Direct and modulated reflectance spectra of MnO,CoO, and NiO

Direct reflectance, thermoreflectance, and electroreflectance have been measured for MnO, CoO, and NiO above the fundamental edge. Spectra of all three materials support a model containing both localized and one-electron band states. In MnO peaks with temperature coefficients of ～ 10^?3 eV/K were observed at 5.7 and 6.9 eV, temperature-independent structure occurred at 5.4, 6.3, and 7.2 eV, and spectral features with indeterminate temperature dependence were seen at 4.6 and 5.5 eV. The temperature-dependent structure was assigned to one-electron interband transitions associated with anion 2p and cation 4s states; the temperature independent structure was assigned to crystal field split localized interionic transitions between the 3d-states of neighboring Mn ions. Thermoreflectance spectra for CoO exhibited temperature dependent structure (9.5 × × 10^?4 eV/K at 5.0, 6.0, and 7.2 eV. A strong, temperature dependent electroreflectance oscillation was seen in NiO near 6.2 eV. On the basis of these data the interband gap between the anion 2p and cation 4s bands was determined to be 5.7 eV in MnO, 6.0 eV in CoO, and 6.2 eV in NiO.     

Luminescence centers generated by chromium ions in potassium-aluminum (indium) diphosphates

Crystals of potassium-aluminum (indium) diphosphates KMeP₂O₇ (Me = Al, In) doped by chromium ions are synthesized for the first time, and their main spectral luminescence properties are described. The luminescence of these crystals is studied in the temperature range 4.2–300 K under excitation by light with a wavelength of 270–650 nm. The luminescence spectrum has two wide bands in the ranges 450–650 nm (“green” photoluminescence) and 700–800 nm (“red” photoluminescence). The green photoluminescence band is assumed to be a superposition of the intrinsic radiation of the matrix and the radiation of molecular centers generated by chromium ions that are surrounded by four oxygen atoms. At low temperatures, the red photoluminescence band consists of a wide unstructured band and narrow lines on its short-wavelength wing and is associated with the radiation of Cr³⁺ ions that replace Al³⁺ matrix ions and are in an octahedral oxygen environment. Parameters of the electron energy level diagram of the Cr³⁺ ion in the matrices of the investigated crystals are determined.     

The effect of the next nearest neighbor ion on the X-ray photoelectron spectra of 2p levels for Co2+, Ni2+ and Cu2+ in MgO

The X-ray photoelectron spectra of Co, Ni and Cu 2p levels for samples of M_xMg_1-xO (M = Co, Ni, Cu), CoO, NiO and CuO were compared. The binding energies of metal 2p_{$\text{3}\text{2}$} levels did not change with their concentration. The shake-up satellite main peak intensity ratios and FWHM of metal 2p levels for Co²⁺ and Cu²⁺ in MgO were smaller than those for CoO and CuO. The Ni 2p_{$\text{3}\text{2}$} spectrum for Ni²⁺ in MgO had no shoulder, unlike NiO. Results indicate that next nearest neighbor ions (metal ions) may influence the final states after photoelectron ejection.     

Consistent LDA’ + DMFT approach to the electronic structure of transition metal oxides: Charge transfer insulators and correlated metals

We discuss the recently proposed LDA’ + DMFT approach providing a consistent parameter-free treatment of the so-called double counting problem arising within the LDA + DMFT hybrid computational method for realistic strongly correlated materials. In this approach, the local exchange-correlation portion of the electron-electron interaction is excluded from self-consistent LDA calculations for strongly correlated electronic shells, e.g., d-states of transition metal compounds. Then, the corresponding double-counting term in the LDA’ + DMFT Hamiltonian is consistently set in the local Hartree (fully localized limit, FLL) form of the Hubbard model interaction term. We present the results of extensive LDA’ + DMFT calculations of densities of states, spectral densities, and optical conductivity for most typical representatives of two wide classes of strongly correlated systems in the paramagnetic phase: charge transfer insulators (MnO, CoO, and NiO) and strongly correlated metals (SrVO₃ and Sr₂RuO₄). It is shown that for NiO and CoO systems, the LDA’ + DMFT approach qualitatively improves the conventional LDA + DMFT results with the FLL type of double counting, where CoO and NiO were obtained to be metals. Our calculations also include transition-metal 4s-states located near the Fermi level, missed in previous LDA + DMFT studies of these monoxides. General agreement with optical and the X-ray experiments is obtained. For strongly correlated metals, the LDA’ + DMFT results agree well with the earlier LDA + DMFT calculations and existing experiments. However, in general, LDA’ + DMFT results give better quantitative agreement with experimental data for band gap sizes and oxygen-state positions compared to the conventional LDA + DMFT method.     

