Structural changes of piezoelectric La3Ga5SiO14 induced by paramagnetic ions revealed by Ga multiple quantum magic angle spinning

Experimental evidence that nuclear magnetic resonance (NMR) can detect structural changes of piezoelectric La₃Ga₅SiO₁₄ induced by dilute paramagnetic ions is presented. Gd³⁺ and Eu³⁺ cations have been incorporated into La₃Ga₅SiO₁₄ monocrystals. As expected, the line-width of the tetrahedral ²⁹Si magic angle spinning (MAS) NMR spectra as well as the inverse of the T₂ relaxation time of ⁷¹Ga increases with the concentration of the paramagnetic ions. A surprising result is shown by ⁷¹Ga multiple quantum (MQ) MAS NMR spectrum, which changes with the concentration of paramagnetic ions. The changes in the ⁷¹Ga MQMAS spectra can be explained by a more ordonated distribution of Ga ions inside the oxygen tetrahedra. The ⁷¹Ga MQMAS NMR spectra allow identification of the one octahedral and two tetrahedral Ga sites.     

Luminescence of Cr ions associated with surpassing the green-emissive defect centers in β-Ga2O3

Photoluminescence of undoped and Cr³⁺-doped β-Ga₂O₃ was investigated. The transparent, undoped β-Ga₂O₃ film was successfully prepared by thermal conversion from GaOOH. The film exhibited predominant green luminescence in response to ultraviolet light excitation at 250 nm. This luminescence behavior, which was proposed to result from the oxygen defect centers, was used in examining excitation and emission mechanisms for Cr³⁺ ions doped in β-Ga₂O₃. It was found that red luminescence of Cr³⁺ surpasses green luminescence of the host lattice, as evidenced by the dependence of the spectral structure on the Cr³⁺ concentration. The excitation of Cr³⁺ was then suggested to be caused by the energy transfer from Ga³⁺O₆ octahedra present in the monoclinic β-Ga₂O₃ lattice.     

Multinuclear MAS NMR Investigation of Sol-Gel and Ball-Milled Nanocrystalline Ga<Subscript>2</Subscript>O<Subscript>3</Subscript>

⁷¹Ga magic-angle spinning (MAS) nuclear magnetic resonance (NMR) has been used to characterize the structural evolution of nanocrystalline Ga₂O₃ samples prepared by sol-gel and ball-milling techniques. ²⁹Si and ²⁷Al MAS NMR have also been used to characterize silica and alumina Zener pinning phases. ⁷¹Ga NMR parameters are reported for the α- and β-Ga₂O₃ phases, and more tentatively for the δ-Ga₂O₃ phase. By simulating the octahedrally coordinated gallium NMR line of β-Ga₂O₃ using Gaussian distributions in χ_Q, the extent of disorder in the Ga₂O₃ crystallites has been quantified. The ball-milled samples contain much more inherent disorder than the sol-gel samples in the nano-phase, which was observed from simulations of the ⁷¹Ga MAS NMR spectra. The silica pinning phase produced highly crystalline and densely aggregated nanocrystalline Ga₂O₃, as well as the smallest nanocrystal sizes. Authors' address: Mark E. Smith, Department of Physics, University of Warwick, Coventry CV4 7AL, UK     

Nuclear resonance measurements of CePd2Ga3

CePd₂Ga₃, a Kondo lattice exhibiting ferromagnetic order below T _C = 6.3 K, has been studied using Ga NMR technique. Measurements of the magnetic susceptibility on an oriented sample proved the strong anisotropy of this quantity, whose major component is in the basal plane. From the analysis of NMR spectra of differently oriented samples, the quadrupole parameters and the temperature-dependent anisotropic Knight-shift have been determined. While the anisotropy of the susceptibility can sufficiently account for the axial anisotropy of the ⁷¹Ga Knight shift, the in-plane anisotropy of the shift points towards dipolar effects enhanced by hybridization of the Ce-4f and Ga-s electrons.     

