Raman spectroscopic investigation of pure and ytterbium‐doped rare earth silicate crystals

Raman spectroscopy was used to study the molecular structure of a series of selected rare earth (RE) silicate crystals including Y₂SiO₅ (YSO), Lu₂SiO₅ (LSO), (Lu_0.5Y_0.5)₂SiO₅ (LYSO) and their ytterbium‐doped samples. Raman spectra show resolved bands below 500 cm⁻¹ region assigned to the modes of SiO₄ and oxygen vibrations. Multiple bands indicate the nonequivalence of the RE O bonds and the lifting of the degeneracy of the RE ion vibration. Low intensity bands below 500 cm⁻¹ are an indication of impurities. The (SiO₄)⁴⁻ tetrahedra are characterized by bands near 200 cm⁻¹ which show a separation of the components of ν₄ and ν₂, in the 500–700 cm⁻¹ region which are attributed to the distorting bending vibration and in the 880–1000 cm⁻¹ region which are attributed to the symmetric and antisymmetric stretching vibrational modes. The majority of the bands in the 300–610 cm⁻¹ region of Re₂SiO₅ were found to arise from vibrations involving both Si and RE ions, indicating that there is considerable mixing of Si displacements with Si O bending modes and RE O stretching modes. The Raman spectra of RE silicate crystals were analyzed in terms of the molecular structure of the crystals, which enabled separation of the bands attributed to distinct vibrational units. Copyright © 2007 John Wiley & Sons, Ltd.     

Transport properties and mangetoresistance of (RE,Sr)2NiO4 (RE=Pr,Nd, Sm and Eu)

We report on the crystal growth and the measurements of resistivity, magnetoresistance and photoemission spectroscopy of (RE,Sr)₂NiO₄ in the heavily Sr-doped region. Although the in-plane resistivity of the heavily Sr-doped crystals was rather small at room temperature, it increased for several orders of magnitude with decreasing temperature. A large negative magnetoresistance was observed for NdSrNiO₄ at low temperature, while only small magnetoresistance was observed for the single crystals of RE=Pr, Sm and Eu. Photoemission spectroscopy measurements revealed a significant influence of the RE 4f states to the electronic structure at relatively low binding energies in PrSrNiO₄ and NdSrNiO₄.     

Electro-optic and dielectric properties of Hafnium-doped congruent lithium niobate crystals

We report the optical and dielectric properties in hafnium (Hf)-doped lithium niobate (LN) crystals. We investigated samples of congruent composition with various doping concentration varying from 0 to 8 mol%. The clamped and unclamped values of the electro-optic coefficient r ₂₂ of Hf-doped LN and the corresponding dielectric permittivity as well, have been experimentally determined and compared with the results obtained in undoped congruent LN crystals. We show that the electro-optic and dielectric properties are only slightly affected by the introduction of hafnium ions, and therefore Hf-doped LN has the advantage of low photorefractive damage compared with the undoped congruent LN.     

PbWO4晶体中的填隙氧及其对晶体光学性质的影响

运用GULP计算软件模拟计算了PbWO₄(PWO)晶体中不同位置的填隙氧原子点缺陷的生成能，计算结果表明：当填隙氧原子存在于(WO₄)^2-的周围时，填隙氧原子点缺陷的生成能最低；进一步运用基于密度泛函理论的全数值自洽DV-Xα方法计算了包含填隙氧原子的PWO晶体的态密度，计算结果表明：当填隙氧处在(WO₄)^2-的周围时，容易与(WO₄)^2-上的一个或两个氧离子相互作用形成分子离子O₂^2-或O₃^4-，通过分析这些计算结果，认为PWO晶体中350 nm吸收带的出现很可能与晶体中的氧分子离子有关.     

