Inelastic neutron scattering and lattice dynamics studies in complex solids

At Trombay, lattice dynamics studies employing coherent inelastic neutron scattering (INS) experiments have been carried out at the two research reactors, CIRUS and Dhruva. While the early work at CIRUS involved many elemental solids and ionic molecular solids, recent experiments at Dhruva have focussed on certain superconductors (cuprates and intermetallics), geophysically important minerals (Al₂SiO₅, ZrSiO₄, MnCO₃) and layered halides (BaFCl, ZnCl₂). In most of the studies, theoretical modelling of lattice dynamics has played a significant role in the interpretation and analysis of the results from experiments. This talk summarises the developments and current activities in the field of inelastic neutron scattering and lattice dynamics at Trombay.     

Inelastic neutron scattering from and lattice dynamics of α-KNO3

Coherent inelastic neutron scattering techniques are employed to measure several branches of the phoon dispersion relation in KNO₃ in its orthorhombic (α-phase or phase II) form at room temperature. Group theoretical selection rules for external modes of the crystal have been used in the measurements along the three symmetry directions Σ(ξ00), Δ(0ξ0) and Λ(00ξ). Theoretical investigation of the lattice dynamics of the crystal is carried out on the basis of a rigid molecular-ion model using the external mode formalism. A two-body potential consisting of the Coulombic interaction and the Born-Mayer type short range interaction is assumed. The effective charges and radii of different atoms are determined by applying the stability criterion for the crystal. Dispersion curves are calculated, representation by representation, making use of group theoretical information. Comparison of theoretical results with experimental information on elastic constants, optical data and neutron results are made. Agreement between theoretical and the various experimental results may be considered very satisfactory.     

Inelastic neutron scattering study of lattice dynamics in α-ZnCl<Subscript>2</Subscript>

Inelastic neutron scattering experiments have been carried out to measure the phonon density of states in polycrystalline α-ZnCl₂ at Dhruva, Trombay. Lattice dynamical calculations, based on an interatomic potential model, are accomplished to study phonons associated with this otherwise extremely hygroscopic compound. Our calculated data are found to be well-compatible with the available measured ones.     

Inelastic neutron scattering and lattice dynamics of GaPO<Subscript>4</Subscript>

We report here measurements of phonon spectrum and lattice dynamical calculations for GaPO₄. The measurements in low-cristobalite phase of GaPO₄ are carried out using high-resolution medium-energy chopper spectrometer at ANL, USA in the energy transfer range 0–160 meV. Semiempirical interatomic potential in GaPO₄, previously determined using ab-initio calculations have been widely used in studying the phase transitions among various polymorphs. The calculated phonon spectrum using the available potential show fair agreement with the experimental data. However, the agreement between the two is improved by including the polarisability of the oxygen atoms in the framework of the shell model. The lattice dynamical models are also exploited for calculations of various thermodynamic properties of GaPO₄.     

Inelastic neutron scattering and lattice dynamics of ZrO2, Y2O3 and ThSiO4

Zirconia (ZrO₂), yttria (Y₂O₃) and thorite (ThSiO₄) are ceramic materials used for a wide range of industrial applications. The dynamical properties of these materials are of interest as they exhibit numerous interesting phase transitions at high temperature and pressure. Using a combination of inelastic neutron scattering and theoretical lattice dynamics we have studied the phonon spectra and thermodynamic properties of these compounds. The experimental data validate the theoretical model, while the model enables microscopic interpretations of the observed data. The calculated thermodynamic properties are in good agreement with the experimental data.      

Inelastic neutron scattering and lattice dynamics of minerals

We review current research on minerals using inelastic neutron scattering and lattice dynamics calculations. Inelastic neutron scattering studies in combination with first principles and atomistic calculations provide a detailed understanding of the phonon dispersion relations, density of states and their manifestations in various thermodynamic properties. The role of theoretical lattice dynamics calculations in the planning, interpretation and analysis of neutron experiments are discussed. These studies provide important insights in understanding various anomalous behaviour including pressure-induced amorphization, phonon and elastic instabilities, prediction of novel high pressure phase transitions, high pressure-temperature melting, etc.      

