Phase transitions in BaCeO3: neutron diffraction and Raman studies

Polycrystalline samples and small single crystals of the perovskite BaCeO₃ were studied by neutron diffraction and Raman spectrometry between 300 and 1200 K. The controversy about the phase transitions originally deduced from our previous Raman study and those observed since by neutron diffraction by Knight has stimulated this work. Pretransitional effects which are detected by Raman much before long-range ordering takes place can partly explain the above disagreement. A continuous monitoring of the structural changes by neutron diffraction and by Raman spectroscopy including polarization analysis has allowed discussion of the transition mechanisms: The first transition Pnma–Imma takes place at 573 K and is of second order. Although some modes soften when the temperature is raised as in many of these perovskite compounds the transition is likely partly displacive partly order–disorder. The Raman modes which disappear transform in modes at the X point of the Brillouin zone of the Imma phase. The second transition Imma–R c takes place at 673 K and is first order. The last transition R c–Pm3m occurs above 1200 K and the transition temperature which can be deduced by extrapolation to zero Raman intensity is in good agreement with neutron results. This second order transition is progressive and begins at about 400 K, the intermediate R c structure appearing as an attempt for slowing down the structural evolution toward the cubic perovskite form.     

Low temperature reorientation of Fe spins in an irradiated hematite single crystal

Irradiation with alpha-particles of 29 and 50 MeV energies leads to essential changes in magnetic properties of hematite single crystals. When temperature decreases, the number of iron ions with high-temperature spin orientation decreases too but does not disappear completely, and at helium temperatures, in contrary, increases (the new transition). Appearance of the new transition is explained by superparamagnetic behaviour of the disordered zones produced by atom-atomic collision cascades. The splitting of the Müssbauer spectra in the temperature interval of the Morin transition as well as at the new transition undoubtedly shows that the both transitions are transitions of the first order.     

Pressure induced spin-reorientation transition in FeBO3

Abstract

It was found out by means of neutron diffraction that “easy plain - easy axis” spin-reorientation transition takes place in FeBO₃ under quasihydrostatic pressure of approximately 17 kbar at room temperature. This is a pressure analog of the Morin transition in hematite.     

Neutron diffraction evidence for the spin-reorientational transition in FeBO3 at high pressures

The spin-reorientational transition from the state with “easy-plane” anisotropy to the state with “easy-axis” anisotropy—a pressure analogue of the Morin temperature transition in hematite— was detected in iron borate at a pressure of P～17 kbar at room temperature by the neutron diffraction method.     

Influence of neutron and heavy-ion irradiation on EPR spectra of CuGeO3

The influence of neutron and heavy-ion irradiation on the electron paramagnetic resonance (EPR) spectra of the spin-Peierls compound CuGeO₃ has been investigated in the wide temperature range of 2–300 K. It is found that the neutron irradiation leads to a decrease of the spin-Peierls transition temperature and induces appreciable changes in the EPR signal intensity, resonance line width andg-factor of this material. These changes may be associated with a partial suppression of both the energy gap and dimerization within the Cu chains due to the irradiation-induced changes in the topological and chemical short-range order. In contrast to this, the heavy-ion irradiation induces only an increase in the intensity of the EPR signal and does not produce appreciable changes in the resonance line width,g-factor and spin-Peierls transition temperature. The experimental results show a large increase in the Curie-Weiss component and complete suppression of the spin-Peierls transition for higher irradiation doses.     

Mössbauer studies of the Morin transition interval of uniform hematite particles

In the vicinity of the Morin temperature Mossbauer spectra of uniform, non-uniform hematite particles and⁵⁷Fe enriched on the surface of the uniform ones were measured. It was established that the wider the distribution of the particle size the larger the temperature interval of the Morin transition, but the surface effect did not affect the interval. The reason of existence of the Morin transition interval was explained based on theoretical analysis.     

