Ivan I. Naumov

Unusual phase transitions in ferroelectric nanodisks and nanorods

Bulk ferroelectrics undergo structural phase transformations at low temperatures, giving multi-stable (that is, multiple-minimum) degenerate states with spontaneous polarization. Accessing these states by applying, and varying the direction of, an external electric field is a key principle for the operation of devices such as non-volatile ferroelectric random access memories (NFERAMs). Compared with bulk ferroelectrics, low-dimensional finite ferroelectric structures promise to increase the storage density of NFERAMs 10,000-fold. But this anticipated benefit hinges on whether phase transitions and multi-stable states still exist in low-dimensional structures. Previous studies have suggested that phase transitions are impossible in one-dimensional systems, and become increasingly less likely as dimensionality further decreases. Here we perform ab initio studies of ferroelectric nanoscale disks and rods of technologically important Pb(Zr,Ti)O3 solid solutions, and demonstrate the existence of previously unknown phase transitions in zero-dimensional ferroelectric nanoparticles. The minimum diameter of the disks that display low-temperature structural bistability is determined to be 3.2 nm, enabling an ultimate NFERAM density of 60 × 1012 bits per square inch—that is, five orders of magnitude larger than those currently available. Our results suggest an innovative use of ferroelectric nanostructures for data storage, and are of fundamental value for the theory of phase transition in systems of low dimensionality.

Atomistic treatment of depolarizing energy and field in ferroelectric nanostructures

An atomistic approach allowing an accurate and efficient treatment of depolarizing energy and field in any low-dimensional ferroelectric structure is developed. Application of this approach demonstrates the limits of the widely used continuum model (even) for simple test cases. Moreover, implementation of this approach within a first-principles-based model reveals an unusual phase transition---from a state exhibiting a spontaneous polarization to a phase associated with a toroid moment of polarization---in a ferroelectric nanodot for a critical value of the depolarizing field.

Vortex-to-polarization phase transformation path in ferroelectric Pb(ZrTi)O3 nanoparticles

Phase transformation in finite-size ferroelectrics is of fundamental relevance for understanding collective behaviors and balance of competing interactions in low-dimensional systems. We report a first-principles effective Hamiltonian study of vortex-to-polarization transformation in Pb(Zr0.5Ti0.5)O3 nanoparticles, caused by homogeneous electric fields normal to the vortex plane. The transformation is shown to (1) follow an unusual macroscopic path that is symmetry nonconforming and characterized by the occurrence of a previously unknown structure as the bridging phase, and (2) lead to the discovery of a striking collective phenomenon, revealing how ferroelectric vortex is annihilated microscopically. Interactions underlying these behaviors are discussed.

Unusual polarization patterns in flat epitaxial ferroelectric nanoparticles.

We investigate the effects of a lattice misfit strain on a ground state and polarization patterns in flat perovskite nanoparticles (nanoislands of BaTiO3 and PZT) with the use of an ab initio derived effective Hamiltonian. We show that the strain strongly controls the balance between the depolarizing field and the polarization anizotropy in determining the equilibrium polarization patterns. Compressive strain favors 180 degrees stripe or tweed domains while a tensile strain leads to in-plane vortex formation, with the unusual intermediate phase(s) where both ordering motifs coexist. The results may allow us to explain contradictions in recent experimental data for ferroelectric nanoparticles.

Fermi surface nesting and pre-martensitic softening in V and Nb at high pressures

First-principles total-energy calculations were performed for the trigonal shear elastic constant (C44) of body-centred cubic (bcc) V and Nb. A mechanical instability in C44 is found for V at pressures of ~2 Mbar which also shows a softening in Nb at pressures of ~0.5 Mbar. We argue that the pressure-induced shear instability (softening) of V (Nb) is due to the intra-band nesting of the Fermi surface.

Potential high-Tc superconducting lanthanum and yttrium hydrides at high pressure

Significance Theoretical predictions and subsequent experimental observations of high-temperature superconductivity in dense hydrogen-rich compounds have reinvigorated the field of superconductivity. A systematic computational study of the hydrides of lanthanum and yttrium over a wide composition range reveals hydrogen-rich structures with intriguing electronic properties under pressure. Electron–phonon coupling calculations predict the existence of new superconducting phases, some exhibiting superconductivity in the range of room temperature. Moreover, the calculated stabilities indicate the materials could be synthesized at pressures that are currently accessible in the laboratory. The results open the prospect for the design, synthesis, and recovery of new high-temperature superconductors with potential practical applications. A systematic structure search in the La–H and Y–H systems under pressure reveals some hydrogen-rich structures with intriguing electronic properties. For example, LaH10 is found to adopt a sodalite-like face-centered cubic (fcc) structure, stable above 200 GPa, and LaH8 a C2/m space group structure. Phonon calculations indicate both are dynamically stable; electron phonon calculations coupled to Bardeen–Cooper–Schrieffer (BCS) arguments indicate they might be high-Tc superconductors. In particular, the superconducting transition temperature Tc calculated for LaH10 is 274–286 K at 210 GPa. Similar calculations for the Y–H system predict stability of the sodalite-like fcc YH10 and a Tc above room temperature, reaching 305–326 K at 250 GPa. The study suggests that dense hydrides consisting of these and related hydrogen polyhedral networks may represent new classes of potential very high-temperature superconductors.