Divalent rare-earth ions Pr,Sm, Нo,Er, Tm,and Yb in crystals of alkaline-earth fluorides

The absorption spectra of radiation-colored CaF₂, SrF₂, and BaF₂ crystals activated by trivalent Pr, Sm, Нo, Er, Tm, and Yb (rare-earth, RE) ions are studied. It is shown that ionizing radiation reduces the impurity ions to the divalent state. The temperature resistance of divalent RE ions of radiation-colored CaF₂ crystals correlates with the chemical stability of the compounds with divalent RE ions. The photochromic centers are produced in CaF₂-Pr crystal colored by radiation at room temperature and heated to 200°C.     

Study of ferromagnetism in Co-doped rutile powders and float-zone grown single crystals

Co-doped rutile samples in the form of both powders and bulk single crystals have been studied with particular emphasis on the dependence of their magnetic, compositional and structural properties upon the type of atmosphere used during their preparation. Both powders and single crystals were characterized using X-ray diffractometry and vibrating sample magnetometry, while the crystals were also studied using the X-ray Laue technique, scanning electron microscopy and energy dispersive X-ray analysis. The results indicate that an oxygen deficient environment during the preparation of Co-doped TiO₂ powders is crucial for the observation of room temperature ferromagnetism, while preparation in oxygen rich conditions destroys the ferromagnetism due to the formation of the paramagnetic second phase CoTiO₃. Floating zone growth of crystals under oxygen also led to the formation of material containing second phase CoTiO₃ that was paramagnetic at room temperature, while crystals grown under argon were ferromagnetic and contained Co-rich inclusions.     

Luminescence spectroscopy of Ln-doped Bi-containing phosphates and molybdates

The photoluminescence (PL) emission and excitation spectra of undoped and doped with rare-earth (RE = Eu, Tb) ions K₃Bi₅(PO₄)₆ and K₂Bi(PO₄)(MoO₄) crystals are studied in 3.7–14 eV region of the excitation photon energies at T = 8 and 300 K. The mechanisms of the host-related and RE-related luminescence in 3.7–7 eV region of the excitation photon energies are revealed in comparative analysis of the PL spectra of studied compounds. It is assumed that the excitation mechanisms of host luminescence of K₃Bi₅(PO₄)₆ and K₂Bi(PO₄) (MoO₄) crystals below 4.8 eV are related to Bi³⁺ ions in oxygen surrounding. An efficient energy transfer from the Bi³⁺-related luminescence centers to the emitting RE centers exists in crystals with low concentration of the RE dopants (1%). The PL excitation spectra of K₃Bi₅(PO₄)₆ crystals with high concentration of Eu dopants are formed by O – Eu CT transitions.     

The Role of Oxygen Containing Impurities in Defects Formation in Cesium Halide Crystals

The dependence of defect formation efficiency in CsI single crystals both on the type of oxygen containing impurities and the value of the absorbed irradiation dose was studied. Correlative results were obtained under investigation by methods of ionic thermocurrent (ITC), thermostimulated exoemission (TSEE), electrical conductivity and optical spectroscopy. The peculiarities of defect formation in γ-irradiated CsI-CO₃(SO₄, OH) and X-irradiated CsI-OH single crystals are discussed.     

ZnO-doped LiNbO<Subscript>3</Subscript> single crystals studied by X-ray and density measurements

Energy Dispersive X-ray Fluorescence Spectroscopy, X-ray diffraction and density measurements were conducted on undoped and ZnO-doped congruent LiNbO₃ single crystals grown by the Czochralski method. Based on the experimental results, an intrinsic defect evolution model was proposed. When ZnO was doped into the congruent LN crystals, the Zn ions replaced first the Li ions and increased the density. Then, the Zn ions simultaneously replaced the Li ions and the antisite Nb_Lis until all Nb_Li ions were replaced, which increased the density further. After that, the Zn ions substituted Nb ions in the Nb-sublattice sites with the reduction of the Li vacancies as self-compensation and thus reduced the density. When the Li vacancies disappeared completely, the Zn ions substituted simultaneously both Li ions in the Li-sublattice sites and Nb ions in the Nb-sublattice sites. The simultaneous substitution might finally lead to the generation of oxygen vacancies and decreased the density further. PACS 61.72.-y; 06.30.Dr; 61.10.-i     

