Manipulating the structural and electronic properties of epitaxial NaNbO3 films via strain and stoichiometry

Due to their intriguing dielectric, pyroelectric, elasto-electric, or opto-electric properties, oxide ferroelectrics are vital candidates for the fabrication of most electronics. However, these extraordinary properties exist mainly in the temperature regime around the ferroelectric phase transition, which is usually several hundreds of K away from room temperature. Therefore, the manipulation of oxide ferroelectrics, especially moving the ferroelectric transition towards room temperature, is of great interest for application and also basic research. In this thesis, we demonstrate this using examples of NaNbO3 films. We show that the transition temperature of these films can be modified via plastic strain caused by epitaxial film growth on a structurally mismatched substrate, and this strain can be fixed by controlling the stoichiometry. The structural and electronic properties of Na1+xNbO3+δ thin films are carefully examined by among others XRD (e.g. RSM) and TEM and cryoelectronic measurements. Especially the electronic features are carefully analyzed via specially developed interdigitated electrodes in combination with integrated temperature sensor and heater. The electronic data are interpreted using existing as well as novel theories and models, they are proved to be closely correlated to the structural characteristics. The major results are: -Na1+xNbO3+δ thin films can be grown epitaxially on (110)NdGaO3 with a thickness up to 140 nm (thicker films have not been studied). Plastic relaxation of the compressive strain sets in when the thickness of the film exceeds approximately 10 – 15 nm. Films with excess Na are mainly composed of NaNbO3 with minor contribution of Na3NbO4. The latter phase seems to form nanoprecipitates that are homogeneously distributed in the NaNbO3 film which helps to stabilize the film and reduce the relaxation of the strain. -For the nominally stoichiometric films, the compressive strain leads to a broad and frequency-dispersive phase transition at lower temperature (125 – 147 K). This could be either a new transition or a shift in temperature of a known transition. Considering the broadness and frequency dispersion of the transition, this is actually a transition from the dielectric state at high temperature to a relaxor-type ferroelectric state at low temperature. The latter is based on the formation of polar nano-regions (PNRs). Using the electric field dependence of the freezing temperature, allows a direct estimation of the volume (70 to 270 nm3) and diameter (5.2 to 8 nm, spherical approximation) of the PNRs. The values confirm with literature values which were measured by other technologies. -In case of the off-stoichiometric samples, we observe again the classical ferroelectric behavior. However, the thermally hysteretic phase transition which is observed around 620 – 660 K for unstrained material is shifted to room temperature due to the compressive strain. Beside to the temperature shift, the temperature dependence of the permittivity is nearly identical for strained and unstrained materials. -The last but not least, in all cases, a significant anisotropy in the electronic and structural properties is observed which arises automatically from the anisotropic strain caused by the orthorhombic structure of the substrate. However, this anisotropy cannot be explained by the classical model which tries to fit an orthorhombic film onto an orthorhombic substrate. A novel “square lattice” model in which the films adapt a “square” shaped lattice in the plane of the film during the epitaxial growth at elevated temperature (~1000 K) nicely explains the experimental results. In this thesis we sketch a way to manipulate the ferroelectricity of NaNbO3 films via strain and stoichiometry. The results indicate that compressive strain which is generated by the epitaxial growth of the film on mismatched substrate is able to reduce the ferroelectric transition temperature or induce a phase transition at low temperature. Moreover, by adding Na in the NaNbO3 film a secondary phase Na3NbO4 is formed which seems to stabilize the main phase NaNbO3 and the strain and, thus, is able to engineer the ferroelectric behavior from the expected classical ferroelectric for perfect stoichiometry to relaxor-type ferroelectric for slightly off-stoichiometry, back to classical ferroelectric for larger off-stoichiometry. Both strain and stoichiometry are proven as perfect methods to optimize the ferroelectric properties of oxide films.