Spectral characterization and energy levels of Cr:Sc2(MoO4)3 crystal

This paper reports the spectral properties and energy levels of Cr³⁺:Sc₂(MoO₄)₃ crystal. The crystal field strength Dq, Racah parameter B and C were calculated to be 1408 cm⁻¹, 608 cm⁻¹ and 3054 cm⁻¹, respectively. The absorption cross sections σ_α of ⁴A₂→⁴T₁ and ⁴A₂→⁴T₂ transitions were 3.74×10⁻¹⁹ cm² at 499 nm and 3.21×10⁻¹⁹ cm² at 710 nm, respectively. The emission cross section σ_e was 375×10⁻²⁰ cm² at 880 nm. Cr³⁺:Sc₂(MoO₄)₃ crystal has a broad emission band with a broad FWHM of 176 nm (2179 cm⁻¹). Therefore, Cr³⁺:Sc₂(MoO₄)₃ crystal may be regarded as a potential tunable laser gain medium.     

Ga2O3组分对Tm3+掺杂GeO2-Ga2O3-Li2O-BaO-La2O3玻璃的光谱性能影响

制备了Tm³⁺(8.0mol%)掺杂(77-x)GeO₂-xGa₂O₃-8Li₂O-10BaO-5La₂O₃(x=4,8,12,16)系列玻璃.系统地研究了Ga₂O₃从4mol%变化到16mol%时,玻璃的光谱性质与热学性质的变化规律.差热分析表明,随着Ga₂O₃含量的增加,锗酸盐玻璃的热稳定性增加.运用Judd-Ofelt(J_O)理论计算得到了Tm³⁺在不同Ga₂O₃含量的GeO₂-Ga₂O₃-Li₂O-BaO-La₂O₃玻璃中的J-O强度参数(Ω₂,Ω₄,Ω₆)及Tm³⁺各激发能级的自发跃迁概率、荧光分支比以及辐射寿命等光谱参量.在808nm激光二极管的激发下,测试并分析了Ga₂O₃对Tm³⁺荧光光谱特性的影响.随着Ga₂O₃从4mol%增加到16mol%,Tm³⁺在1.8μm处的荧光强度呈现先减弱后增强的特性.当Ga₂O₃含量大约在12mol%时,Tm³⁺在1.8μm处的荧光强度最弱,受激发射截面达到最小.还初步讨论了Ga₂O₃对玻璃结构与光谱参数的影响规律. 关键词： 3+掺杂锗酸盐玻璃')" href="#">Tm³⁺掺杂锗酸盐玻璃 光谱性能 Judd-Ofelt参数 热稳定性     

Third-order nonlinear optical properties of GeSe2-Ga2Se3-PbI2 glasses

The third-order nonlinear optical (NLO) properties of new selenium-based GeSe₂-Ga₂Se₃-PbI₂ glasses have been measured using the optical Kerr effect (OKE) technique, with picosecond and femtosecond laser pulses. The 0.70GeSe₂-0.15Ga₂Se₃-0.15PbI₂ glass has the largest third-order optical nonlinear susceptibility in GeSe₂-Ga₂Se₃-PbI₂ glass system with χ⁽³⁾ of 5.28×10¹² esu. In addition, the response time of glasses is sub-picosecond, which is predominantly associated with electron cloud. Local structure of the glasses has been identified by using Raman studies, while the origins of the observed nonlinear optical response are discussed. The [Ge(Ga)Se₄] tetrahedral and lone-pair electrons from highly polarizable Pb atom in glasses play an important role in enhanced NLO response. These results as well as their good chemical stability indicate that GeSe₂-Ga₂Se₃-PbI₂ glasses are promising materials for photonic applications of third-order nonlinear optical signal processing.     

Long-lasting afterglow in Tb-doped SiO2-Ga2O3-CaO-Na2O glasses and its sensitization by Yb

Long-lasting afterglow due to Tb³⁺ ions has been observed in a Tb³⁺-doped SiO₂-Ga₂O₃-CaO-Na₂O glass, where a 4s empty orbital of Ga³⁺ probably works as an electron-trapping center. The sensitization effect of Yb³⁺ on the afterglow has been noticed.     