Inelastic neutron scattering in Zr<Subscript>2</Subscript>NiH<Subscript>1.9</Subscript> and Zr<Subscript>2</Subscript>NiH<Subscript>4.6</Subscript>

In this paper we report the results obtained from inelastic neutron scattering measurements on Zr₂NiH_1.9 and Zr₂NiH_4.6 using triple-axis spectrometer at Dhruva reactor, Trombay. The spectrum up to 35 meV represents largely the lattice modes of Zr and Ni atoms. The vibrational frequencies of hydrogen atoms are expected predominantly at higher energies. The phonon spectra from 35–180 meV were recorded using a Be filter as analyser. In order to analyse the observed neutron spectra, we assume a set of Ein-stein modes due to the hydrogen atoms which are delta functions in energy. These delta functions are broadened by the resolution of the instrument. The vibrational frequencies obtained from the fitting of the observed phonon spectra have been assigned to various tetrahedral sites in both the compounds.     

Preparation of TiO<Subscript>2</Subscript>-coated LiCo<Subscript>1/3</Subscript>Ni<Subscript>1/3</Subscript>Mn<Subscript>1/3</Subscript>O<Subscript>2</Subscript> by electrostatic self-assembly method and its properties

A precursor of TiO₂–LiCo_1/3Ni_1/3Mn_1/3O₂ was prepared by electrostatic self-assembly method. The final product was obtained by heating the precursor at 400–450 °C for 4–6 h in air. X-ray diffraction (XRD), scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), and electrochemical tests were used to examine the structural, morphology, elementary valence, and electrochemical characteristics. XRD indicated that the TiO₂-coated material can be indexed by α-NaFeO₂ layered structure, which belongs to hexagonal-type space group R3m. XPS results confirmed the existence of TiO₂ compound on the surface of the coated sample. The SEM image showed that the material had spherically porous morphology with the uniform size about 6 μm. The initial charge–discharge capacity of the TiO₂-coated LiCo_1/3Ni_1/3Mn_1/3O₂ material was 168.8/160.0 mAh/g. After 60 cycles, the discharge capacity of the TiO₂-coated LiCo_1/3Ni_1/3Mn_1/3O₂ sample was 147.0 mAh/g, and the coulombic efficiency was 94.0%. Compared with the uncoated sample, the electrochemical performance of TiO₂-coated LiCo_1/3Ni_1/3Mn_1/3O₂ was improved.     

Effects of sintering on microstructure and dielectric response in YCrO<Subscript>3</Subscript> nanoceramic

Effects of sintering on pore morphology and dielectric response have been investigated. Pore structure has been probed by small angle neutron scattering (SANS). It has been observed that the size distribution becomes less polydisperse with a slight modification in the distribution as sintering temperature is increased. Dielectric response in the frequency range 0.02–1000 kHz is significantly altered by modification of pore structure because of sintering. A transition from non-Debye type to near-Debye type response has been observed as the sintering temperature is increased.      

Lattice dynamics of cubic PbTiO3 by inelastic neutron scattering

High-temperature dispersion relations of the phonon modes in a cubic PbTiO₃ single crystal have been investigated along the [ξ 0 0] and [ξ ξ 0] directions by inelastic neutron scattering. Above T _c, the phonon dispersions are only temperature-dependent close to the Brillouin zone centre where the mode softening comes through. The measurements indicate large cubic anisotropy of the elastic tensor and relatively low anisotropy of the soft mode dispersion. The differences from an earlier inelastic neutron scattering study are discussed.     

黑索金的非弹性中子散射及第一性原理计算

黑索金(环三亚甲基三硝胺, RDX, C₃H₆O₆N₆)是一种非常重要的次级炸药, 因其高能量密度及对外界刺激的低感度而具有广泛的军事和工业应用. 为了能在生产、运输、存储以及使用中对其行为进行有效控制, 人们对它的化学性质、力学性质, 尤其是起爆进行了大量的研究. 炸药的起爆是一个非常复杂的过程, 其中最主要的问题之一就是能量是如何从连续介质尺度的刺激转移到原子尺度引起吸热分解的. 根据冲击波致爆的非平衡态Zel'dovich-von Neumann-Doering模型, 声子作为最初的热载体在整个过程中起着非常重要的作用. 实验上, 非弹性中子散射技术是研究晶体中原子和分子运动动力学的有力手段, 尤其是对于包含了大部分声子晶格模式的低频区域来说极具优势. 利用非弹性中子散射技术测得了RDX 在10–104 cm^-1 范围内的振动谱, 结合固态量子化学计算, 对所测的12个振动模式进行指认. 研究结果有助于人们对起爆详细机理的认识.     

