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Chuanlian Xiao

Publications and source records attributed to Chuanlian Xiao.

4 recordsLinked to original sources

A nanoionic diode: Equilibrium rectifying junction enabling large and stable resistance variations

We report on a new type of rectifier which is in full contact equilibrium and thus, if down-sized to the nanoscale, shows no drift even if exposed to elevated temperatures and/or extreme waiting times. This is in contrast to existing diodes which rely on frozen doping profiles and are hence non-equilibrium devices. Our rectifiers are related to Schottky diodes but employ "dopants" whose mobilities are high enough to follow the electrical field quickly but low enough to not compete with the electrons in terms of conductivities. In order to realize such a device based on mixed conductors, we use nanosized TiO2 films on Ru as a substrate which can store Li at the interface according to a job-sharing mechanism (Li-ions on the TiO2 side, electrons on the Ru side). The excellent functionality of this nanoionic device is demonstrated (e.g., current on-off ratio can exceed 6-7 orders of magnitude) and the additional advantages stressed (such as ease of preparation and tuning the characteristics electrochemically).

cond-mat.other↗

Substrate tuning of the structural and electronic transition in thin flakes of the excitonic insulator candidate Ta$_2$NiSe$_5$

Ta$_2$NiSe$_5$ continues to draw interest for its 326 K phase transition, whose dual electronic and structural nature reflects a complex interplay of electron-hole (excitonic) and electron-lattice interactions. Most studies that have attempted to decipher the relative importance of these interactions, particularly through charge transfer, have been limited to bulk samples. We utilized a thin-flake approach to modify the excitonic interactions in Ta$_2$NiSe$_5$ via an underlying film of Au. Using polarized Raman spectroscopy, we found that four layers of Ta$_2$NiSe$_5$ supported on conducting Au show a transition temperature that is both reduced by over 100 K and broadened due to an interfacial charge gradient effect, manifesting the presence of excitonic interactions. In contrast, four layers of Ta$_2$NiSe$_5$ supported on insulating Al$_2$O$_3$ show nearly bulk-like properties. We also report the development of an all-dry exfoliation and transfer protocol that generalizes substrate engineering for strongly correlated van der Waals materials.

cond-mat.str-el↗

Anomalous Sodium Insertion in Highly Oriented Graphite: Thermodynamics, Kinetics and Evidence for Two-Sided Intercalation

The difficult intercalation of sodium (Na) into graphite is studied by systematic and long-time investigations (of up to 2 years) using highly oriented pyrolytic graphite (HOPG). By studying chemical insertion of solid, liquid and gaseous Na at low and high temperatures (LT, HT) as well as using electrochemical insertion at 25 degree Celsius into uncoated and coated HOPG, it became clear that insertion equilibrium requires HT. On decreasing chemical intercalation temperature from HT (500 degree Celsius) to LT (25 degree Celsius), thermodynamic control was found to change to diffusion control and finally to interfacial control. For the electrochemical insertion, coating (TiO2) proved advisable (to avoid co-intercalation) and efficient in reducing the interfacial resistance. Measured saturation values were found to be not higher than about 1 mol %. Towards room temperature higher equilibrium values cannot be excluded but would in view of the very low driving force kinetically be very difficult to reach. The reversible cell voltage of the saturated composition (versus alkali metal) is distinctly lower than for the analogous cells using lithium (Li) or potassium (K). Detailed transmission electron microscopy (TEM) studies reveal the unexpected fact that at HT Na predominantly enters HOPG in the form of two-sided intercalation sandwiching carbon layers (bilayers), while at LT more highly aggregated layers appear to a comparable degree, accompanied with the formation of higher-dimensional crystal imperfections. The reasons for this peculiar feature and the non-monotonic thermodynamics in the sequence Li-Na-K-Rb-Cs are discussed not only from an energetic but also from an entropic point of view.

cond-mat.mtrl-sci↗

Lithium storage in titania films as a function of position: Unification of intercalation electrode and super-capacitor concepts

We carefully investigated the storage of lithium in titania films on various substrates as a function of thickness. The experiments enable us to precisely separate contributions from bulk and boundary storage. The battery capacity measurements are complemented by bias dependent measurements of impedance, yielding interfacial resistance as well as interfacial capacitance. Independent information on electron and Li distribution is gained by scanning transmission electron microscopy (STEM), electron energy loss spectroscopy (EELS), aberration-corrected annular-bright-field (ABF) STEM. As a result, we obtain the full picture in terms of equilibrium storage (lithium content) and charge carrier concentrations as a function of spatial coordinates with cell voltage as a parameter. More importantly, both bulk storage which obeys electroneutrality and boundary storage which follows the space charge picture can be traced back to a common thermodynamic conception, and are obtained from it as special cases. This corresponds to no less than a unification of intercalation storage and super-capacitive storage, which are usually considered as independent phenomena, the reason for this lying in the hitherto lack of an adequate defect-chemical and nanoionic picture.

physics.chem-ph↗