Neutron diffraction investigation of a metamagnetic transition in the Tb<Subscript>0.1</Subscript> Tm<Subscript>0.9</Subscript>Co<Subscript>2</Subscript> compound

The Tb_0.1Tm_0.9Co₂ compound is investigated using neutron diffraction. It is shown that this compound undergoes an irreversible band metamagnetic transition induced by an external magnetic field. The magnetization of the Co sublattice increases from 0.2 to 0.6 μ_B. The critical field strength is approximately equal to 1 T at temperatures of 1.8 and 4.0 K. As the temperature increases, the effect of the magnetic field on the magnetic state of the sample weakens and, at 25 K, no noticeable changes are observed in an external field of 0.75 T. The metamagnetic transition at 1.8 K is accompanied by the disappearance of rhombohedral distortions and brings about a lattice expansion by approximately 1%.     

Molecular dynamics in crystalline acetone studied by dielectric spectroscopy and neutron diffraction

Dielectric spectroscopy and neutron diffraction experiments in acetone have been performed in order to clarify the dynamical behavior and the structural changes associated to the unsolved thermal transition that takes place in the solid state around 130 K. The combination of dielectric experiments with neutron diffraction reveals the existence of a dielectric process in the stable crystalline phase of acetone. The evolution with temperature of the dielectric process, within the temperature range where the peak of the heat capacity was reported, supports that the transition is not of order–disorder type. The origin of the dielectric dispersion has been assigned to structural defects in the orthorhombic crystal phase of acetone.     

Effect of impurities on surface self-diffusion and surface structure

Measurements using field emission techniques of the activation energy for surface selfdiffusion of several of the refractory transition metals when carbon or silicon is present on the surface show large increases which are dependent on the degree of surface coverage. Maximum values obtained were: 8.5 eV for carbon on tungsten, 7.0 eV for silicon on tungsten, 4.9 eV for carbon on tantalum, 4.5 eV for carbon on molybdenum and 2.8 eV for silicon on molybdenum. In addition, two anomalous effects have been observed in which surface changes occur at critical temperatures, (a) Sharp discontinuities occur in the plots of activation energy versus temperature for carbon on tungsten at about 2300 °K and for silicon on tungsten at about 2000 °K. In both cases the activation energy drops from the respective high value to that for the clean substrate material of 3.0 eV. Concomitant with this transition the emission patterns change in appearance from those typical of a contaminated surface to those typical of a clean surface, (b) For carbon on tungsten and silicon on tungsten, (433) planes are observed which decrease in size with temperature and suddenly disappear at a very sharp critical temperature. It is suggested that the presence of these impurities causes a restructuring of the surface layers even when present in much less than stoichiometric amounts and that surface phase changes occur independent of bulk changes.     

Morin transition suppression in Polycrystalline 57Hematite (α-Fe2O3) exposed to 56Fe(II)

We used the isotope selectivity of ⁵⁷Fe Mössbauer spectroscopy to investigate changes in the magnetic properties of polycrystalline hematite exposed to ferrous iron (Fe(II)). We found that sorption of ⁵⁶Fe(II), followed by interfacial electron exchange, alters the bulk magnetic properties of ⁵⁷hematite. After reaction with ⁵⁶Fe(II), we observed partial suppression of the Morin transition of ⁵⁷hematite to below 13 K. This is significantly lower than the Morin temperature (T _M) of ～230 K measured for isotopically enriched polycrystalline ⁵⁷hematite, as well as the T _M of 264?±?2 K reported for normal polycrystalline hematite.     

Structure and proton conduction in CsDSO4

Caesium hydrogen sulphate is one of the most extensively studied superprotonic conductors with hydrogen bonds. A first order phase transition, from the low conductivity to the high conductivity phase, takes place at 414 K. The crystallographic structure of both phases has been established using high-resolution neutron powder diffraction. Quasielastic neutron scattering has provided information about the spatial and temporal characteristics of proton transport. In the present paper we report the results of reverse Monte Carlo modelling of neutron diffraction (total scattering) data which makes it possible to obtain the diffusion pathways for protons. The results are in good agreement with the qualitative model for proton transport proposed previously; in particular we show clearly that the proton motion is highly correlated with the rotation of the sulphate groups. In the low temperature phase we identify a weak correlation between protons and oxygens on the next-nearest-neighbour sulphate group which increases with temperature and probably drives the phase transition.     

