistance and the ratio of green emission to UV emission have the similar trends.     

Photoionization cross section of Ne-like Cu XX with J=1

Relativistic calculations of photoionization cross sections of Ne-like Cu XX using the Breit–Pauli R-matrix method in close-coupling approximation and fully relativistic distorted-wave method are reported. In the present work, the relativistic distorted-wave method is employed to calculate the fine-structure energy levels and radial functions, and the Breit–Pauli R-matrix method is employed to calculate photoionizaton cross section for photon energy from 124.2 Ryd to 208 Ryd. Resonance structure in the photoionization of Ne-like Cu XX for ejection of 2p or 2s electron from the ground 2s²2p^{6 1}S₀ has been studied.     

Influence of the orthorhombic distortion on the van Hove singularities in the DOS and ARPES spectra of layered cuprates

Four atom states Cu3d_{x² −  y²}, Cu4s, O_a2p_xare involved in a tight-binding model for the superconducting CuO₂plane. The orthorhombic distortion is taken into account by the differences of Cu–O hopping amplitudes and single-site oxygen energies ε_aand ε_bof two oxygen positions in the elementary cell as well. An effective ‘oxygen’ Hamiltonian including only the electron amplitudes at the oxygen ions is derived. Simple expressions for the constant energy contours and the Fermi surface are obtained and they qualitatively describe the photoemission spectra. Extended saddle points nearp = (π,0) andp = (0,π) are observed in qualitative agreement with the ARPES data. The van Hove singularities of the density of states (DOS) related to the extended saddle points are calculated by a Monte Carlo method. It is found that the splitting of the singularity of the DOS at the bottom of the conduction band is created by the energy difference ε_a −  ε_b = 2δ.     

Magnetic and dielectric study of Bi2CuO4

Magnetic and dielectric properties have been investigated for Bi₂CuO₄, which has the same chemical formula as that of the parent materials of cuprate superconductors R₂CuO₄ (R: rare earths). Magnetization measurements show the antiferromagnetic transition of the Cu²⁺ spins at ～42 K, as reported previously. Dielectric measurements for the frequencies of 1 kHz to 1 MHz show that the dielectric constants are 100–500 at room temperature. The dielectric dispersion reveals that the dielectric response lacks spatial coherence, a property which indicates the possible existence of phase separation as suggested for La₂CuO₄. The imaginary part of dielectric response gives the activation energy of 0.22 eV, suggesting that the dielectric response is governed by the electron hopping between the Cu ions.     

Spectroscopic properties of Sm3+ ions in lead fluorophosphate glasses

The Sm³⁺-doped lead fluorophosphate glasses of composition 44P₂O₅–17K₂O–9Al₂O₃–(24?x)PbF₂–6Na₂O–xSm₂O₃, where x=0.01, 0.05, 0.1, 0.5, 1.0 and 2.0 mol%, have been prepared by conventional melt quenching technique and are characterized through differential thermal analysis, Raman, absorption and emission spectra and decay rate measurements. Free-ion Hamiltonian model for energy level analysis and Judd–Ofelt theory for spectral intensities have been used to analyze the spectroscopic properties of Sm³⁺ ions in lead fluorophosphate glasses. The decay rates for the ⁴G_5/2 level of Sm³⁺ ions have been measured and are found to be single exponential at lower concentration (≤0.1 mol% Sm₂O₃) and turn into non-exponential at higher concentrations (≥0.5 mol% Sm₂O₃) due to energy transfer through cross-relaxation. The experimental lifetimes for ⁴G_5/2 level of Sm³⁺ ions are found to decrease from 2.54 to 0.92 ms when the concentration increased from 0.01 to 2.0 mol% Sm₂O₃ due to energy transfer. In order to know the nature of the energy transfer mechanism, the non-exponential decay rates are well fitted to Inokuti–Hirayama model for S=6, which indicates that the energy transfer process is of dipole–dipole type.     

The layered iron phosphate KMgFe(PO4)2: Crystal structure,Mössbauer spectroscopy and ionic conductivity

A new iron phosphate, KMgFe(PO₄)₂ has been synthesized and investigated by X-ray diffraction, Mössbauer spectroscopy and ionic conductivity. This compound crystallizes in the monoclinic space group C2/c with the parameters a = 18.529(7) Å, b = 5.402(3) Å, c = 9.374(9) Å, β = 120.64(5)° and Z = 4. Its original structure can be described as the stacking along the [101] direction of [MgFe(PO₄)^?₂]_∞ layers of corner-sharing MO₄ (M = 0.5 Fe + 0.5 Mg) and PO₄ tetrahedra. The K⁺ ions are occupying the inter-layer space. The Mössbauer spectroscopy confirms the occurrence of only tetrahedral Fe³⁺ ions and gives a definitive proof of the disordered character of their distribution. Ionic conductivity results obtained by the impedance spectroscopy technique show that this material is a two-dimensional ionic conductor, with low activation energy, 0.51 eV, that is interpreted on the basis of two-dimensional pathways.     

Spatially varying effective mass effects on energy level populations in semiconductor quantum devices

For the analysis and design of semiconductor intersubband devices, accurate values for the Fermi energy and the subband electron population are needed. The effect of the position-dependent electron effective massm ^*  (z) is commonly neglected in the determination of these two intersubband device parameters. This approach is nearly valid for single-well devices in the GaAs/Al _xGa_1 − x As material system. However, in multiple-coupled-well devices, the variable nature of the effective mass must be taken into account. In material systems other than the ones based on GaAs, failure to include the position-dependence of the electron mass may give rise to significant errors in the values of the Fermi energy and other device parameters such as the intersubband absorption coefficient. In this paper, the effects ofm ^*  (z) on the Fermi level and the intersubband charge distribution are explored and quantified.Theoretical formulation for the intersubband Fermi energy and the subband electron distribution, with the inclusion of position-dependent electron mass, is presented. The eigenenergies of the intersubband structures are obtained by solving the single-band effective-mass Schroedinger equation using the argument principle method. The electron distribution and the Fermi energy are calculated using both the approximate method ( m₀ ^* ) and the rigorous formulation [ m ^* (z)], and the relative differences in the corresponding values are presented. It is demonstrated that these differences are small in the GaAs/Al _xGa_1 − x As material system, but can become very significant in other materials. In addition, the variable nature of carrier effective mass plays an important role in other types of devices such as interband quantum well photodetectors and lasers that employ optical transitions between the valence and the conduction bands. Electronic devices such as the resonant tunneling diode are also affected by the position-dependence of carrier mass and thus the results are applicable to both optoelectronic and electronic quantum devices.     

Microstructure change in poly(ethersulfone) films by swift heavy ions

PES membrane of thickness 25 μm was irradiated by Cl⁹⁺ ions of energy 100 MeV at IUAC, New Delhi. Microstructure changes due to exposure to high-energy ions were investigated by Fourier transform infrared (FTIR) and ultraviolet/visible (UV/vis) absorption spectroscopies, X-ray diffraction technique and by dynamic mechanical analysis (DMA). A significant loss of crystallinity is observed by the XRD data. Particle size or grain size calculated using Scherrer formula indicates measurable change in particle size of irradiated samples. The polymer chain scissions and structure degradations are expected to occur for irradiated samples. Optical properties of the films were changed due to irradiation that could be clearly seen in the absorption spectra. FTIR does not show the remarkable change in the irradiated samples, but there is some change in the surface roughness observed by AFM.