Molecular dynamics study of a dual-cation ionomer electrolyte

The poly(N1222)xLi1-x[AMPS] ionomer system with dual cations has previously shown decoupled Li ion dynamics from polymer segmental motions, characterized by the glass transition temperature, which can result in a conductive electrolyte material whilst retaining an appropriate modulus (ie. stiffness) so that it can suppress dendrite formation, thereby improving safety when used in lithium metal batteries. To understand this ion dynamics behavior, molecular dynamics techniques have been used in this work to simulate structure and dynamics in these materials. These simulations confirm that the Li ion transport is decoupled from the polymer particularly at intermediate N1222+ concentrations. At 50 mol% N1222+ concentration the polymer backbone is more rigid than for higher N1222+ concentrations, but with increasing temperature Li ion transport is more significant than polymer or quaternary ammonium cation motions. Here we suggest an ion hopping mechanism for Li+, arising from structural rearrangement of ionic clusters that could explain its decoupled behavior. Higher temperatures favor an aggregated ionic structure as well as enhancing these hopping motions. The simulations discussed here provide an atomic-level understanding of ion dynamics that could contribute to designing an improved ionomer with fast ion transport and mechanical robustness.

Mechanism of dehydroxylation temperature decrease and high temperature phase transition of coal-bearing strata kaolinite intercalated by potassium acetate

The thermal decomposition and dehydroxylation process of coal-bearing strata kaolinite–potassium acetate intercalation complex (CSKK) has been studied using X-ray diffraction (XRD), infrared spectroscopy (IR), thermal analysis, mass spectrometric analysis and infrared emission spectroscopy. The XRD results showed that the potassium acetate (KAc) have been successfully intercalated into coal-bearing strata kaolinite with an obvious basal distance increase of the first basal peak, and the positive correlation was found between the concentration of intercalation regent KAc and the degree of intercalation. As the temperature of the system is raised, the formation of KHCO3, KCO3 and KAlSiO4, which is derived from the thermal decomposition or phase transition of CSKK, is observed in sequence. The IR results showed that new bands appeared, the position and intensities shift can also be found when the concentration of intercalation agent is raised. The thermal analysis and mass spectrometric analysis results revealed that CSKK is stable below 300 °C, and the thermal decomposition products (H2O and CO2) were further proved by the mass spectrometric analysis. A comparison of thermal analysis results of original coal-bearing strata kaolinite and its intercalation complex gives new discovery that not only a new mass loss peak is observed at 285 °C, but also the temperature of dehydroxylation and dehydration of coal bearing strata kaolinite is decreased about 100 °C. This is explained on the basis of the interlayer space of the kaolinite increased obviously after being intercalated by KAc, which led to the interlayer hydrogen bonds weakened, enables the dehydroxylation from kaolinite surface more easily. Furthermore, the possible structural model for CSKK has been proposed, with further analysis required in order to prove the most possible structures.

High-Temperature Phase Transition Studies in a Novel Fast Ion Conductor, Na2Cd(SO4)2, Probed by Raman Spectroscopy

Temperature-dependent Raman spectroscopic studies were carried out on Na2Cd(SO4)(2) from room temperature to 600 degrees C. We observe two transitions at around 280 and 565 degrees C. These transitions are driven by the change in the SO4 ion. On the basis of these studies, one can explain the changes in the conductivity data observed around 280 and 565 degrees C. At 280 degrees C, spontaneous tilting of the SO4 ion leads to restriction of Na+ mobility. Above 565 degrees C, the SO4 ion starts to rotate freely, leading to increased mobility of Na+ ion in the channel.

Dynamical Transition of Water in the Grooves of DNA Duplex at Low Temperature

At low temperature (below its freezing/melting temperature), liquid water under confinement is known to exhibit anomalous dynamical features. Here we study structure and dynamics of water in the grooves of a long DNA duplex using molecular dynamics simulations with TIP5P potential at low temperature. We find signatures of a dynamical transition in both translational and orientational dynamics of water molecules in both the major and the minor grooves of a DNA duplex. The transition occurs at a slightly higher temperature (TGL ≈ 255 K) than the temperature at which the bulk water is found to undergo a dynamical transition, which for the TIP5P potential is at 247 K. Groove water, however, exhibits markedly different temperature dependence of its properties from the bulk. Entropy calculations reveal that the minor groove water is ordered even at room temperature, and the transition at T ≈ 255 K can be characterized as a strong-to-strong dynamical transition. Confinement of water in the grooves of DNA favors the formation of a low density four-coordinated state (as a consequence of enthalpy−entropy balance) that makes the liquid−liquid transition stronger. The low temperature water is characterized by pronounced tetrahedral order, as manifested in the sharp rise near 109° in the O−O−O angle distribution. We find that the Adams−Gibbs relation between configurational entropy and translational diffusion holds quite well when the two quantities are plotted together in a master plot for different region of aqueous DNA duplex (bulk, major, and minor grooves) at different temperatures. The activation energy for the transfer of water molecules between different regions of DNA is found to be weakly dependent on temperature.