Low‐temperature Raman spectroscopic studies in NaNbO3

Raman spectroscopic measurements were carried out in the temperature range 10–300 K to understand the low‐temperature antiferroelectric (AFE)–ferroelectric (FE) phase transition in NaNbO₃. Several modes in the low wavenumber range were found to disappear, while some new modes appeared across the transition. The temperature dependence of mode wavenumbers suggests that, during cooling, the AFE–FE phase transition begins to occur at 180 K, while the reverse transition starts at 260 K during heating. During cooling, the two phases were found to coexist in the temperature range of 220–160 K. Upon heating, the FE phase is retained up to 240 K and both FE and AFE phases coexist in the temperature range 240–300 K. In contrast to the earlier reports, the present results suggest a different coexistence region and the reverse transition temperature. The reported relaxor‐type FE behaviour over a broad temperature is consistent with the observed coexistence of phases during cooling and heating cycles. Copyright © 2010 John Wiley & Sons, Ltd.     

Surface effect on the Morin transition of α-Fe2O3 particles coated with surfactant

Uniform hematite particles with an average size of 400 Å were prepared for reducing the influence of the particle-size distribution on the measurement of the Morin temperature. A series of Mössbauer spectra at different temperatures have been recorded. The Morin transition occurs at 216 K for sample B coated with a surfactant-oleic acid, and it occurs at 192 K for uncoated sample A. The temperature intervals in the region of the spin flip are almost the same for both samples. These results show that aT _m shift could arise from surface effects such as spin pinning directly induced by a surfactant, and that the distortion produces restriction not only on the top few layers, but also on the whole volume of the particle.     

Behavior of the atomic and magnetic structure of La0.35Pr0.35Ca0.30MnO3 at a metal-insulator phase transition

The evolution of the structural and magnetic properties of the CMR (colossal-magnetoresistance) compound La_0.35Pr_0.35Ca_0.30MnO₃ as the temperature changes from 10 to 293 K is investigated by means of neutron diffraction. It is shown that the changes in the transport and magnetic properties are directly related with the rearrangement of the atomic structure. A phase transition to the metallic state occurs together with simultaneous ferromagnetic ordering of the manganese moments and is accompanied by a jump in volume. The static distortions of the oxygen octahedra which are observed to occur prior to the magnetic phase transition and which are practically absent at room temperature and in the FM phase attest to the orbital ordering of oxygen atoms on the bonds, with freezing-in of the Jahn-Teller modes. Pis’ma Zh. éksp. Teor. Fiz. 67, No. 9, 672–677 (10 May 1998)     

On the ground-state magnetic structure in Er2Ni2Pb

We have studied the unusual low-temperature magnetic phase of Er₂Ni₂Pb using powder neutron diffraction measurements in zero field down to 460 mK. Our previous neutron diffraction experiments down to 1.5 K showed that magnetic Bragg reflections seen in Er₂Ni₂Pb can be indexed by several propagation vectors that partially coexist. All the incommensurate propagation vectors seemed to disappear in the low temperature limit. The present study, however, shows that reflections belonging to the propagation vector q’ = (0.47 0 1/2) do not disappear but remain present down to 460 mK. This highly unexpected result suggests that the magnetic structure described by this propagation vector might not be a simple sine-wave modulation. One interesting possibility here is a spin-slip structure as the ground state.     

Biaxial strain in the hexagonal plane of MnAs thin films: the key to stabilize ferromagnetism to higher temperature

The alpha-beta magnetostructural phase transition in MnAs/GaAs(111) epilayers is investigated by elastic neutron scattering. The in-plane parameter of MnAs remains almost constant with temperature from 100 to 420 K, following the thermal evolution of the GaAs substrate. This induces a temperature dependent biaxial strain that is responsible for an alpha-beta phase coexistence and, more importantly, for the stabilization of the ferromagnetic alpha phase at a higher temperature than in the bulk. We explain the premature appearance of the beta phase at 275 K and the persistence of the ferromagnetic alpha phase up to 350 K with thermodynamical arguments based on the MnAs phase diagram. It results that the biaxial strain in the hexagonal plane is the key parameter to extend the ferromagnetic phase well over room temperature.     