Growth and optical properties of In:Nd:LiNbO3 crystals

In, Nd double-doped LiNbO₃ (LN) crystals have been grown for the first time. Their infrared (IR) transmission spectra were measured and discussed to investigate their structure and defects. The optical damage resistance of Nd:In:LiNbO₃ crystals were characterized by straightly observing transmission facula distortion method. The optical damage resistance of In (4.0 mol%):Nd:LiNbO₃ was much higher than that of Nd:LiNbO₃. The defects were discussed in this paper to explain the optical damage resistance in the In:Nd:LiNbO₃ crystals.     

Crystal growth and optical properties of Cr3+, Er3+, RE3+: Gd3Ga5O12 (RE=Tm,Ho, Eu) for mid-IR laser applications

In this paper we report on the optical properties of triply Cr³⁺, Er³⁺, and RE³⁺ (RE=Tm, Ho, Eu) doped Gd₃Ga₅O₁₂ crystals that were grown by the Czochralski method. Optical absorption, near-infrared (NIR), and mid-infrared (mid-IR) fluorescence spectra were characterized for the fabricated crystals and corresponding luminescence decay measurements under 654 nm excitation were also carried out. Based on the analysis of energy transfer process between Er and RE (RE=Tm, Ho, Eu) ions, the energy transfer efficiency (ETE) values were evaluated, correspondingly. From the spectral data of all the studied crystals, it is observed that the co-doped Cr³⁺ ion highly increases the absorption pump power and the three kinds of co-doped RE³⁺ ions depopulate the Er:⁴I_13/2 energy level effectively. The spectral analysis shows that titled rare earth doped crystals are promising materials for ～3.0 μm mid-IR laser applications and among them Cr,Er,Eu:GGG is relatively more suitable due to its excellent optical properties compared with others.     

Crystal fields of hexameric rare-earth clusters in fluorites

In solid solutions of alkaline-and rare-earth fluorides with a fluorite structure, ions of most elements of the rare-earth (RE) row form hexameric clusters that assimilate the minor component of the solid solutions (fluorine) and build it into the cubic fluorite lattice without changing its shape. An analysis of the EPR spectra of paramagnetic RE ions (Er³⁺, Tm³⁺, Yb³⁺) in clusters of diamagnetic ions (Lu³⁺, Y³⁺) confirms their hexagonal structure, which was established when studying the superstructures of the compounds under study. In such a cluster, a RE ion is in a nearly tetragonal crystal field, with the parameters of this field differing radically from those of single cubic and tetragonal RE centers in crystals with a fluorite structure. In particular, this field causes high (close to limiting) values of the g_∥ factors of the ground states of the paramagnetic RE ions. Computer simulation is used to determine the atomic structure of a hexameric cluster in MF₂ crystals (M = Ca, Sr, Ba). The crystal field and energy spectrum of Er³⁺, Tm³⁺, and Yb³⁺ ions in such clusters are calculated, and the spectroscopic parameters of the ground states of these ions are determined. The calculations confirm the earlier assumption that the unusual EPR spectra of nonstoichiometric fluorite phases are related to RE ions in hexameric clusters.     

Synthesis under ambient pressure and tri-axial magnetic orientation in REBa2Cu4O8 (RE = Y,Sm, Eu,Gd, Dy,Ho, Er)

We report the rare-earth (RE)-dependent magnetization axes of REBa₂Cu₄O₈, which was synthesized by a flux method under ambient pressure, using powder samples tri-axially oriented in a modulated rotating magnetic field of 10 T. By optimizing the growth temperature and cooling rate, RE124 crystals were successfully grown for RE = Y, Sm, Eu, Gd, Dy, Ho, and Er. From the X-ray diffraction measurement, the magnetically oriented directions were largely dependent on the type of RE ions of RE124. However, the tri-axial magnetic anisotropies of RE124 could be qualitatively understood in terms of the magnitude relation between the single-ion magnetic anisotropy of RE³⁺ ions and the magnetic anisotropy generated by the CuO₂ plane and Cu–O chain. For the practical use of this magneto-scientific process, the control of magnetization axes and tri-axial magnetic anisotropies through crystallochemical control is indispensable.     

