Upconversion properties of TM3+/Yb3+ codoped fluorophosphate glasses with low phonon density of states

Fluorophosphate glasses codoped with Tm3+ and Yb3+ were prepared and their thermal stability, phonon states, and upconversion properties were studied. It is found that the increment of phosphate content is good for the thermal stability but increases the phonon density of states. However, the phonon density of states of these fluorophosphate glasses is very low due to the low phosphate content in their composition. The upconversion luminescence spectra were measured under excitation of 970 nm laser diode, and the intense blue (476 nm) and near infrared (794 nm) emission were simultaneous obtained at room temperature. The sensitizing mechanisms of Yb3+ to Tm3+ for blue and red emission contain both sequential and cooperative sensitization. The near infrared emission is a two-photon upconversion process. These researches suggest that when the phosphate content in the composition is low enough, fluorophosphate glass can be suitable host material of Tm3+ codoped with Yb3+ for blue and near infrared upconversion luminescence. (c) 2005 Elsevier B.V All rights reserved.

Comparative investigation of up-conversion luminescence in Tm3+/Yb3+-codoped germanate-niobic and germanium-bismuth glasses: effect of phonon density on up-conversion emission

Tm3+/Yb3+-codoped gernianate-niobic (GN) and germanium-bismuth (GB) glasses have been synthesized by conventional ruching and quenching method. Intense blue and weak red emissions centered at 477 and 650 nm, corresponding to the transitions (1)G(4)->H-3(6) and (1)G(4)->H-3(4), respectively, were observed at room temperature. The possible Up-conversion mechanisms are discussed and estimated. GN glass showed a weaker up-conversion emission than GB glass, which is inconsistent with the prediction from the difference of maximum phonon energy between GN and GB glasses. In this paper, Raman spectroscopy was employed to investigate the origin of the difference in up-conversion luminescence in the two glasses. Compared with phonon side-band spectroscopy, Raman spectroscopy extracts more information including both phonon energy and phonon density. For the first time, our results reveal that, besides the maximum phonon energy, the phonon density of host glasses is also an important factor in determining the up-conversion efficiency. (c) 2005 Elsevier Ltd. All rights reserved.

Phonon modes of MgB2 : Super-lattice structures and spectral response

Micrometre-sized MgB2 crystals of varying quality, synthesized at low temperature and autogeneous pressure, are compared using a combination of Raman and Infra-Red (IR) spectroscopy. These data, which include new peak positions in both spectroscopies for high quality MgB2, are interpreted using DFT calculations on phonon behaviour for symmetry-related structures. Raman and IR activity additional to that predicted by point group analyses of the P6/mmm symmetry are detected. These additional peaks, as well as the overall shapes of calculated phonon dispersion (PD) models are explained by assuming a double super-lattice, consistent with a lower symmetry structure for MgB2. A 2x super-lattice in the c-direction allows a simple correlation of the pair breaking energy and the superconducting gap by activation of corresponding acoustic frequencies. A consistent physical interpretation of these spectra is obtained when the position of a phonon anomaly defines a super-lattice modulation in the a-b plane.

Coherent phonon decay and the boron isotope effect for MgB2

Ab-initio DFT calculations for the phonon dispersion (PD) and the Phonon Density Of States (PDOS) of the two isotopic forms (10B and 11B) of MgB2 demonstrate that use of a reduced symmetry super-lattice provides an improved approximation to the dynamical, phonon-distorted P6/mmm crystal structure. Construction of phonon frequency plots using calculated values for these isotopic forms gives linear trends with integer multiples of a base frequency that change in slope in a manner consistent with the isotope effect (IE). Spectral parameters inferred from this method are similar to that determined experimentally for the pure isotopic forms of MgB2. Comparison with AlB2 demonstrates that a coherent phonon decay down to acoustic modes is not possible for this metal. Coherent acoustic phonon decay may be an important contributor to superconductivity for MgB2.

Phonon properties of one-dimensional nanocrystalline solids

We study phonon properties of one-dimensional nanocrystalline solids that are associated with a model nanostructured sequence. A real-space renormalization-group approach, connected with a series of renormalization-group transformations, is developed to calculate numerically the local phonon Green's function at an arbitrary site, and then the phonon density of states of these kinds of nanocrystalline chains. Some interesting phonon properties of nanocrystalline chains are obtained that are in qualitative agreement with the experimental results for the optical-absorption spectra of nanostructured solids.

Electronic structure and phonon thermodynamics of iron alloys

Inelastic neutron scattering (INS) and nuclear-resonant inelastic x-ray scattering (NRIXS) were used to measure phonon spectra of FeV as a B2- ordered compound and as a bcc solid solution. Contrary to the behavior of ordering alloys studied to date, the phonons in the B2-ordered phase are softer than in the solid solution. Ordering increases the vibrational entropy, which stabilizes the ordered phase to higher temperatures. Ab initio calculations show that the number of electronic states at the Fermi level increases upon ordering, enhancing the screening between ions, and reducing the interatomic force constants. The effect of screening is larger at the V atomic sites than at the Fe atomic sites.

