Thermodynamic Control of Two-Dimensional Molecular Ionic Nanostructures on Metal Surfaces

Bulk molecular ionic solids exhibit fascinating electronic properties, including electron correlations, phase transitions, and superconducting ground states. In contrast, few of these phenomena have been observed in low-dimensional molecular structures, including thin films, nanoparticles, and molecular blends, not in the least because most of such structures have been composed of nearly closed-shell molecules. It is therefore desirable to develop low-dimensional ionic molecular structures that can capture potential applications. Here, we present detailed analysis of monolayer-thick structures of the canonical TTF–TCNQ (tetrathiafulvalene 7,7,8,8-tetracyanoquinodimethane) system grown on low-index gold and silver surfaces. The most distinctive property of the epitaxial growth is the wide abundance of stable TTF/TCNQ ratios, in sharp contrast to the predominance of a 1:1 ratio in the bulk. We propose the existence of the surface phase diagram that controls the structures of TTF–TCNQ on the surfaces and demonstrate phase transitions that occur upon progressively increasing the density of TCNQ while keeping the surface coverage of TTF fixed. Based on direct observations, we propose the binding motif behind the stable phases and infer the dominant interactions that enable the existence of the rich spectrum of surface structures. Finally, we also show that the surface phase diagram will control the epitaxy beyond monolayer coverage. Multiplicity of stable surface structures, the corollary rich phase diagram, and the corresponding phase transitions present an interesting opportunity for low-dimensional molecular systems, particularly if some of the electronic properties of the bulk can be preserved or modified in the surface phases

Enhanced Dynamics of Hydrated tRNA on Nanodiamond Surfaces: A Combined Neutron Scattering and MD Simulation Study

Nontoxic, biocompatible nanodiamonds (ND) have recently been implemented in rational, systematic design of optimal therapeutic use in nanomedicines. However, hydrophilicity of the ND surface strongly influences structure and dynamics of biomolecules that restrict <i>in situ</i> applications of ND. Therefore, fundamental understanding of the impact of hydrophilic ND surface on biomolecules at the molecular level is essential. For tRNA, we observe an enhancement of dynamical behavior in the presence of ND contrary to generally observed slow motion at strongly interacting interfaces. We took advantage of neutron scattering experiments and computer simulations to demonstrate this atypical faster dynamics of tRNA on ND surface. The strong attractive interactions between ND, tRNA, and water give rise to unlike dynamical behavior and structural changes of tRNA in front of ND compared to without ND. Our new findings may provide new design principles for safer, improved drug delivery platforms

High‑<i>T</i>_c Layered Ferrielectric Crystals by Coherent Spinodal Decomposition

Research in the rapidly developing field of 2D electronic materials has thus far been focused on metallic and semiconducting materials. However, complementary dielectric materials such as nonlinear dielectrics are needed to enable realistic device architectures. Candidate materials require tunable dielectric properties and pathways for heterostructure assembly. Here we report on a family of cation-deficient transition metal thiophosphates whose unique chemistry makes them a viable prospect for these applications. In these materials, naturally occurring ferrielectric heterostructures composed of centrosymmetric In_4/3P₂S₆ and ferrielectrically active CuInP₂S₆ are realized by controllable chemical phase separation in van der Waals bonded single crystals. CuInP₂S₆ by itself is a layered ferrielectric with a ferrielectric transition temperature (<i>T</i>_c) just over room temperature, which rapidly decreases with homogeneous doping. Surprisingly, in our composite materials, the ferrielectric <i>T</i>_c of the polar CuInP₂S₆ phase increases. This effect is enabled by unique spinodal decomposition that retains the overall van der Waals layered morphology of the crystal, but chemically separates CuInP₂S₆ and In_4/3P₂S₆ within each layer. The average spatial periodicity of the distinct chemical phases can be finely controlled by altering the composition and/or synthesis conditions. One intriguing prospect for such layered spinodal alloys is large volume synthesis of 2D in-plane heterostructures with periodically alternating polar and nonpolar phases

Influence of Nonstoichiometry on Proton Conductivity in Thin-Film Yttrium-Doped Barium Zirconate

Proton-conducting perovskites have been widely studied because of their potential application as solid electrolytes in intermediate temperature solid oxide fuel cells. Structural and chemical heterogeneities can develop during synthesis, device fabrication, or service, which can profoundly affect proton transport. Here, we use time-resolved Kelvin probe force microscopy, scanning transmission electron microscopy, atom probe tomography, and density functional theory calculations to intentionally introduce Ba-deficient planar and spherical defects and link the resultant atomic structure with proton transport behavior in both stoichiometric and nonstoichiometric epitaxial, yttrium-doped barium zirconate thin films. The defects were intentionally induced through high-temperature annealing treatment, while maintaining the epitaxial single crystalline structure of the films, with an overall relaxation in the atomic structure. The annealed samples showed smaller magnitudes of local lattice distortions because of the formation of proton polarons, thereby leading to decreased proton-trapping effect. This resulted in a decrease in the activation energy for proton transport, leading to faster proton transport

Cation–Eutectic Transition <i>via</i> Sublattice Melting in CuInP₂S₆/In_4/3P₂S₆ van der Waals Layered Crystals

Single crystals of the van der Waals layered ferrielectric material CuInP₂S₆ spontaneously phase separate when synthesized with Cu deficiency. Here we identify a route to form and tune intralayer heterostructures between the corresponding ferrielectric (CuInP₂S₆) and paraelectric (In_4/3P₂S₆) phases through control of chemical phase separation. We conclusively demonstrate that Cu-deficient Cu_1–<i>x</i>In_1+<i>x</i>/3P₂S₆ forms a single phase at high temperature. We also identify the mechanism by which the phase separation proceeds upon cooling. Above 500 K both Cu⁺ and In³⁺ become mobile, while P₂S₆^4– anions maintain their structure. We therefore propose that this transition can be understood as eutectic melting on the cation sublattice. Such a model suggests that the transition temperature for the melting process is relatively low because it requires only a partial reorganization of the crystal lattice. As a result, varying the cooling rate through the phase transition controls the lateral extent of chemical domains over several decades in size. At the fastest cooling rate, the dimensional confinement of the ferrielectric CuInP₂S₆ phase to nanoscale dimensions suppresses ferrielectric ordering due to the intrinsic ferroelectric size effect. Intralayer heterostructures can be formed, destroyed, and re-formed by thermal cycling, thus enabling the possibility of finely tuned ferroic structures that can potentially be optimized for specific device architectures