In situ observation and simulation of growth process of faceted RE123 crystals

To clarify the growth mechanism of faceted REBa₂Cu₃O_7−δ (RE123, RE = Sm, Y) crystals, the growth process of the crystals was observed in situ by using a high temperature microscope. The growth rate of each faceted interface of a crystal growing from the liquid + 211 phases under an undercooling was obtained from the relationship between the position of each interface and growth time. It was observed that some of the faceted interfaces of a growing crystal stopped growing after a period of time, while other interfaces continued to grow with a growth rate approximated by a function of the undercooling. The above stoppage of the growth was observed in situ for the first time, and this fact could give powerful support to the mechanism for a similar phenomenon in REBCO films which were fabricated by the trifluoroacetates metal organic deposition method: growing microstructures of RE123 crystals in the film were revealed by transmission electron microscopy (TEM) for quenched specimens. Some very thin a-axis grains were formed by a change in c-axis growth rate. Furthermore, we showed the above growth and stop phenomena of faceted interfaces of REBCO crystal grains using numerical simulations.     

Upconversion luminescence dynamics of Er-doped fluoride crystals for optical converters

Erbium (Er)-doped fluoride crystals (YLF, BYF, CaF₂, etc.) are well-known as active media for solid-state lasers emitting in IR and VIS spectral domains, and as materials for efficient near-IR to VIS upconversion. In this paper, we report on the study of conversion of IR light from an ～1.5 μm spectral region to an ～1 μm spectral domain in low-phonon RE-doped fluoride crystals CaF₂ (RE=Er³⁺ Yb³⁺). Energy transfer processes taking place at selective pulsed and CW laser excitation are investigated experimentally. It is shown that in the CaF₂:RE crystals efficient conversion of IR radiation from the ～1.5 μm region to the ～1 μm region occurs, and these crystals are perspective for using in spectral converters for enhancing solar cell efficiency.     

X-ray investigations and possible mechanism for the ionic conductivity in the Na5RESi4O12 (RE=Y,Sc) class of compounds

X-ray investigations on single crystals of the series of rare-earth compounds Na₅RESi₄O₁₂ with RE as Sc or Y were carried out at room temperature and 300°C. They show a dependence of the inner symmetry of the main conductive channels on the type of the RE ion. A simple analysis of the conductivity mechanism is presented.     

A-site and B-site substitutions and the emission properties of Eu3+ ions in ABO3 –type cubic perovskite: A case study of BaZrO3

The emission properties of the rare earth (RE) elements have been found to be sensitive to the local lattice environment around them, and could be employed for probing the local lattice environment. Because each constituent ion of a material should have its own particular structural environment, the emission profiles in RE elements depend strongly on the doping sites of RE elements inside the host crystals. We investigated the emission properties of the Eu³⁺ ion doped BaZrO₃ (BaZrO₃:Eu) with doping site dependence (A-site vs. B-site), as well as ambient dependence in the post-annealing process. The site-selective doping was identified from the Rietveld refinement analysis on the XRD patterns of our BaZrO₃:Eu samples. Photoluminescence and photoluminescence excitation measurements showed that the emission properties of the samples with the Eu³⁺ ions substituted at Zr sites revealed much greater emission properties than those at the Ba sites. This behavior was found to accord with the change in intensity ratio of ⁵D₀ → ⁷F_0,2 to ⁵D₀ → ⁷F₁ in Eu ions, which should be a measure of the local lattice asymmetry around the Eu ions. We also found that with post-annealing in H₂ atmosphere, the emission intensities of the Eu ions increased significantly, while with post-annealing in O₂ atmosphere, they were suppressed. Our findings indicated that the cation/oxygen vacancies could change the local lattice environment around the Eu ions, as well as the valence states of Eu ions, depending on the doping site in the cubic perovskite.     