The phonon spectra of Au-rich alloys of fcc Au-Fe were also measured. The main effect on the vibrational entropy of alloying comes from a stiffening of the Au partial phonon density of states (DOS) with Fe concentration that increases the miscibility gap temperature. The magnitude of the effect is non- linear and it is reduced at higher Fe concentrations. Force constants were calculated for several compositions and show a local stiffening of Au–Au bonds close to Fe atoms, but Au–Au bonds that are farther away do not show this effect. Phonon DOS curves calculated from the force constants reproduced the experimental trends. The Au–Fe bond is soft and favors ordering, but a charge transfer from the Fe to the Au atoms stiffens the Au–Au bonds enough to favor unmixing. The stiffening is attributed to two main effects comparable in magnitude: an increase in electron density in the free-electron-like states, and stronger sd-hybridization.

INS and NRIXS measurements were performed at elevated temperatures on B2-ordered FeTi and NRIXS measurements were performed at high pressures. The high-pressure behavior is quasi- harmonic. The softening of the phonon DOS curves with temperature is strongly nonharmonic. Calculations of the force constants and Born-von Karman fits to the experimental data show that the bonds between second nearest neighbors (2nn) are much stiffer than those between 1nn, but fits to the high temperature data show that the former softens at a faster rate with temperature. The Fe–Fe bond softens more than the Ti–Ti bond. The unusual stiffness of the 2nn bond is explained by the calculated charge distribution, which is highly aspherical and localized preferentially in the t2g orbitals. Ab initio molecular dynamics (AIMD) simulations show a charge transfer from the t2g orbitals to the eg orbitals at elevated temperatures. The asphericity decreases linearly with temperature and is more severe at the Fe sites.

Phonon spectra and thermal properties of some fcc metals using embedded-atom potentials /

By employing the embedded-atom potentials of Mei et ai.[l], we have calculated the dynamical matrices and phonon dispersion curves for six fee metals (Cu,Ag,Au,Ni,Pd and Pt). We have also investigated, within the quasiharmonic approximation, some other thermal properties of these metals which depend on the phonon density of states, such as the temperature dependence of lattice constant, coefficient of linear thermal expansion, isothermal and adiabatic bulk moduli, heat capacities at constant volume and constant pressure, Griineisen parameter and Debye temperature. The computed results are compared with the experimental findings wherever possible. The comparison shows a generally good agreement between the theoretical values and experimental data for all properties except the discrepancies of phonon frequencies and Debye temperature for Pd, Pt and Au. Further, we modify the parameters of this model for Pd and Pt and obtain the phonon dispersion curves which is in good agreement with experimental data.

PHONON-SPECTRA OF RANDOMLY DISORDERED SYSTEM

We study the phonon density of states of a three dimensional disordered mixed crystal NaCl(x)Br1-x. The phonon structure is obtained by using a cluster method based on a continued fraction expansion of the Green function. The proposed dynamic model includes only short range interactions (first and second neighbors) but supports some qualitative features of the constituents binary alloys.

Vibronic model for band A emission in diamond

In this paper, recent results on band A emission in chemical vapor-deposited diamond films have been analyzed within a vibronic model. The blue-band A (2.8 eV) spectra from undoped diamond films grown by two different techniques have been simulated using the same phonon density distribution g(Omega) and Huang-Rhys factor (S). The same g(Omega) at higher S gives a good fit with the green band A (2.32 eV) as well. This model provides a reasonable alternative approach to the long standing donor-acceptor pair recombination model.

Characterisation of carbon nano-onions using Raman spectroscopy

Characteristics of the Raman spectrum from carbon onions have been identified in terms of the position of the G peak and appearance of the transverse optic phonon peaks. Five new peaks were observed in the low wavenumber region, at about 1100, 861, 700, 450 and 250 cm(-1). The origins of these peaks are discussed in terms of the phonon density of states (PDOS) and phonon dispersion curves of graphite. The curvature of the graphene planes is invoked to explain the relaxation of the Raman selection rules and the appearance of the new peaks. The Raman spectrum of carbon onions is compared with that of highly oriented pyrolytic graphite (HOPG). The strain of graphene planes due to curvature has been estimated analytically and is used to account for the downward shift of the G peak. (C) 2003 Elsevier Science B.V. All rights reserved.