Structure electronique des oxydes de cobalt CoO et Co3O4

The total density of occupied states in the valence band of CoO and Co₃O₄ is determined by XPS and UPS. From variations of excitation probability of the bands, the 4 e V wide O2_p band is shown to be located around 5 eV for both oxides, while structures obtained from photoionisation of the localized 3d band spread over 10 eV range below the Fermi level overlapping with O2_p band. The 3d peaks located at binding energy <3 eV correspond to the calculated energy of the d_n ?1 manifold final state in the octahedral and tetrahedral crystal field of CoO and Co₃O₄. The 3d levels at higher binding energy are shown to occur from configuration interaction in both final and initial states. These last peaks are higher in intensity for CoO relative to Co₃O₄. A superior limit for the width of the 3d initial band in a one electron energy diagram is given to be <3 eV. This value associated to the Coulomb correlation energy measured equal to ~3 eV. This value associated to the Coulomb correlation energy measured equal to ~3 eV from shake-up and Auger energy confirms the Mott insulator nature of CoO.     

Preparation of NiO and CoO nanoparticles using M2+-oleate (M = Ni,Co) as precursor

The preparation of NiO and CoO nanoparticles was reported. The dot-like NiO and flower-like CoO nanoparticles were obtained using M²⁺-oleate (M = Ni, Co) as precursor via thermal decomposition method. Transmission electron microscopic (TEM) images monitored the growth of NiO and CoO nanoparticles. When the reaction complex including M²⁺-oleate (M = Ni, Co) precursor, oleic acid and 1-octadecene was heated to the refluxing temperature (320 °C), the formed NiO and CoO nanoparticles were needle-like and very small, indicating low growth speed. However, when the reaction complex was kept refluxing for 30 min, dot-like NiO and flower-like CoO nanoparticles were observed, suggesting the accelerated growth at this refluxing stage. The difference of the morphology of the resultant NiO and CoO nanoparticles resulted from the difference of their growth mode. Selected-area electron diffraction (SAED) patterns showed the face-centered cubic structures of NiO and CoO nanoparticles. The magnetic property of the nanoparticles was studied using vibrating sample magnetometer (VSM).     

Small-polaron versus band conduction in some transition-metal oxides

In this paper an attempt is made to establish the nature of free charge carriers and of charge carriers bound to centres in p-type NiO, CoO and MnO and in n-type MnO and α-Fe₂O₃.

For free charge carriers, d.c. conductivity, Seebeck coefficient and Hall effect are considered. Effects arising from inhomogeneous conduction and impurity conduction are discussed. Impurity conduction appears to have a strong influence on transport properties in the case of α-Fe₂O₃, less so in NiO, whereas no influence of this effect has been found in CoO and MnO. It is shown that NiO and CoO do not exhibit the features characteristic of small-polaron conductors but rather can be consistently conceived of as large-polaron band semiconductors. It is suggested that magnetic resistance due to exchange coupling between charge-carrier spin and cation spins plays an important role. The anomalous behaviour of the Hall effect in NiO and α-Fe₂O₃ is extensively discussed. In contradistinction to NiO, CoO and n-type MnO, free charge carriers in p-type MnO seem to have small-polaron character.

For charge carriers bound to centres, dielectric loss, high-frequency conduction and optical absorption are considered. The dielectric loss data relate to Li or Na centres in NiO, CoO and MnO and to Ti, Zr, Sn, Ta, Nb and presumably oxygen vacancy centres in α-Fe₂O₃. It is concluded from the dependence of dielectric loss on frequency and temperature that bound charge carriers are small polarons. It is shown for the cases of NiO and α-Fe₂O₃ that apart from small-polaron effects, disorder due to locally varying electric fields determines the nature of dielectric loss. The small-polaron character of bound charge carriers in NiO is corroborated by the behaviour of high-frequency conduction and optical absorption due to centres and also by the magnitude of impurity conduction.     

Luminescence of thulium-activated cubic boron nitride

Under high pressure and temperature conditions, we have obtained samples of thulium-activated cubic boron nitride in the form of micropowders, ceramics, and polycrystals activated by thulium in the presence of aluminum. We studied the cathodoluminescence (CL), photoluminescence (PL), and photoluminescence excitation spectra of the samples. In the luminescence spectra we observe structured bands with maxima at ∼370, ∼475, ∼660, and ∼ 800 nm, assigned to electronic transitions in the triply charged thulium ions. We have established that the most efficient method for excitation of “blue” luminescence at ∼475 nm for thulium ions in cBN is excitation by an electron beam. The cBN samples synthesized in the presence of Al have photoluminescence spectra with a more complex structure compared with samples not containing Al, with the band of dominant intensity at about 660 nm. Hypothetically, this is a consequence of incorporation of thulium ions into the crystalline phases cBN and AlN, which are equally likely to be formed during synthesis. The observed photoluminescence spectrum of the indicated samples is the superposition of the photoluminescence spectra of the Tm³⁺ ions located in the crystal fields of cBN and AlN of different symmetries. The presence in the photoluminescence excitation spectra (at 450, 490, and 660 nm) of structure, with features at wavelengths shorter than the excited photoluminescence, suggests a nonresonant mechanism for its excitation. We have established that luminescence of Tm³⁺ ions is less intense than for other rare earth elements incorporated into cubic boron nitride. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 4, pp. 547–555, July–August, 2008.     