Effect of adding Ar gas on the pulse height distribution of BF<Subscript>3</Subscript>-filled neutron detectors

Boron trifluoride (BF₃) proportional counters are used as detectors for thermal neutrons. They are characterized by high neutron sensitivity and good gamma discriminating properties. Most practical BF₃ counters are filled with pure boron trifluoride gas enriched up to 96% ¹⁰B. But BF₃ is not an ideal proportional counter gas. Worsening of plateau characteristics is observed with increasing radius due to impurities in gas. To overcome this problem, counters are filled with BF₃ with an admixture of a more suitable gas such as argon. The dilution of BF₃ with argon causes a decrease in detection efficiency, but the pulse height spectrum shows sharper peaks and more stable plateau characteristics than counters filled with pure BF₃. The present investigations are undertaken to study the pulse height distribution and other important factors in BF₃+Ar filled signal counters for neutron beam applications. Tests are performed with detectors with cylindrical geometry filled with BF₃ gas enriched in ¹⁰B to 90%, and high purity Ar in different proportions. By analysing pulse height spectra, a value of 6.1 ± 0.2 has been obtained for the branching ratio of the ¹⁰B(n,α) reaction.      

Neutron scattering investigations of multiferroic YMnO<Subscript>3</Subscript>

Multiferroic materials are the materials that show several cooperative ordering phenomena simultaneously. Here we consider only those materials that show both antiferromagnetism and ferroelectricity and in which the ordering parameters are coupled to each other. I shall review our recent neutron scattering investigations on multiferroic hexagonal manganites YMnO₃. We have determined the spin wave dispersions in YMnO₃ in symmetry directions by inelastic neutron scattering and have fitted the results with a simple nearest-neighbour anisotropic Heisenberg model. We have investigated the spin dynamics of YMnO₃ above T _N ∼ 70 K and have shown the existence of persistent albeit heavily damped spin waves.      

One-step synthesis of colloidal Mn<Subscript>3</Subscript>O<Subscript>4</Subscript> and γ-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoparticles at room temperature

A facile room-temperature synthesis has been developed to prepare colloidal Mn₃O₄ and γ-Fe₂O₃ nanoparticles (5 to 25 nm) by an ultrasonic-assisted method in the absence of any additional nucleation and surfactant. The morphology of the as-prepared samples was observed by transmission electron microscopy. High-resolution transmission electron microscopy observations revealed that the as-synthesized nanoparticles were single crystals. The magnetic properties of the samples were investigated with a superconducting quantum interference device magnetometer. The possible formation process has been proposed.     

Investigation on structural characteristics of PVDF–AgCF<Subscript>3</Subscript>SO<Subscript>3</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanocomposite solid polymer electrolyte system

There has been an increasing interest towards the incorporation of nanosize ceramic fillers in polymer electrolytes. Solid polymer electrolytes based on polyvinylidene fluoride (PVDF), silver triflate (AgCF₃SO₃), and x wt% of aluminum oxide (Al₂O₃) nanopowders (where x = 1, 3, 5, and 10, respectively) have been prepared using solution casting technique. The structural characteristics of these thin film specimens were studied using Fourier transform infrared (FTIR) and X-ray diffraction (XRD) patterns at room temperature. The appearance of new absorption bands and gradual shifts observed in some characteristic peaks confirmed the complex formation between polyvinylidene fluoride and silver triflate. Furthermore, the addition of nanosized filler Al₂O₃ has also indicated the interaction of the filler with the polymer salt complex. The XRD patterns obtained for all these samples in the 2θ range 10° to 70° showed the amorphous nature of these samples. Paper presented at the Third International Conference on Ionic Devices (ICID 2006), Chennai, Tamilnadu, India, December 7–9, 2006.     