Spectroscopic properties of Er3+/Yb3+ codoped fluorophosphate glasses

Er3+/Yb3+ cocloped fluorophosphate glasses were prepared and their thermal stabilities, Raman spectra, absorption spectra, and fluorescence spectra were measured. It is found that proper content of NaF or PbF2 is helpful for the increase of stability against crystallization. The variation of AI(PO3)3 or NaF content in the composition affects not the maximum phonon energy but the phonon density. The introduction of PbF2 decreases the phonon energy slightly. Intense green and red upconversion luminescence was observed for the fluorophosphate glass with low phosphate content. A glass matrix for upconversion luminescence requiring neither expensive raw material nor special atmospheric conditioned preparation is provided. Infrared luminescence around 1530 nm was researched. Fluorophosphate glasses with bandwidth properties and stimulated-emission cross sections better than tellurite, germanate and silicate glasses are obtained. Through the introduction of NaF, the bandwidth properties are decreased. Through the introduction of PbF2 the gain properties are increased. On the whole, it is difficult to obtain a material with the best gain properties and bandwidth properties simultaneously. There should be a compromise between them according to the demand. (C) 2006 Elsevier B.V. All rights reserved.

Stability against crystallization and spectroscopic properties of Tm3+ doped fluorophosphate glasses

Fluorophosphate glasses with various content of Al(PO3)(3) were prepared. With the increment of Al(PO3)(3) content, density decreases while refractive index increases, and transition temperature, crystallization peak temperature and melt temperature increase which were suggested by differential scanning calorimetry. These glasses exhibit the best stability against crystallization with 7-9 mol'Yo Al(PO3)(3) content. Normalized Raman spectra were used to analyze structure and phonon state. The increment of Al(PO3)(3) content does not affect phonon energy but results in the augment of phonon density. Absorption spectra were measured. H-3(6) -> F-3(4) transition exhibits absorption at L band of the third communication window. Compared with the energy of Tm3+ excited states in other glass system, F-3(4) energy of Tm3+ in these glasses is considerable higher and H-3(4) energy is considerable lower, and it can be predicted that emission band of H-3(4) -> F-3(4) transition is close to the amplified band of gain-shift Tm3+ doped fiber amplifier. Analyses of Judd-Ofelt theory suggest when Al(PO3)(3) content is no more than 7 mol%, Judd-Ofelt parameters Omega(t) and the lifetime of H-3(4) energy level of TM3+ vary little with the increment of Al(PO3)(3) content, and when Al(PO3)(3) content is more than 7 mol%, Omega(2) and Omega(6) increase and radiative lifetime of H-3(4) energy level of Tm3+ drops sharply with the increment of Al(PO3)(3) content. (c) 2006 Elsevier B.V. All rights reserved.

Effect of oxygen substitution by halide ions on structure, thermal stability and upconversion fluorescence in Er3(+)/Yb3(+)-codoped germanium-bismuth glasses

For the first time. effect of halide ions (F-, Cl-, Br-, and I-) introduction on structure, thermal stability, and upconversion fluorescence in Er3+/Yb3+-codoped oxide-halide germanium-bismuth glasses has been systematically investigated. The results show that halide ions modified germanium-bismuth glasses have lower maximum phonon energy and phonon density, worse thermal stability. longer measured lifetimes of I-4(l1/2) level, and stronger upconversion emission than germanium-bismuth glass. All these results indicate that halide ions play an important role in the formation of glass network, and have an important influence on the upconversion luminescence. The possible upconversion mechanisms of Er3+ ion are also evaluated. © 2005 Elsevier Ltd. All rights reserved.

Effect of PbCl2 addition on structure, OH- content, and upconversion luminescence in Yb3+/Er3+-codoped germanate glasses

Yb3+/ Er3+-codoped oxychloride germanate glasses have been synthesized by a conventional melting and quenching method. Structural properties were obtained based on Raman-spectra investigation, indicating that PbCl2 plays an important role in the formation of the glass network and has an important influence on the phonon density and the maximum phonon energy. The Judd - Ofelt intensity parameters and quantum efficiencies were calculated based on the Judd - Ofelt theory and lifetime measurements. The enhanced upconversion luminescence intensity of Er3+ with increasing PbCl2 content could not be explained only by the maximum phonon-energy change of the host glasses. For the first time, the effect of PbCl2 addition on phonon density, OH- content, and upconversion luminescence in oxychloride glasses has been discussed and evaluated. The results show that the effect of phonon density and OH- content on upconversion luminescence in oxychloride glasses is much stronger than that of the decrease of the maximum phonon energy. The possible upconversion luminescence mechanisms have also been estimated and are discussed.

Investigation of the effect of fluoride ions introduction on structural, OH- content and up-conversion luminescence properties in Er3+-doped heavy metal oxide glasses

Effect of fluoride ions introduction on structural, OH- content and up-conversion luminescence properties in Er3+-doped heavy metal oxide glasses have been investigated. Structure was investigated, indicating that fluoride has an important influence on the phonon density, maximum phonon energy of host glasses. With increasing fluoride content, the up-conversion luminescence intensity and quantum efficiencies increase notably, which could not be explained only by the maximum phonon energy change of host glasses. Our results show that, with the introduction of PbF2, the decrease of phonon density and OH- content contributes more to the enhanced up-conversion emissions than that of maximum phonon energy. (c) 2005 Elsevier B.V. All rights reserved.