Luminescent properties of LiCl-Cu single crystals

The absorption, photoluminescence, x-ray luminescence, and thermoluminescence spectra, and the photoluminescence excitation spectra of LiCl-Cu single crystals with different activator concentration were investigated at temperatures of 79–450°K. The absorption spectrum at room temperature has two bands with maxima at 237 and 259 nm. The absorption coefficient of the 237 nm band is proportional to the copper concentration in the crystal (C_Cu ≤ 7·10^?4 mole %). The photoluminescence and x-ray luminescence spectrum at room temperature consists of one emission band at 324 nm, which conforms with the Mollwo-Ivey rule in the homologous series RbCl → KCl → NaCl → LiCl. The copper ions create trapping levels for electrons and holes at different depths in the forbidden band of the LiCl crystal. The correlation between the thermoluminescence peaks and the recombination-luminescence excitation bands (infrared stimulation) is investigated.     

Optical properties of silylene-biphenylene copolymer films

We have measured absorption, photoluminescence, and photoluminescence excitation spectra, and the photoluminescence time response for films of silylene-biphenylene copolymer, ((C₆H₄)₂(Si(CH₃)₂)_m)_n with m=1,2,4, and 6. The excitation spectra clearly reveal that the lowest absorption band in each copolymer consists of two bands, i.e., a band at 4.7 eV and a band of which energy depends on m. Since the latter band is absent in the copolymer with m=1, the former band is attributed to the lowest π−π* transition in biphenylene subunits. The latter band is attributed to the lowest σ−σ* transition in the silylene subunits, considering its dependence on m. In contrast to the result for solution, the peak energy of photoluminescence band is independent of m. The band has a Stokes shift of more than 1 eV and a large band width of 0.5 eV. The time responses of photoluminescence intensity consist of more than two decay components and the intensity decays more slowly at smaller energy. The large Stokes shift is explained as due to excimer formation between biphenylene subunits. In order to explain the energy dependence of time responses, energy migration is discussed.     

Photoluminescence investigations of cubic boron nitride doped with neodymium during high-pressure synthesis

Micropowders of cubic boron nitride doped with neodymium are prepared under high-pressure and high-temperature conditions. The phase composition of the micropowders is studied using X-ray diffractometry and X-ray fluorescence analysis. The photoluminescence, photoluminescence excitation spectra, and the life-time of the ⁴ F _3/2 excited state of Nd ions introduced into cubic boron nitride are investigated. In photoluminescence spectra of the micropowders, structured bands are recorded in the range of the ⁴ F _3/2 → ⁴ I _9/2 and ⁴ F _3/2 → ⁴ I _11/2 electronic transitions. A higher intensity of the first structured band indicates that the corresponding photoluminescence in cubic boron nitride doped with neodymium is excited by the “three-level scheme.” It is demonstrated that an increase in the concentration of the neodymium compound in the growth batch leads to the formation of two luminescence centers Nd1 and Nd2 formed by neodymium ions located in different low-symmetry crystal fields in the micropowders. This is confirmed by X-ray diffraction investigations and the study of the photoluminescence decay curves. The ⁴ F _3/2 short-lived state is assigned to the Nd ions forming the Nd1 centers, and the long-lived state is attributed to the Nd ions forming the Nd2 centers.     

Low-temperature time-resolved vacuum ultraviolet luminescent spectroscopy of KH2PO4 crystals with defects

Low-temperature photoluminescence (PL) of unactivated KDP crystals under selective synchrotron excitation is for the first time measured with subnanosecond time resolution. Time-resolved PL (2–6 eV) and PL excitation (4–35 eV) spectra, as well as PL kinetics, are measured at 7 K. From the acquired experimental data, luminescent bands related to intrinsic defects of the KDP lattice are identified; in particular, the long-wave band at 2.6 eV is assigned to L defects, and the band at 3.5–3.6 eV is attributed to D defects. An efficient energy transfer over the hydrogen sublattice is shown to take place in KDP at low temperatures. It results in the efficient excitation of L and D center photoluminescence in the fundamental absorption region, at electron transitions to the bottom levels of the conduction band, corresponding to the states of the hydrogen atom. The band gap E _g is evaluated to be 8.0–8.8 eV.     