On the compensation of heterovalent ferric ions in the lattice of barium titanate single crystals

The introduction of heterovalent ferric ions into the titanium sites of the BaTiO₃-lattice of single crystals prepared by the fluoride process is due to the formation of oxygen vacancies and to the introduction of F-ions into the oxygen sites. Experimental results obtained by physical and chemical methods show the dependence of both mechanisms of compensation on the iron content of the crystals.     

Oxygen-phase-state changes in ZnS single crystals annealed in vapors of the constituents

Exciton reflection and emission spectra and edge emission have been investigated in ZnS sinle crystals grown from the melt and containing oxygen and then subjected to annealing in vapors of the constituents. The study of optical properties of the crystals cooled to 77°K were conducted in parallel with structural investigations of the crystals using proton and x-ray diffraction analyses. Based on the experimental data it was concluded that in the ZnS lattice, oxygen exists in a number of phase states: as part of a ZnS·O solid solution in the host lattice; as a precipitate from the saturated solid solutionβ=ZnS·O_sat; as an impurity atmosphere in the vicinity of packing faults; as ZnO precipitated on dislocations. The effect of oxygen in these various phase states on the exciton spectra and edge emission of ZnS was investigated. It was shown that oxygen is not very mobile in ZnS crystals annealed in sulfur vapor and it becomes concentrated mainly at packing defects. This leads to an increase in the concentration of packing defects and makes possible a transition from the cubic to the hexagonal modification of ZnS. The concentration of oxygen at packing defects leads to the appearance in reflection spectra and in the edge emission spectra ofα-ZnS of an additional hexagonal band located on the long wavelength side which is caused by the formation ofβ-ZnS·O solid solution. Oxygen diffuses quite rapidly through ZnS which has been annealed in zinc vapor and it precipitates from the crystals as the distinct phases ZnO orβ-ZnS · O_sat, and as a result the defect content of the hostα-ZnS lattice decreases. The concentration of the ZnO-phase is quite small and its exciton bands do not appear in the reflection spectra. The precipitation of the solid solution in the form of the phaseβ-ZnS · O_sat leads to the appearance of an additional long wavelength absorption edge in the 334 to 335 nm region (at 77°K). In addition, because single crystals of ZnS annealed in zinc vapor contain a large concentration of sulfur vacancies, there occurs a rather rapid formation of the solid solution on the layers ofα-ZnS close to the surface; this leads to a broadening and a shift toward longer wavelengths of the sphalerite exciton spectra. A similar shift is observed for the edge emission band ofα-ZnS. When the crystals are aged, theα-ZnS·O solid solution decomposes and the bands assume the standard sphalerite positions. Changes in the intensity of edge and exciton emission were investigated taking into account changes in the phase state of oxygen in the crystals.     

Ferromagnetism in defective yttria-stabilized zirconia

Significant research attention has been devoted to identifying and synthesizing new magnetic materials via doping of non-magnetic materials. The material defects offer an approach to stabilize ferromagnetism in non-magnetic materials such as oxygen-deficient HfO₂ and oxygen-deficient ZrO₂. In this study, we demonstrated room-temperature ferromagnetism via nitrogen ion implantation on yttria-stabilized zirconia (YSZ) single crystals. The results of structural and chemical analyses indicate the formation of a distinct surface layer through the implantation of nitrogen ions and potential oxygen vacancies. The lattice constant in this surface layer increased by 0.6% compared to the bulk value. Nitrogen ions were observed in this region, and their concentration was estimated to be 2.32 atoms per unit cell. In contrast to the lack of magnetic hysteresis in a YSZ single crystal, ferromagnetic hysteresis was observed in the ion-implanted YSZ crystals, owing to defects—nitrogen ions and oxygen vacancies in the surface layer.