Phase stability and pressure dependence of defect formation in Gd2Ti2O7 and Gd2Zr2O7 pyrochlores

We report dramatically different behaviors between isostructural Gd2Ti2O7 and Gd2Zr2O7 pyrochlore at pressures up to 44 GPa, in which the substitution of Ti for Zr significantly increases structural stability. Upon release of pressure, the Gd2Ti2O7 becomes amorphous. In contrast, the high-pressure phase of Gd2Zr2O7 transforms to a disordered defect-fluorite structure. First-principle calculations for both compositions revealed that the response of pyrochlore to high pressure is controlled by the intrinsic energetics of defect formation.     

Dipolar interactions and origin of spin ice in ising pyrochlore magnets

Recent experiments suggest that the Ising pyrochlore magnets Ho2Ti2O7 and Dy2Ti2O7 display qualitative properties of the nearest-neighbor "spin ice" model. We discuss the dipolar energy scale present in both these materials and discuss how spin-ice behavior can occur despite the presence of long-range dipolar interactions. We present results of numerical simulations and a mean field analysis of Ising pyrochlore systems. Based on our quantitative theory, we suggest that the spin-ice behavior in these systems is due to long-range dipolar interactions, and that the nearest-neighbor exchange in Dy2Ti2O7 is antiferromagnetic.     

Evidence for gapped spin-wave excitations in the frustrated Gd2Sn2O7 pyrochlore antiferromagnet from low-temperature specific heat measurements

We have measured the low-temperature specific heat of the geometrically frustrated pyrochlore Heisenberg antiferromagnet Gd2Sn2O7 in zero magnetic field. The specific heat is found to drop exponentially below approximately 350 mK. This provides evidence for a gapped spin-wave spectrum due to an anisotropy resulting from single-ion effects and long-range dipolar interactions. The data are well fitted by linear spin-wave theory, ruling out unconventional low-energy magnetic excitations in this system, and allowing a determination of the pertinent exchange interactions in this material.     

Magnetic order in hybrid frustrated magnets Gd(2-x)Tb(x)Ti2O7 (x = 0.2 and 0.5)

We report on the specific heat, magnetization and ac susceptibility measurements of single crystals of hybrid frustrated magnets Gd(1.8)Tb(0.2)Ti(2)O(7) and Gd(1.5)Tb(0.5)Ti(2)O(7). The analysis of experimental data revealed that, although partial replacing of the Gd(3+) ions by the Tb(3+) ions in the Gd(2)Ti(2)O(7) host lattice slightly enhances antiferromagnetic coupling, as inferred from the evolution of the paramagnetic Curie-Weiss temperature, the ordering temperature gradually decreases. Paramagnetic correlations introduced by the Tb(3+) ions cause this perturbation, altering the effective further neighbor interactions and destabilizing the ground state in Gd(2)Ti(2)O(7). In addition, the low-energy states of Gd(2-x)Tb(x)Ti(2)O(7) are suggested to possess a nature different from those in parent members Tb(2)Ti(2)O(7) and Gd(2)Ti(2)O(7). Finally, the frequency-dependent magnetic susceptibility behavior in Gd(1.5)Tb(0.5)Ti(2)O(7) is consistent with the formation of a spin-glass-like state indicating a pronounced slowing down of the dynamical response of the studied hybrid magnets.     

Long-range order at low temperatures in dipolar spin ice

It has recently been suggested that long-range magnetic dipolar interactions are responsible for spin ice behavior in the Ising pyrochlore magnets Dy2Ti2O7 and Ho2Ti2O7. We report here numerical results on the low temperature properties of the dipolar spin ice model, obtained via a new loop algorithm which greatly improves the dynamics at low temperature. We recover the previously reported missing entropy in this model, and find a first order transition to a long-range ordered phase with zero total magnetization at very low temperature. We discuss the relevance of these results to Dy2Ti2O7 and Ho2Ti2O7.     

Field-induced transition on a triangular plane in the spin-ice compound Dy2Ti2O7

The origin of the lowest-temperature anomaly reported several years ago using a polycrystalline sample of the spin-ice compound Dy2Ti2O7 has remained unresolved. Here we finally clarify its origin by susceptibility measurements down to 65 mK using single crystals under accurate control of the magnetic fields in two independent directions. We demonstrate that the transition is induced under a subtle field combination that precisely cancels the nearest-neighbor spin interactions acting on the spins on the triangular lattice within the pyrochlore structure. Contrary to the other two field-induced transitions, this transition is driven only by the interactions beyond the nearest neighbors. Our observation thus provides the first qualitative evidence for the essential importance of the dipolar interaction beyond the nearest neighbors in the spin ice.     

