The spin-glass state in Y2Co2/3Mo4/3O7 and Y2Fe2/3Mo4/3O7 complex oxides

The magnetic properties of Y₂ B _2/3Mo_4/3O₇ complex oxides (B = Co, Fe) were studied in the temperature range 2–300 K. At low temperatures, these compounds exhibit spin-glass properties with freezing temperatures T _f=26 and 33 K, respectively, and typical features in the magnetic hysteresis and in the dependences of the real part of the dynamic magnetic susceptibility on temperature and ac magnetic field frequency. Above T _f, the static magnetic susceptibility of the samples studied depends on the applied magnetic field, which is tentatively assigned to the presence of metallic cobalt and/or yttrium orthoferrite YFeO₃ introduced in the course of sample preparation. __________ Translated from Fizika Tverdogo Tela, Vol. 47, No. 12, 2005, pp. 2182–2188. Original Russian Text Copyright ? 2005 by Bazuev, Korolev.     

Phase stability in the LnCa2Mn2O7 (Ln=Pr, Nd, Sm and Gd) Ruddlesden-Popper series

The synthesis of the Ruddlesden-Popper series, LnCa₂Mn₂O₇, (Ln=Pr, Nd, Sm and Gd) is described and their structure and electronic properties investigated. The reduction in size of the A-site cation causes an increase in the distortion of their orthorhombic structures (space group Cmcm). All of these compounds form with a perovskite impurity, the amount of which increases on reduction of the cation size. The synthesis temperature also alters the amount of perovskite impurity in the phase, but only to a lower limit, implying the perovskite phase is intrinsic to the material and that a phase equilibrium exists between the layered Ruddlesden-Popper and perovskite phases, which is controlled by the cation size. The magnetic susceptibility show transitions characteristic of the perovskite phase, therefore little direct information can be obtained about the Ruddlesden-Popper phases, except that ferromagnetism is not observed in any of these materials.     

Ce3+在Ln2SO6中的发光(Ln=La,Gd或Y)

Ce3+在La2SO6中的发光光谱和激发光谱与在Gd2SO6和Y2SO6中的比较有显著差别。从被Ce3+敏化的中心的激发光谱上观察到在La基质中于300和330nm附近还有二个激发峰,显示出在这三个基质中Ce3+有很接近的激发态情况,从漫反射光谱也得到证实。不过在La2SO6中Ce3+的发光起源于次最低的而不是最低的5d能级。     

MBa2Cu3O7-δ( M=Y,Sm,Gd,Eu)高温超导体的远红外反射光谱

本文报道多晶MBa₂Cu₃O_7-δ(M=Y,Sm,Gd,Eu)高温超导体的远红外反射光谱,其频率和温度范围分别为40—360cm^-1和4.2—300K。对于不同M的样品,反射光谱具有相似的结构。在测量范围内,所有样品都有5个反射峰,最低频率的两个峰均属B_1a对称类,分别对应Ba,Cu,O离子团振动以及M,O离子团振动,其余3个峰来自CU—O键的弯曲振动;另外,不同M的样品的反射率曲线都具有三处反转 关键词：     

Ce3+和Tb3+, Eu3+在六方NaLnF4(Ln=La,Gd或Y)中的发光和能量传递

本文报道Ce3+掺杂和Ce3+—Tb3+、Ce3+—Eu3+共掺杂的六方NaLnF4(Ln=La,Gd或Y)发光体的研究结果:氟配位环境使Ce3+在300nm附近发射并有很低的猝灭浓度;阳离子缺陷发光中心可能形成于NaGdF4基质中并被Ce3+—Gd3+共同敏化;Ce3+的发光可以因Tb3+掺杂而增强,反过来Ce3+亦会使Tb3+的5D3/5D4发射强度比减小;Ce3+含量增加使Eu3+的5D2/5D1及5D2/5D0发射强度比减小,这与Ce3+的2F5/2→2F7/2跃迁和Eu3+的5D2→D1跃迁能级差匹配而产生共振能量传递有关。     