Cooperative response of Pb(ZrTi)O3 nanoparticles to curled electric fields.

We investigate cooperative responses, as well as a microscopic mechanism for vortex switching, in Pb(Zr0.5Ti0.5)O3 nanoparticles under curled electric fields. We find that the domain coexistence mechanism is not valid for toroid switching. Instead dipoles display unusual collective behavior by forming a new vortex with a perpendicular (not opposite) toroid moment. The correlation between the new and original vortices is revealed to be critical for reversing the toroid moment. We further describe a technological approach that is able to drastically reduce the curled electric field needed for vortex switching.

Electronic excitations and metallization of dense solid hydrogen

Theoretical calculations and an assessment of recent experimental results for dense solid hydrogen lead to a unique scenario for the metallization of hydrogen under pressure. The existence of layered structures based on graphene sheets gives rise to an electronic structure related to unique features found in graphene that are well studied in the carbon phase. The honeycombed layered structure for hydrogen at high density, first predicted in molecular calculations, produces a complex optical response. The metallization of hydrogen is very different from that originally proposed via a phase transition to a close-packed monoatomic structure, and different from simple metallization recently used to interpret recent experimental data. These different mechanisms for metallization have very different experimental signatures. We show that the shift of the main visible absorption edge does not constrain the point of band gap closure, in contrast with recent claims. This conclusion is confirmed by measured optical spectra, including spectra obtained to low photon energies in the infrared region for phases III and IV of hydrogen.

Chemical bonding in hydrogen and lithium under pressure

Though hydrogen and lithium have been assigned a common column of the periodic table, their crystalline states under common conditions are drastically different: the former at temperatures where it is crystalline is a molecular insulator, whereas the latter is a metal that takes on simple structures. On compression, however, the two come to share some structural and other similarities associated with the insulator-to-metal and metal-to-insulator transitions, respectively. To gain a deeper understanding of differences and parallels in the behaviors of compressed hydrogen and lithium, we performed an ab initio comparative study of these systems in selected identical structures. Both elements undergo a continuous pressure-induced s-p electronic transition, though this is at a much earlier stage of development for H. The valence charge density accumulates in interstitial regions in Li but not in H in structures examined over the same range of compression. Moreover, the valence charge density distributions or electron localization functions for the same arrangement of atoms mirror each other as one proceeds from one element to the other. Application of the virial theorem shows that the kinetic and potential energies jump across the first-order phase transitions in H and Li are opposite in sign because of non-local effects in the Li pseudopotential. Finally, the common tendency of compressed H and Li to adopt three-fold coordinated structures as found is explained by the fact that such structures are capable of yielding a profound pseudogap in the electronic densities of states at the Fermi level, thereby reducing the kinetic energy. These results have implications for the phase diagrams of these elements and also for the search for new structures with novel properties.

Aromaticity, Closed-Shell Effects, and Metallization of Hydrogen

CONSPECTUS: Recent theoretical and experimental studies reveal that compressed molecular hydrogen at 200-350 GPa transforms to layered structures consisting of distorted graphene sheets. The discovery of chemical bonding motifs in these phases that are far from close-packed contrasts with the long-held view that hydrogen should form simple, symmetric, ambient alkali-metal-like structures at these pressures. Chemical bonding considerations indicate that the realization of such unexpected structures can be explained by consideration of simple low-dimensional model systems based on H6 rings and graphene-like monolayers. Both molecular quantum chemistry and solid-state physics approaches show that these model systems exhibit a special stability, associated with the completely filled set of bonding orbitals or valence bands. This closed-shell effect persists in the experimentally observed layered structures where it prevents the energy gap from closing, thus delaying the pressure-induced metallization. Metallization occurs upon further compression by destroying the closed shell electronic structure, which is mainly determined by the 1s electrons via lowering of the bonding bands stemming from the unoccupied atomic 2s and 2p orbitals. Because enhanced diamagnetic susceptibility is a fingerprint of aromaticity, magnetic measurements provide a potentially important tool for further characterization of compressed hydrogen. The results indicate that the properties of dense hydrogen are controlled by chemical bonding forces over a much broader range of conditions than previously considered.