X-ray photoelectron spectroscopy study of disordering in Gd2(Ti1-xZrx)2O7 pyrochlores

The dramatic increases in ionic conductivity in Gd2(Ti1-xZrx)2O7 solid solution are related to disordering on the cation and anion lattices. Disordering in Gd2(Ti1-xZrx)2O7 was characterized using x-ray photoelectron spectroscopy (XPS). As Zr substitutes for Ti in Gd2Ti2O7 to form Gd2(Ti1-xZrx)2O7 (0.25 < x < or =0.75), the corresponding O 1s XPS spectrum merges into a single symmetric peak. This confirms that the cation antisite disorder occurs simultaneously with anion disorder. Furthermore, the O 1s XPS spectrum of Gd2Zr2O7 experimentally suggests the formation of a split vacancy.     

Spin waves and quantum criticality in the frustrated XY pyrochlore antiferromagnet Er2Ti2O7

We report detailed measurements of the low temperature magnetic phase diagram of Er2Ti2O7. Heat capacity and time-of-flight neutron scattering studies of single crystals reveal unconventional low-energy states. Er3+ magnetic ions reside on a pyrochlore lattice in Er2Ti2O7, where local XY anisotropy and antiferromagnetic interactions give rise to a unique frustrated system. In zero field, the ground state exhibits coexisting short and long-range order, accompanied by soft collective spin excitations previously believed to be absent. The application of finite magnetic fields tunes the ground state continuously through a landscape of noncollinear phases, divided by a zero temperature phase transition at micro{0}H{c} approximately 1.5 T. The characteristic energy scale for spin fluctuations is seen to vanish at the critical point, as expected for a second order quantum phase transition driven by quantum fluctuations.     

Finite-temperature transitions in dipolar spin ice in a large magnetic field

We use Monte Carlo simulations to identify the mechanism that allows for phase transitions in dipolar spin ice to occur and survive for an applied magnetic field H much larger in strength than that of the spin-spin interactions. In the most generic and highest symmetry case, the spins on one out of four sublattices of the pyrochlore decouple from the total local exchange+dipolar+applied field. In the special case where H is aligned perfectly along the [110] crystallographic direction, spin chains perpendicular to H show a transition to q=X long-range order, which proceeds via a one- to three-dimensional crossover. We propose that these transitions are relevant to the origin of specific heat features observed in powder samples of the Dy2Ti2O7 spin ice material for H above 1 Tesla.     

Magnetic density of states at low energy in geometrically frustrated systems

Using muon-spin-relaxation measurements we show that the pyrochlore compound Gd(2)Ti(2)O(7), in its magnetically ordered phase below approximately 1 K, displays persistent spin dynamics down to temperatures as low as 20 mK. The characteristics of the induced muon relaxation can be accounted for by a scattering process involving two magnetic excitations, with a density of states characterized by an upturn at low energy and a small gap depending linearly on the temperature. We propose that such a density of states is a generic feature of geometrically frustrated magnetic materials.     

Nanoscale manipulation of pyrochlore: new nanocomposite ionic conductors

The ionic conductivity of isometric pyrochlore, ideally A2B2O (7), is extremely sensitive to disordering of A- and B-site cations and oxygen anion vacancies. We report the first use of ion beam irradiation-induced disordering in Gd 2Ti 2O (7) to produce a strain-free, buried, disordered defect-fluorite layer approximately 12 nm thick within an ordered pyrochlore matrix. This approach provides a new means of creating nanoscale, mixed ionic-electronic conductors in pyrochlore ceramics, such as those required for solid-state electrochemical cells.     

An57Fe Mössbauer study of rare-earth intermetallic compounds R(Fe11Ti)

⁵⁷Fe Mössbauer spectra are reported for the ThMn₁₂ structure series of intermetallic compounds R(Fe₁₁Ti) (R=Y, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Lu). The Mössbauer spectroscopy of oriented absorbers has been used to study the spin reorientation transitions exhibited by the members of the series where the second-order Stevens coefficient α_J of the rare-earth (Nd, Tb and Dy) is negative. A simple model has been established to deduce the canting angle from the Mössbauer spectra of oriented absorbers. The results are analyzed in terms of a crystal-field model. The crystal field parameters must be increased significantly to account for the observed large anisotropy in the Sm(Fe₁₁Ti) compound, which may find applications as a permanent magnet.     