Magnetic properties of RE0.7Ca0.3Mn0.95Fe0.05O3 (RE=Sm and Gd) manganites at low temperature

The magnetic properties of RE_0.7Ca_0.3Mn_0.95Fe_0.05O₃ perovskite with rare-earth cations (RE=Sm and Gd) were investigated by means of X-ray diffraction, Mössbauer spectroscopy, and low temperature (4.2-266 K) magnetization measurements. Structural characterization of these compounds shows that they both have orthorhombic (Pbnm) structure. The Mössbauer spectra show clear evidence of local structural distortion of the Mn(Fe)O₆ octahedron, which is based on the non-zero nuclear quadrupole interactions for high-spin Fe³⁺ ions. It was found that the local structural distortion increases significantly when Sm³⁺ is replaced by Gd³⁺. This distortion is attributed to the Jahn-Teller coupling strength as estimated from the Mössbauer effect results. The magnetic results indicate that the Curie temperature decreases as a result of replacing Sm by Gd. This is due to the decrease of the average A-site cationic radius 〈r_A〉. The rapid increase of magnetization at low temperature indicates the magnetic ordering of rare earth ions at the A-site.     

VUV-UV excited luminescent properties of LnCa4O(BO3)3:RE (Ln=Y, La, Gd; Re=Eu, Tb, Dy, Ce)

Calcium lanthanide oxyborate doped with rare-earth ions LnCa₄O(BO₃)₃:RE³⁺ (LnCOB:RE, Ln=Y, La, Gd, RE=Eu, Tb, Dy, Ce) was synthesized by the method of solid-state reaction at high temperature. Their fluorescent spectra were measured from vacuum ultraviolet (VUV) to visible region at room temperature. Their excitation spectra all have a broadband center at about 188 nm, which is ascribed to host absorption. Using Dorenbos’ and Jφrgensen's work [P. Dorenbos, J. Lumin. 91 (2000) 91, R. Resfeld, C.K. Jφrgensen, Lasers and Excite States of Rare Earth [M], Springer, Berlin, 1977, p. 45], the position of the lowest 5d levels E(Ln,A) and charge transfer band E_ct were calculated and compared with their excitation spectra.Eu³⁺ and Tb³⁺ ions doped into LnCOB show efficient luminescence under VUV and UV irradiation. In this system, Ce³⁺ ions do not show efficient luminescence and quench the luminescence of Tb³⁺ ions when Tb³⁺ and Ce³⁺ ions are co-doped into LnCOB. GdCOB doped with Dy³⁺ shows yellowish white light under irradiation of 254 nm light for the reason that Gd³⁺ ions transfer the energy from itself to Dy³⁺. Because of the existence of Gd³⁺, the samples of GdCOB:RE³⁺ show higher excitation efficiency than LaCOB:RE³⁺ and YCOB:RE³⁺, around 188 nm, which indicates that the Gd³⁺ ions have an effect on the host absorption and can transfer the excitation energy to the luminescent center such as Tb³⁺, Dy³⁺ and Eu³⁺.     

Tb掺杂双层锰氧化物La_(4/3)Sr_(5/3)Mn_2O_7的磁熵变和电输运性质

研究了Tb掺杂对双层锰氧化物La_(4/3)Sr_(5/3)Mn_2O_7磁熵变和电输运性质的影响.样品采用传统固相反应法制备,两样品的名义组分可以表示为(La_(1-x)Tb_x)_(4/3)Sr_(5/3)Mn_2O_7(x=0,0.025),磁场为7 T时的最大磁熵变?S_M分别为-4.60 J/(kg·K)和-4.18 J/(kg·K).比较后发现,Tb元素的掺杂使得最大磁熵变值减小,但同时增大了相对制冷温区.电性测量结果表明,x=0.025的样品在高温区的导电机制可以用小极化子模型解释,与母体三维变程跳跃模型不同;当温度降低至三维长程铁磁有序温度(T_c~(3D))附近时,掺杂样品发生金属绝缘相变;掺杂后样品在T_c~(3D)附近,磁电阻取得极大值(约为56%),表明是本征磁电阻效应.     