Absence of relaxor-like ferroelectric phase transition in (Pb,Sr)TiO3 thin films

We have performed dielectric and micro-Raman spectroscopy measurements in the 298–673 K temperature range in polycrystalline Pb_0.50Sr_0.50TiO₃ thin films prepared by a soft chemical method. The phase transition have been investigated by dielectric measurements at various frequencies during the heating cycle. It was found that the temperature corresponding to the peak value of the dielectric constant is frequency-independent, indicating a non-relaxor ferroelectric behavior. However, the dielectric constant versus temperature curves associated with the ferroelectric to paraelectric phase transition showed a broad maximum peak at around 433 K. The observed behavior is explained in terms of a diffuse phase transition. The obtained Raman spectra indicate the presence of a local symmetry disorder, due to a higher strontium concentration in the host lattice. The monitoring of some modes, conducted in the Pb_0.50Sr_0.50TiO₃ thin films, showed that the ferroelectric tetragonal phase undergoes a transition to the paraelectric cubic phase at around 423 K. However, the Raman activity did not disappear, as would be expected from a transition to the cubic paraelectric phase. The strong Raman spectrum observed for this cubic phase is indicative that a diffuse-type phase transition is taking place. This behavior is attributed to distortions of the perovskite structure, allowing the persistence of low-symmetry phase features in cubic phase high above the transition temperature. This result is in contrast to the forbidden first-order Raman spectrum, which would be expected from a cubic paraelectric phase, such as the one observed at high temperature in pure PbTiO₃ perovskite. PACS 78.30.-j; 77.80.Bh; 64.70.Kb; 68.55.-a; 77.22.-a; 77.55.+f     

Proton momentum distribution in a protein hydration shell

The momentum distribution of protons in the hydration shell of a globular protein has been measured through deep inelastic neutron scattering at 180 and 290 K, below and above the crossover temperature Tc=1.23Tg, where Tg=219 K is the glass transition temperature. It is found that the mean kinetic energy of the water hydrogens shows no temperature dependence, but the measurements are accurate enough to indicate a sensible change of momentum distribution and effective potential felt by protons, compatible with the transition from a single to a double potential well. This could support the presence of tunneling effects even at room temperature, playing an important role in biological function.     

Defect concentration dependent phase transition in the organic quasi-one-dimensional conductor N-Propyl-Quinolinium (TCNQ)2

Anomalous changes in magnetic and electrical properties indicative of a phase transition at T_c ～ 220 K is found in the quasi one dimensional complex charge transfer salt N-propyl-quinolinium (TCNQ)₂. A series of samples with defects induced by neutron irradiation is investigated. The physical properties above 220 K are little affected by the radiation damage, however the temperature of the anomaly is shifted to lower temperatures. A dose which is estimated to damage of the order of 1 % of the molecules lowers T_c from 220 K to 150 K.     

Spectrum of vibrational frequencies of crystalline tungsten at temperatures of 293 and 2400 K

The slow neutron inelastic scattering spectra for a refractory (T _melt = 3680 K) Group VI transition metal of the Periodic Table, namely, tungsten, were measured for the first time in the range from room temperature to 2400 K. Measurements of the neutron scattering spectra of tungsten were performed on a DIN-2PI time-of-flight spectrometer installed at the IBR-2 reactor (Dubna, Russia). The sample was heated in a TS3000 K high-temperature thermostat. The spectrum of vibrational frequencies of the crystal lattice of tungsten at temperatures of 293 and 2400 K was determined from the measured neutron scattering spectra by the iterative method. A softening of the frequency spectrum of tungsten was observed with increasing temperature. This was explained by the increasing role of vibrational anharmonicity effects at high temperatures. The experimental results were compared with model calculations of the frequency spectrum of tungsten.