Novel nanostructures of β-Ga2O3 synthesized by thermal evaporation

In this study, we report the novel β-Ga₂O₃ nanostructures synthesized by the thermal evaporation of Ga droplet in the presence of Au catalysts at 900 °C. The morphology and structure of the products were analyzed by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray diffraction (XRD). The single-crystalline β-Ga₂O₃ nanosheets have lateral dimensions up to several tens of microns. Large arrays of column-like layered crystal β-Ga₂O₃ structures that consisted of many nanosheets were formed on the Au-coated silicon substrate under the suitable vapor concentration. These novel β-Ga₂O₃ nanostructures are expected to have potential application in functional nanodevices.     

Synthesis of Cr2O3/TNTs nanocomposite and its photocatalytic hydrogen generation under visible light irradiation

A novel Cr₂O₃/TNTs nanocomposite was prepared by loaded suitable amount of amorphous Cr₂O₃ on titanate nanotubes (TNTs) via hydrothermal reaction and impregnation process. XRD, SEM and TEM results demonstrated that the amorphous Cr₂O₃ nanoparticles were homogeneously dispersed on the surface of TNTs. The diffuse reflectance UV–visible absorption spectra exhibited that the spectral response of TNTs was extended to visible light region by coupled with Cr₂O₃. The 2.5Cr₂O₃/TNTs nanocomposite showed the highest activity of hydrogen generation by photocatalytic water-splitting under visible light irradiation (λ > 400 nm). The high activity of H₂ evolution for Cr₂O₃/TNTs nanocomposites was associated with the donor level in the forbidden band of TNTs semiconductor provided by dopant Cr³⁺ and a probably photocatalytic mechanism was proposed.     

Sonochemical synthesis of supersaturated Ga–Al liquid-alloy fine particles and Al3+-doped γ-Ga2O3 nanoparticles by direct oxidation at near room temperature

In this study, we investigated the fabrication of supersaturated gallium (Ga)–aluminum (Al) liquid alloy and Al³⁺-doped γ-Ga₂O₃ nanoparticles (NPs) at near room temperature (60 °C) using sonochemical and sonophysical effects. Supersaturated Ga–Al liquid alloy microparticles (D_av = 1.72 µm) were formed and stabilized at 60 °C by the thermal nonequilibrium field provided by sonochemical hot spots. Compared with liquid Ga, supersaturated Ga–Al liquid alloy was rapidly oxidized to a uniform oxide without Al₂O₃ or Al deposition. Thus, ultrafine Al³⁺-doped γ-Ga₂O₃ NPs were obtained after only 1 h of ultrasonic irradiation at 60 °C. The oxidation of liquid Ga was remarkably accelerated by alloying with metallic Al and ultrasonic irradiation, and the time was shortened. The average diameter and surface area of the γ-Ga₂O₃-based NPs were 59 nm and 181 m²/g, respectively. Compared with γ-Ga₂O₃, the optical bandgap of the Al³⁺-doped γ-Ga₂O₃ NPs was broadened, and the thermal stability improved, indicating Al³⁺-doping into the γ-Ga₂O₃ lattice. However, the lattice constant of γ-Ga₂O₃ was almost unchanged with or without Al³⁺-doping. Al³⁺ was introduced into the defect sites of Ga³⁺, which were massively induced in the defective spinel structure during ultrasonic processing. Therefore, sonochemical processing, which provides nonequilibrium reaction fields, is suitable for the synthesis of supersaturated and metastable materials in metals and ceramics fields.     

Investigation of spectroscopic properties and thermal stability of Er/Yb-co-doped Bi2O3-B2O3-Ga2O3 glasses

A series of Er³⁺/Yb³⁺-co-doped 60Bi₂O₃-(40−x) B₂O₃ -xGa₂O₃ (BBGA x=0, 4, 8, 12, 16 mol%) glasses have been prepared. The absorption spectra, emission spectra, fluorescence lifetime of Er³⁺:⁴I_13/2 level and thermal stability were measured and investigated. Three Judd-Ofelt intensity parameters Ω_t (t=2,4,6) (Ω₂=(4.67-5.93)×10⁻²⁰ cm², Ω₄=(1.50-1.81)×10⁻²⁰ cm², Ω₆=(0.92-1.17)×10⁻²⁰ cm²) of Er³⁺ ions were calculated by Judd-Ofelt theory. It is found that the Ω₆ first increases with the increase of Ga₂O₃ content from 0 to 8 mol% and then decreases, which is mainly affected by the number of non-bridging oxygen ions of the glass network. The high peak of stimulated emission cross-section () of Er³⁺: ⁴I_13/2→⁴I_15/2 transition were obtained according to McCumber theory and broad full width at half maximum (FWHM=69-76 nm) of the ⁴I_13/2→⁴I_15/2 transition of Er³⁺ ions were measured. The results indicate that these new BBGA glasses can be used as a candidate host material for potential broadband optical amplifiers.     