Luminescent properties of SrAl2B2O7: Ce, Tb

By using metal nitrates as starting materials, SrAl₂B₂O₇: Tb³⁺ and SrAl₂B₂O₇: Ce³⁺, Tb³⁺ powder phosphors were prepared by sol-gel method. X-ray diffraction (XRD), photoluminescence excitation and emission, as well as kinetic decays were employed to characterize the resulting samples. The results show that energy transfers from Ce³⁺ to Tb³⁺ ions. The emission intensity of Tb³⁺ ions in SrAl₂B₂O₇ could be greatly intensified when Ce³⁺ ions are doped into SrAl₂B₂O₇: Tb³⁺. The decay times of SrAl₂B₂O₇: Tb³⁺ were prolonged when Ce³⁺ ions were doped. The doping of Ce³⁺ ions not only improved the luminescent intensity, but also made the materials gets stable luminescent properties.     

Luminescence properties of Ba2NaNb5O15 crystals activated with Sm, Eu, Tb or Dy ions

Single crystals of Ba₂NaNb₅O₁₅ (BNN) singly doped with Sm³⁺, Eu³⁺, Tb³⁺ or Dy³⁺ have been grown by means of the flux growth method. Their visible emission and excitation spectra and the decay profiles of the luminescence have been measured at room temperature. All spectral features are significantly inhomogeneously broadened in consequence of the structural disorder of the host and of the doping mechanisms. The analysis of the observed spectra allows formulating an hypothesis about the site occupancy of the active ions in the BNN lattice.     

Oxygen migration in A2B2O7 pyrochlores

Atomic scale computer simulation has been used to predict activation energies for oxygen migration. In total, 54 compounds with the A₂B₂O₇ pyrochlore structure were simulated. In each case, oxygen migration was assumed to proceed via an oxygen vacancy mechanism with oxygen ions hopping between 48f sites. For some compounds the unoccupied 8a interstitial position played an important role in the migration mechanism. The results were analyzed using a contour map of activation energy versus A cation radius along the ordinate and B cation radius along the abscissa. This identified areas of similar cation radii, which exhibit lower activation energy. Results compare favourably with available experimental data.     

Photoluminescence properties of Sr(Y, Gd)2O4:Euunder VUV excitation

Vacuum ultraviolet (VUV) excitation and photoluminescence (PL) properties of Sr(Y, Gd)₂O₄ doped with Eu³⁺ were studied. The excitation spectra of SrY_1.9Eu_0.1O₄ and SrY_1.0Gd_0.9Eu_0.1O₄ had absorption in the VUV region with the absorption band edge at 149 nm, while the absorption of SrGd_1.9Eu_0.1O₄ in the VUV region was weak, which could be due to the narrow host band gap and no efficient energy transfer occurred in the VUV region. The PL spectra of all samples exhibited the characteristic emission of Eu³⁺ with the red ⁵D₀-⁷F₂ transition (611 nm) being the most prominent group.     

Magnetic properties of CoFe1.9RE0.1O4 nanoparticles (RE=La,Ce, Nd,Sm, Eu,Gd, Tb,Ho) prepared in polyol

Highly crystalline CoFe_1.9RE_0.1O₄ ferrite nanoparticles, where RE=La, Ce, Nd, Sm, Eu, Gd, Tb, and Ho, have been synthesized by forced hydrolysis in polyol. X-ray diffraction (XRD), transmission electron microscopy (TEM), electron energy-loss spectroscopy (EELS), ⁵⁷Fe Mössbauer spectrometry, Co K-edge X-ray absorption spectroscopy and magnetic measurements using a SQUID magnetometer were employed to investigate the effect of the substitution RE³⁺ ions for Fe³⁺ ones on the structure, the microstructure, the chemical homogeneity, and the magnetic properties of the cobalt ferrite system. All the produced particles are superparamagnetic at room temperature. Nevertheless, the substitution causes reduction of the blocking temperature which is mainly ascribed to partial cation exchange among the spinel-like sublattices of CoFe₂O₄ induced by the insertion of the relatively large RE³⁺ ions. The low-temperature saturation magnetization and coercivity appear to be greatly affected by the nature of RE³⁺ ions—maxima values were found for Gd³⁺ and Eu³⁺, respectively.     