Optical waveguides in LiNbO<Subscript>3</Subscript> and stoichiometric LiNbO<Subscript>3</Subscript> crystals by proton exchange

The formation of optical planar waveguides in LiNbO₃ and stoichiometric LiNbO₃ crystals by proton exchange was reported. The prism-coupling method was used to characterize the dark-line spectroscopy at the wavelength of 633 and 1539 nm, respectively. The mode optical near-field outputs from proton-exchanged LiNbO₃ and SLN waveguides at 633 nm were presented. The mode field from stoichiometric LiNbO₃ (SLN) waveguide is lighter and more uniform than that from LiNbO₃ waveguide, which means the quality of the waveguide in SLN crystal is better than that of the LiNbO₃ waveguide. For proton-exchanged LiNbO₃ waveguides, the evolution of the refractive index profile with annealing was presented. The disorder profiles of Nb atoms in proton-exchanged LiNbO₃ waveguides were obtained by Rutherford backscattering/channeling technique. It is shown that the longer the exchange time, the larger the displacement of Nb atoms. Supported by the National Natural Science Foundation of China (Grant No. 10475052) and the Scientific Research Start-up Financing of Qufu Normal University     

Hyperfine structure in EPR spectra of the catalytic system TiCl<Subscript>4</Subscript> + Al(i-C<Subscript>4</Subscript>H<Subscript>9</Subscript>)<Subscript>3</Subscript>

In an EPR study of the catalytic system TiCl₄ + Al(i-C₄H₉)₃ in toluene and isopentane in TiCl₄/oligopiperylene + Al(i-C₄H₉)₃ in toluene, we have observed a dependence of the linewidth of the hyperfine structure on the mobility of the complex in solution. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 2, pp. 174–177, March–April, 2007.     

Atomic force microscopy studies of SrTiO<Subscript>3</Subscript> (001) substrates treated by chemical etching and annealing in oxygen

The SrTiO₃ (001) substrates treated by chemical etching in NH₄F-buffered HF solution and annealing in oxygen ambient have been studied by an atomic force microscopy (AFM). The SrTiO₃ substrates with TiO₂-termineted and atomically smooth surfaces and single unit cell steps have been obtained. The surface morphologies of SrTiO₃ substrates strongly depend on the treated conditions and the quality of the substrates.     

VUV luminescence of Er<Superscript>3+</Superscript> ions in LiYF<Subscript>4</Subscript> and BaY<Subscript>2</Subscript>F<Subscript>8</Subscript> crystals

Vacuum ultraviolet luminescence of Er³⁺ ions in LiYF4 and BaY₂F₈ crystals has been investigated. It is revealed that under excitation by 193 nm radiation from an ArF excimer laser the interconfigurational 5d–4f radiative transitions in Er³⁺ ions are observed. It is shown that from the LiYF₄:Er crystal only the spin-forbidden luminescence (λ = 165 nm) is detected, whereas both the spin-forbidden (λ = 169 nm) and spin-allowed (λ = 160.5 nm) components are observed from the BaY₂F₈:Er crystal.     

Up-conversion emissions of Er<Superscript>3+</Superscript>-Yb<Superscript>3+</Superscript> codoped Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoparticles by the arc discharge synthesis method

The Er³⁺-Yb³⁺ codoped Al₂O₃ nanoparticles with an average particle size of about 50 nm have been synthesized by an arc discharge synthesis method. The green and red up-conversion emissions centered at about 526, 547 and 677 nm, corresponding respectively to the ²H_11/2→⁴I_15/2, ⁴S_3/2→⁴I_15/2 and ⁴F_9/2→⁴I_15/2 transitions of Er³⁺, were detected by a 978-nm semiconductor laser diode excitation. The Annealing has evident effect on the up-conversion emissions of the samples: The red up-conversion emission is noticeable before annealing; however, the green up-conversion emission becomes predominant after annealing. The mixture of (Er,Yb)₃Al₅O₁₂ and α-(Al,Er,Yb)₂O₃ phases is more favorable for green up-conversion emissions due to an enhancement of the ESA (I) of ⁴I_11/2+a photon→⁴F_7/2 and ET (III) of ²F_5/2(Yb³⁺)+⁴I_11/2(Er³⁺)→²F_7/2(Yb³⁺)+⁴F_7/2(Er³⁺) processes. The two-photon absorption up-conversion process is involved in the green and red up-conversion emissions. The results have proved that arc discharge synthesis is a new promising preparation technology for optical materials. Supported by National Natural Science Foundation of China (Grant No. 10804015), the Scientific Research Foundation for Doctor of Liaoning Province (Grant No. 20071095), and the Educational Committee Foundation of Liaoning Province (Grant No. 2008123)