Structural Fluctuations in the spin-liquid state of Tb2Ti2O7

High-resolution x-ray scattering measurements on single crystal Tb2Ti2O7 reveal finite structural correlations at low temperatures. This geometrically frustrated pyrochlore is known to exhibit a spin-liquid or cooperative paramagnetic state at temperatures below approximately 20 K. Parametric studies of structural Bragg peaks appropriate to the Fd3[over ]m space group of Tb2Ti2O7 reveal substantial broadening and peak intensity reduction in the temperature regime 20 K to 300 mK. We also observe a small, anomalous lattice expansion on cooling below a density maximum at approximately 18 K. These measurements are consistent with the development of fluctuations above a cooperative Jahn-Teller, cubic-tetragonal phase transition at very low temperatures.     

Anomalous nernst effects in pyrochlore molybdates with spin chirality

The transverse thermoelectric (Nernst) effect on pyrochlore molybdates is investigated experimentally. In Nd(2)Mo(2)O(7) and Sm(2)Mo(2)O(7) with the spin chirality, the Nernst signal, which mostly arises from the transverse heat current (or equivalently the transverse Peltier coefficient alpha(xy)), shows a low-temperature (20-30 K) positive extremum, whereas it is absent in (Gd(0.95)Ca(0.05))(2)Mo(2)O(7) with no single-spin anisotropy of the rare-earth ion and hence with no spin chirality. The correlation between the Hall conductivity sigma(xy) and alpha(xy) in Nd(2)Mo(2)O(7) also indicates the spin chirality plays a significant role in the spontaneous (anomalous) Nernst effect.     

Mott-Anderson transition controlled by a magnetic field in pyrochlore molybdate

The pyrochlore molybdate Gd2MO2O7 locates near the phase boundary between the ferromagnetic-metallic and the spin-glass insulating state. This metal-insulator transition is governed on a large energy scale by the electron-correlation effect, while the geometrical frustration causes the random potential. The magnetic field can tune the randomness of the potential and control, under a suitable pressure, the continuous Mott-Anderson transition precisely. The critical exponent (mu = 1.04 +/- 0.1) of the Mott-Anderson transition has been determined for this ferromagnetic orbital-degenerate electron system.     

Order-order and order-disorder transitions in the quantum spin-1 Ising-Heisenberg models

The critical properties of a quantum spin-1 ferromagnetic multidimensional Ising-Heisenberg model with uniaxial and single-ion anisotropy are examined in the framework of a mean-field approximation. A Landau free energy expansion is performed to identify critical lines and surfaces. The resulting phase diagram, defined in a three-dimensional space characterized by a single-ion anisotropy variable, a parameter measuring the interaction anisotropy and the temperature, is particularly interesting because it exhibits three different phases, one paramagnetic and two ferromagnetic; the latter two differing for the orientation of the dipolar ordering. The presence of both first order reorientation transitions (order-order transitions) and order-disorder transitions makes the present model promising for describing several physical systems.     

La4(P2O7)3：Ce,Gd,Tb磷光体的合成与光谱性质

本文首次采用溶液沉淀法合成了一系列La4(P2O7)3;Ce,Gd,Tb磷光体.经X射线分析表明,它们属于纯的La4(P2O7)3相。测定了这些化合物的激发和发射光谱、相对亮度及Ce3+的发光寿命,观察到在此基质中Ce3+与Gd3+的光谱重叠,它们之间存在着一定的相互作用,使(La0.64Ce0.3Gd0.064(P2O7)3的亮度比(La0.7Ce0.34(P2O7)3和(La0.94Gd0.064(P2O7)3有少许增加.此外,Ce3+能有效地敏化Tb3+9,从而大大增强Tb3+的发射.然而,Gd3+与Tb3+共存时存在着竞争吸收和独自发射,使(La0.80Gd0.06Tb0.144(P2O7)3的亮度与单掺的(La0.86Tb0.144(P2O7)3相比有少许降低.相应地在Ce,Gd和Tb共掺时,由于Gd3+的影响,使Tb3+的发射减弱,从而总的发光相对亮度有所降低。     

Sr2Bi4Ti5O18的压致结构相变

 使用4∶1的甲醇-乙醇混合液作传压介质，利用金刚石对顶砧装置（DAC），研究了层状铁电体Sr₂Bi₄Ti₅O₁₈的在位高压拉曼光谱和压致结构相变（0～27 GPa）。发现在8.31 GPa，Sr₂Bi₄Ti₅O₁₈经历了一次结构相交。在23.13 GPa以上，Sr₂Bi₄Ti₅O₁₈似乎出现了压致非晶相交的先兆。并使用内模方法对Sr₂Bi₄Ti₅O₁₈的内模进行了指认。