A new family of magnetoelectric materials: A2M4O9(A = Ta, Nb; M = Mn, Co)

The existence of the magnetoelectric (ME) effect in the transition metal niobates and tantalates A₂M₄O₉(A = Ta, Nb; M = Mn, Co) has been confirmed by the observation of the electrically induced magnetic moment in these materials. Both parallel and prependicular ME susceptibilities were measured as a function of temperature in powder specimens. The transition temperatures were found to be 110 ±1 (Nb₂Mn₄O₉), 103 ±1 (Ta₂Mn₄O₉), 27.0 ±0.5 (Nb₂Co₄O₉), and 20.6 ±0.5°K (Ta₂Co₄O₉) from the ME measurements.     

Luminescent properties of RE-activated CaAl2B2O7 (RE=Tb, Ce) in VUV-visible region

RE³⁺-activated α- and β-CaAl₂B₂O₇ (RE=Tb, Ce) were synthesized with the method of high-temperature solid-state reaction. Their VUV excitation and VUV-excited emission spectra are measured and discussed in the present article. The charge transfer band of Tb³⁺ and Ce³⁺ is respectively calculated to be at 151±2 and 159±3 nm. All the samples show an activator-independent excitation peak at about 175 nm and an emission peak at 350-360 nm ascribed to the host absorption and emission band, respectively.     

Synthesis and luminescent properties of nanoparticles LaSrAl3O7:Eu, Tb

Phosphors of nanoparticles LaSrAl₃O₇:RE³⁺(REEu, Tb) have been prepared by a sol–gel method. The structure and luminescent properties of LaSrAl₃O₇:Eu³⁺ and LaSrAl₃O₇:Tb³⁺ phosphors were characterized by X-ray diffraction and atomic force microscopy (AFM), photoluminescence excitation and emission spectra were utilized. From X-ray diffraction (XRD) patterns, it is indicated that the phosphor LaSrAl₃O₇ forms without impurity phase at 900 °C. From atomic force microscopy (AFM) images, it is shown that the crystal size of the phosphores are about 60–80 nm. Upon excitation with UV irradiation, it is shown that there is a strong emission at around 617 nm corresponding to the forced electric dipole ⁵D₀–⁷F₂ transition of Eu³⁺, and at around 545 nm corresponding to the ⁵D₄–⁷F₅ transition of Tb³⁺. The dependence of photoluminescence intensity on Eu³⁺(or Tb³⁺) concentration and annealing temperature were also studied in detail.     

钙钛矿锰氧化物(La1-xGdx)4/3Sr5/3Mn2O7 (x=0, 0.025) 磁性和输运性质研究

采用传统的高温固相烧结法制备了双层钙钛矿锰氧化物(La_1-xGd_x)_4/3Sr_5/3Mn₂ O₇ (x=0, 0.025)多晶样品. 通过X射线衍射仪研究发现样品为Sr₃Ti₂O₇型四方结构, 空间群为I4/mmm; 磁性测量表明, Gd³⁺掺杂后的样品(La_0.975Gd_0.025)_4/3Sr_5/3Mn₂O₇的三维磁有序转变温度(T_C1^3D)、磁化强度(M)均降低, 这是由于Gd³⁺的掺杂引起晶格的畸变, 从而使得晶格常数发生改变, 减弱了铁磁耦合而导致的; 通过电子自旋共振谱测量发现, 在T_C^3D<T<300 K温度范围内, 两样品在顺磁的基体上均有短程的铁磁团簇存在, 出现了相分离现象. 电性测量表明: 两样品分别在T_C1^3D (La_4/3Sr_5/3Mn₂O₇ 样品的三维磁有序转变温度, T_C0^3D)<T<300 K温度范围内均以三维变程跳跃的方式导电, 分析得出Gd³⁺的掺杂使得载流子局域长度的减小. 这表明载流子需要吸收更多的能量才能克服晶格的束缚进行跳跃, 因此(La_0.975Gd_0.025)_4/3Sr_5/3Mn₂ O₇ 样品的电阻较高.     