Novel RCo5Ga7 intermetallic compound

The novel RCo₅Ga₇ (R=Y, Tb, Dy, Ho and Er) intermetallic compounds have been synthesized, and their crystallographic and magnetic properties have been studied using X-ray diffraction and magnetic measurement. RCo₅Ga₇ crystallizes in an orthorhombic structure with ScFe₆Ga₆ type. The space group is Immm, and Z=2. According to the structural refinement result, the 2a, 4e, 4f, 4g, 4h, and 8k crystal positions are occupied by 2R, 4Ga^I, 4(Ga^II, Co^I), 4Ga^III, 4(Ga^IV,Co^II), and 8(Co^III,Ga^V), respectively. The RCo₅Ga₇ intermetallic compound can be stabilized in the range of the radius ratio of R_Re/R_(Co,Ga)<1.36. The RCo₅Ga₇ compound exhibits a paramagnetic behavior. The magnetization at 5 K ranges from 28.93 to 40.62 emu/g.     

The optical properties and laser characteristics of Cr and Nd co-doped Y3Al5O12 ceramics

We have fabricated Cr³⁺ and Nd³⁺ co-doped YAG (Cr;Nd:YAG) ceramics, and investigated their optical properties and laser characteristics. The Cr;Nd:YAG has two broad absorption bands at around 440 nm (⁴A₂→⁴T₁) and 600 nm (⁴A₂→⁴T₂) respectively, caused by Cr³⁺ ions. In the case of pumping at 440 nm, the maximum effective lifetime of the Cr;Nd:YAG was 737 μs with a 0.1 at% Cr³⁺ and 1.0 at% Nd³⁺ co-doped YAG sample. Cr³⁺ ions take a role of an effective sensitizer to convert the UV light of flashlamp. For single-shot laser operation, a 10.4 J output energy at 1064 nm was obtained with 0.1 at% Cr³⁺ and 1.0 at% Nd³⁺ co-doped YAG ceramic rod with a laser efficiency of 4.9%. The laser efficiency was found to be more than twice that of a 1.0 at % Nd³⁺:YAG ceramic rod.     

Analysis of the nuclear quadrupole interaction of Disulfur Dichloride, S2Cl2

Pure rotational spectra of S₂³⁵Cl₂ and S₂³⁵Cl³⁷Cl have been observed using a Fourier-transform microwave spectrometer. An analysis of the hyperfine structure made by considering the nuclear spin statistics showed that S₂Cl₂ has C₂symmetry, where the hyperfine splittings due to the two Cl nuclei were analyzed precisely. The nuclear quadrupole coupling constants including the off-diagonal (χ_ab, χ_ac, χ_bc) components and the nuclear spin–rotation interaction constants associated with the two Cl nuclei have been determined for the first time. We have shown that the nuclear quadrupole interaction plays an important role in the ortho–para mixing.     

Structural investigations of GeS2-Ga2S3-CdS chalcogenide glasses using Raman spectroscopy

Raman investigations were carried out for various compositions of chalcogenide glasses in the GeS₂-Ga₂S₃-CdS system. Addition of Ga₂S₃ into GeS₂ results in the formation of metal-metal bonds and edge-shared GaS_4/2 tetrahedra. Ge²⁺ ions may surround [GaS_4/2]¹⁻ tetrahedra acting as charge compensators. Upon the addition of CdS into the GeS₂-Ga₂S₃ system, the number of the metal-metal bonds and edge-shared GaS_4/2 tetrahedra decreases, resulting in the formation of corner-shared tetrahedra with non-bridging sulfurs (NBS). Cd²⁺ ions can be dissolved into the glass network as charge compensators for these NBS and exited few [GaS_4/2]¹⁻ tetrahedra. The high solubility of CdS is ascribed to the dissociation of metal-metal bonds and edge-shared tetrahedra in these Ga-containing glasses.     