Low-temperature and high-pressure Raman and x-ray studies of pyrochlore Tb2Ti2O7: Phonon anomalies and possible phase transition

We have carried out temperature- and pressure-dependent Raman and x-ray measurements on single crystals of Tb2Ti2O7. We attribute the observed anomalous temperature dependence of phonons to phonon-phonon anharmonic interactions. The quasiharmonic and anharmonic contributions to the temperature-dependent changes in phonon frequencies are estimated quantitatively using mode Grüneisen parameters derived from pressure-dependent Raman experiments and bulk modulus from high-pressure x-ray measurements. Further, our Raman and x-ray data suggest a subtle structural deformation of the pyrochlore lattice at ~9 GPa. We discuss possible implications of our results on the spin-liquid behavior of Tb2Ti2O7.

NMR relaxation study of disorder in the mixed system BP x GPI(1-x) and the low temperature transition from classical to quantum rotation

1H NMR spin-lattice relaxation time (T1) studies have been carried out in the temperature range 100 K to 4 K, at two Larmor frequencies 11.4 and 23.3 MHz, in the mixed system of betaine phosphate and glycine phosphite (BPxGPI(1-x)), to study the effects of disorder on the proton group dynamics. Analysis of T1 data indicates the presence of a number of inequivalent methyl groups and a gradual transition from classical reorientations to quantum tunneling rotations. At lower temperatures, microstructural disorder in the local environments of the methyl groups, result in a distribution in the activation energy (Ea) and the torsional energy gap (E01). For certain values of x, the magnetisation recovery shows biexponential behaviour at lower temperatures.

Mixed valency in the high-temperature phases of transition metal molybdates,AMoO4 (A=Fe, Co, Ni)

Transition metal molybdates of the formulaAMoO4 whereA=Fe, Co or Ni exhibit a first-order phase transition between 670K–970K. An investigation of the lowtemperature (lt) and high-temperature (ht) phases by x-ray photoelectron spectroscopy, x-ray absorption spectroscopy, magnetic susceptibility and other physical methods shows that the phase transition is associated with a valence change of the typeA 2++Mo6+αA 3++Mo5+ in the cases of iron and cobalt molybdates.

Towards a temperature-guided molecular switch: an unusual reversible low-temperature polymorphic phase transition in a conformational locked environment

A conformationally locked tetraacetate undergoes, quite akin to a temperature-guided molecular switch, a reversible thermal switching between two polymorphic modifications; the room-temperature alpha-form converted at -4 degrees C to a low-temperature denser beta-form, which displayed an unusual kinetic stability till 67 degrees C and transformed back to the alpha-form beyond this temperature.

Transition from radiatively inefficient to cooling dominated phase in two temperature accretion disks around black holes

We investigate the transition of a radiatively inefficient phase of a viscous two temperature accreting flow to a cooling dominated phase and vice versa around black holes. Based on a global sub-Keplerian accretion disk model in steady state, including explicit cooling processes self-consistently, we show that general advective accretion flow passes through various phases during its infall towards a black hole. Bremsstrahlung, synchrotron and inverse Comptonization of soft photons are considered as possible cooling mechanisms. Hence the flow governs a much lower electron temperature similar to 10(8) - 10(9.5) K compared to the hot protons of temperature similar to 10(10.2) - 10(11.8) K in the range of the accretion rate in Eddington units 0.01 less than or simiar to (M) over dot less than or similar to 100. Therefore, the solutions may potentially explain the hard X-rays and the gamma-rays emitted from AGNs and X-ray binaries. We finally compare the solutions for two different regimes of viscosity and conclude that a weakly viscous flow is expected to be cooling dominated compared to its highly viscous counterpart which is radiatively inefficient. The flow is successfully able to reproduce the observed minosities of the under-fed AGNs and quasars (e.g. Sgr A*), ultra-luminous X-ray sources (e.g. SS433), as well as the highly luminous AGNs and ultra-luminous quasars (e.g. PKS 0743-67) at different combinations of the mass accretion rate and ratio of specific heats.