Luminescence of CdS generated by high intensity excitation below the bandgap

High excitation photoluminescence of CdS at low temperatures excited by photons below the bandgap show the same general features as those obtained by one-photon band to band absorption. The excitation spectrum of the M-line shows no structure corresponding to a giant two-photon absorption expected for the direct creation of excitonic molecules.     

A preliminary investigation upon the electrochemical behavior of CoO and NiO anodes — comparative study

Among the variety of alternate anode materials being studied, the research on the exploration of 3d-metal oxide anodes gains paramount importance in the recent time, as it is bestowed with an easy preparation method and a less complicated decomposition mechanism. Towards this direction, an attempt to synthesize the compound CoO and to investigate the electrochemical behavior of the same both individually and in comparison with NiO compounds was made with a view to understand the extent to which the chosen candidates, viz., CoO and NiO can be exploited as high capacity anodes. Between the two oxides, CoO exhibited a specific capacity of at least 550 mAh/g, against NiO with an average capacity of ∼330 mAh/g. Also, the magnitude of irreversible capacity loss and the extent of capacity fade upon cycling corresponding to CoO anode were found to be lesser than NiO anodes. The enhanced specific capacity values and the better cycleability properties of CoO anodes are believed to be due to the inherent electrochemical characteristics of the compound. The type and the nature of SEI formed over the electrode surface and the formation of possible progressive agglomeration of the products of decomposition are expected to be the factors responsible for the difference in the electrochemical behavior of CoO and NiO anodes. In short, electrochemical characterization of the individual oxides are studied and probable reasons for the observed difference in the charge-discharge behavior of CoO and NiO anodes are discussed in this communication.     

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.     

Evidence for exciton binding at Ni impurity sites in ZnSe

A broad charge transfer band is observed in the photoluminescence excitation (PLE) spectrum of the 2.5 μ Ni²⁺ luminescence in ZnSe : Ni. This band lies above the highest energy d-d excitation bands and exhibits a ZPL at 1.8163 eV and LO(#38;0lambda;) phonon replicas at higher energy. In contrast, PLE spectra of Co²⁺ luminescence in ZnSe:Co contain only d-d excitation bands. The charge transfer band in ZnSe:Ni is interpreted as evidence for bound exciton formation at the Ni site. The recombination energy of this exciton is transferred efficiently to the excited d-band states of the Ni ion, leading to characteristic Ni²⁺d-d luminescence.     

Non-geminate recombination in amorphous silicon

The excitation power dependence of the light-induced EPR signal in intrinsic a-Si: H is found to be sub-linear over the entire accessible range of excitation power. This result is shown to require a distant-pair model of the recombination of the carriers giving the LESR. If, as is thought, the same carriers give LESR and the 1.4 eV photoluminescence band, we show that the luminescence is also distant-pair.     

Electronic structures of N- and C-doped NiO from first-principles calculations

The large intrinsic band gap of NiO has hindered severely its potential application under visible-light irradiation. In this Letter, we have performed first-principles calculations on the electronic properties of N- and C-doped NiO to ascertain if its band gap may be narrowed theoretically. It was found that impurity bands driven by N 2p or C 2p states appear in the band gap of NiO and that some of these locate at the conduction band minimum, which leads to a significant band gap narrowing. Our results show that N-doped NiO may serve as a potential photocatalyst relative to C-doped NiO, due to the presence of some recombination centres in C-doped NiO.     

Crystal structure and photoluminescence of (Y1−xCex)2Si3O3N4

Oxonitridosilicate phosphors with compositions of (Y_1−xCe_x)₂Si₃O₃N₄ (x=0−0.2) have been synthesized by solid state reaction method. The structures and photoluminescence properties have been investigated. Ce³⁺ ions have substituted for Y³⁺ ions in the lattice. The emission and excitation spectra of these phosphors show the characteristic photoluminescence spectra of Ce³⁺ ions. Based on the analyses of the diffuse reflection spectra and the PL spectra, a systematic energy diagram of Ce³⁺ ion in the forbidden band of sample with x=0.02 is given. The best doping Ce content in these phosphors is ∼2 mol%. The quenching temperature is ∼405 K for the 2 mol% Ce content sample. The luminescence decay properties were investigated. The primary studies indicate that these phosphors are potential candidates for application in three-phosphor-converted white LEDs.     

Alloying induced shift between excitation and luminescence of the nitrogen bound exciton in GaPxAs1−x alloys

Photoluminescence and luminescence excitation spectra have been performed on epitaxial layers of nitrogen doped GaP_xAs_1?x alloys (x > 0.85). The main luminescence excitation band A appears above the photoluminescence band N_x. The composition dependence of this energy shift suggests an alloying energy shift. The origin of this new effect would be the thermalization of the bound exciton population to the lower energy states of the A absorption band which reflects the density of states broadening due to As-P disorder around N atoms