Investigation of the Mn-doped compound CuGaTe<Subscript>2</Subscript> by <Superscript>63</Superscript>Cu AND <Superscript>69</Superscript>Ga nuclear magnetic resonance techniques

The synthesized base compound CuGaTe₂ and the Mn-doped compounds Cu_0.97Ga_0.97Mn_0.06Te₂ and Cu_0.93Ga_0.93Mn_0.14Te₂ have been investigated by using ⁶³Cu and ⁶⁹Ga NMR spectroscopy. The NMR spectra obtained testify to substantial structural distortions near the cationic positions in the crystal lattice of Mndoped samples. The constants of quadrupole coupling between ⁶³Cu and ⁶⁹Ga nuclei in the compounds investigated have been estimated.     

Raman scattering studies of the GeS2-Ga2S3-CsCl glassy system

Room temperature Raman spectra of samples on four serials within GeS₂-Ga₂S₃-CsCl glassy system have been investigated systematically. Based on the analysis of the local coordination surroundings of Cs⁺ ions, the similarities and changes of Raman spectra for glass Ga₂S₃-2CsCl and bridged molecular GaCl₃ were explained successfully. With a profound consideration of the effect of Cs⁺ ions on mixed anion units (GaS_4−xCl_x) and bridged units (Ga₂S_6−xCl_x) and the corresponding micro-structural model, the Raman spectral evolution of the samples within GeS₂-Ga₂S₃-CsCl glassy system was reasonably elucidated.     

Oxygen nonstoichiometry of Sr(Co,Fe)O3−δ-based perovskites: I. Coulometric titration of SrCo0.85Fe0.10Cr0.05O3−δ by the two-electrode technique

The p(O₂)–T–δ diagram of perovskite-type SrCo_0.85Fe_0.10Cr_0.05O_3−δ was determined by the coulometric titration technique in the temperature range 770–1250 K at oxygen partial pressures from 8 10⁻¹⁰ to 0.5 atm. Stability of the cubic perovskite phase of SrCo_0.85Fe_0.10Cr_0.05O_3−δ, existing down to the oxygen pressures of 10⁻³–10⁻⁵ atm, was found to be slightly higher than that of SrCo_0.80Fe_0.20O_3−δ, probably due to stabilization of oxygen octahedra neighboring Cr⁴⁺ cations. When the oxygen nonstoichiometry of the Cr-containing perovskite decreases from 0.47 to 0.38, the partial molar enthalpy and entropy for overall oxygen incorporation reaction vary in the ranges −165 to −60 kJ mol⁻¹ and 90 to 150 J mol⁻¹ K⁻¹, respectively. Within the stability limits of the single perovskite phase, the p(O₂)–T–δ diagram can be adequately described by equilibrium processes of oxygen incorporation, cobalt disproportionation and interaction of cobalt and iron cations, with the thermodynamic functions independent of defect concentrations. Increasing grain size in SrCo_0.85Fe_0.10Cr_0.05O_3−δ ceramics from submicron size to 100–200 μm has no effect on the oxygen thermodynamics. The two-electrode coulometric titration technique, based on the alternate use of electrodes for oxygen pumping and e.m.f. measurements, is described and verified by studying oxygen nonstoichiometry of La_0.3Sr_0.7CoO_3−δ and PrO_x.     

Growth of β-gallium oxide nanostructures by the thermal annealing of compacted gallium nitride powder

Various β-gallium oxide (β-Ga₂O₃) nanostructures such as nanowire, nanobelt, nanosheet, and nanocolumn were synthesized by the thermal annealing of compacted gallium nitride (GaN) powder in flowing nitrogen. We suggest that Ga₂O₃ vapor might be formed by the reaction of oxygen with the gaseous Ga formed by GaN decomposition. The Ga₂O₃ vapor diffuses into voids derived by compacting GaN powder and is supersaturated there, resulting in the growth of Ga₂O₃ nanostructures via the vapor–solid (VS) mechanism. Ga₂O₃ plate-like hillocks and nanostructures were also grown on the surface of a c-plane sapphire placed on the GaN pellet.