RE2Ti2O7(RE=Gd,Y,Ho,Er)的结构、机械性能及热学性质的第一性原理研究(英文)

本文利用第一性原理和准谐近似的方法研究了一系列钛酸盐烧绿石,即RE₂Ti₂O₇（RE=Gd,Y,Ho,Er）的结构、机械性能及热学性质。研究结果表明,在基态下RE₂Ti₂O₇具有良好的抗压、抗剪切能力。并且,由于这些化合物的齐纳指数接近于1,可近似地看作各向同性材料。此外,计算得到的热膨胀系数在高温区与实验值符合得较好。在500~1 500 K温度区间内,平均热膨胀系数为（10.4~13.1）×10-6 K-1。基于Slack模型,我们还计算了这些材料的晶格热导率,当温度等于1 000 K时,这四种物质的热导率在区间（1.5~4.9）W·m-1·K-1内。     

Magnetocaloric effect in R2Fe17 (R=Sm,Gd, Tb,Dy, Er)

A series of R₂Fe₁₇ (R=Sm, Gd, Tb, Dy, Er) have been synthesized. The magnetocaloric effect (MCE) of these compounds has been investigated by means of magnetic measurements in the vicinity of their Curie temperature. The Curie temperature of Er₂Fe₁₇ is 294 K. The maximum magnetic entropy change of Er₂Fe₁₇ under 5 T magnetic field is ∼3.68 J/kg K. In the R₂Fe₁₇ (R=Sm, Gd, Tb, Dy, Er) system, the maximum magnetic entropy change under 1.5 T magnetic field is 1.72, 0.89, 1.32, 1.59, 1.68 J/kg K corresponding to their Curie temperature (400, 472, 415, 364, 294 K), respectively.     

Line strength measurements of carbonyl sulfide (OCS) in the 2v3, v1+2v2+v3, and 4v2+v3 bands

To support planetary studies of the Venus atmosphere, we measured line strengths of the 2v₃, v₁+2v₂+v₃, and 4v₂+v₃ bands of the primary isotopologue of carbonyl sulfide (¹⁶O¹²C³²S), whose band centers are located at 4101.387, 3937.427, and 4141.212 cm⁻¹, respectively. For this, infrared absorption spectra in normal carbonyl sulfide (OCS) sample gas were recorded at an unapodized resolution of 0.0033 cm⁻¹ at ambient room temperatures using a Bruker Fourier transform spectrometer (FTS) at the Jet Propulsion Laboratory. The FTS instrumental line shape (ILS) function was investigated, which revealed no significant instrumental line broadening or distortions. Various custom-made short cells and a multi-pass White cell were employed to achieve optical densities sufficient to observe the strong 2v₃ and the weaker bands in the region. Gas sample impurities and the isotopic abundances were determined from mass spectrum analysis. Line strengths were retrieved spectrum by spectrum using a non-linear curve fitting algorithm adopting a standard Voigt line profile, from which Herman–Wallis factors were derived for the three bands. The band strengths of 2v₃, v₁+2v₂+v₃, and 4v₂+v₃ of ¹⁶O¹²C³²S (normalized at 100% of isotopologue) are observed to be 6.315(13)×10⁻¹⁹, 1.570(2)×10⁻²⁰, and 7.949(20)×10⁻²¹ cm⁻¹/molecule cm⁻², respectively, at 296 K. These results are compared with earlier measurements and the HITRAN 2004 database.