Phase has emerged as an important structural parameter - in addition to composition, morphology, architecture, facet, size and dimensionality - that determines the properties and functionalities of nanomaterials. In particular, unconventional phases in nanomaterials that are unattainable in the bulk state can potentially endow nanomaterials with intriguing properties and innovative applications. Great progress has been made in the phase engineering of nanomaterials (PEN), including synthesis of nanomaterials with unconventional phases and phase transformation of nanomaterials. This Review provides an overview on the recent progress in PEN. We discuss various strategies used to synthesize nanomaterials with unconventional phases and induce phase transformation of nanomaterials, by taking noble metals and layered transition metal dichalcogenides as typical examples. Moreover, we also highlight recent advances in the preparation of amorphous nanomaterials, amorphous-crystalline and crystal phase-based hetero-nanostructures. We also provide personal perspectives on challenges and opportunities in this emerging field, including exploration of phase-dependent properties and applications, rational design of phase-based heterostructures and extension of the concept of phase engineering to a wider range of materials.© 2020. Springer Nature Limited.

Quantum spin liquids (QSLs) are topological states of matter exhibiting remarkable properties such as the capacity to protect quantum information from decoherence. Whereas their featureless ground states have precluded their straightforward experimental identification, excited states are more revealing and particularly interesting owing to the emergence of fundamentally new excitations such as Majorana fermions. Ideal probes of these excitations are inelastic neutron scattering experiments. These we report here for a ruthenium-based material, alpha-RuCl3, continuing a major search (so far concentrated on iridium materials) for realizations of the celebrated Kitaev honeycomb topological QSL. Our measurements confirm the requisite strong spin-orbit coupling and low-temperature magnetic order matching predictions proximate to the QSL. We find stacking faults, inherent to the highly two-dimensional nature of the material, resolve an outstanding puzzle. Crucially, dynamical response measurements above interlayer energy scales are naturally accounted for in terms of deconfinement physics expected for QSLs. Comparing these with recent dynamical calculations involving gauge flux excitations and Majorana fermions of the pure Kitaev model, we propose the excitation spectrum of alpha-RuCl3 as a prime candidate for fractionalized Kitaev physics.

Graphene-based materials are promising candidates for nanoelectronic devices because very high carrier mobilities can be achieved without the use of sophisticated material preparation techniques. However, the carrier mobilities reported for single-layer and bilayer graphene are still less than those reported for graphite crystals at low temperatures, and the optimum number of graphene layers for any given application is currently unclear, because the charge transport properties of samples containing three or more graphene layers have not yet been investigated systematically. Here, we study charge transport through trilayer graphene as a function of carrier density, temperature, and perpendicular electric field. We find that trilayer graphene is a semimetal with a resistivity that decreases with increasing electric field, a behaviour that is markedly different from that of single-layer and bilayer graphene. We show that the phenomenon originates from an overlap between the conduction and valence bands that can be controlled by an electric field, a property that had never previously been observed in any other semimetal. We also determine the effective mass of the charge carriers, and show that it accounts for a large part of the variation in the carrier mobility as the number of layers in the sample is varied.

Epitaxial growth of atomically thin two-dimensional crystals such as transition metal dichalcogenides remains challenging, especially for producing large-size transition metal dichalcogenides bilayer crystals featuring high density of states, carrier mobility and stability at room temperature. Here we achieve in epitaxial growth of the second monolayer from the first monolayer by reverse-flow chemical vapor epitaxy and produce high-quality, large-size transition metal dichalcogenides bilayer crystals with high yield, control, and reliability. Customized temperature profiles and reverse gas flow help activate the first layer without introducing new nucleation centers leading to near-defect-free epitaxial growth of the second layer from the existing nucleation centers. A series of bilayer crystals including MoS and WS, ternary MoWS and quaternary MoWSSe are synthesized with variable structural configurations and tunable electronic and optical properties. The robust, potentially universal approach for the synthesis of large-size transition metal dichalcogenides bilayer single crystals is highly-promising for fundamental studies and technological applications.

Interface engineering is critical for enriching the electronic and transport properties of two-dimensional materials. Here, we identify a new stacking, named Aδ, in few-layer phosphorenes (FLPs) and black phosphorus (BP) based on first-principles calculation. With its low formation energy, the Aδ stacking could exist in FLPs and BP as a stacking fault. The presence of the Aδ stacking fault induces a direct to indirect transition of the band gap in FLPs. It also affects the carrier mobilities by significantly increasing the carrier effective masses. More importantly, the Aδ stacking enables the fabrication of a whole spectrum of lateral junctions with all the type-I, II, and III alignments simply through the manipulation of the van der Waals stacking without resorting to any chemical modification. This is achieved by the widely tunable electron affinity and ionization potential of FLPs and BP with the Aδ stacking.

While traditional ferroelectrics are based on polar crystals in bulk or thin film form, two-dimensional and layered materials can support mechanisms for symmetry breaking between centrosymmetric building blocks, e.g., by creating low-symmetry interfaces in van der Waals stacks. Here, we introduce an approach toward symmetry breaking in van der Waals crystals that relies on the spontaneous incorporation of stacking faults in a nonpolar bulk layer sequence. The concept is realized in nanowires consisting of Se-rich group IV monochalcogenide (GeSeS) alloys, obtained by vapor-liquid-solid growth. The single crystalline wires adopt a layered structure in which the nonpolar A-B bulk stacking along the nanowire axis is interrupted by single-layer stacking faults with local A-A' stacking. Density functional theory explains this behavior by a reduced stacking fault formation energy in GeSe (or Se-rich GeSeS alloys). Computations demonstrate that, similar to monochalcogenide monolayers, the inserted A-layers should show a spontaneous electric polarization with a switching barrier consistent with a Curie temperature above room temperature. Second-harmonic generation signals are consistent with a variable density of stacking faults along the wires. Our results point to possible routes for designing ferroelectrics via the layer stacking in van der Waals crystals.

We demonstrate a van der Waals Schottky junction defined by crystalline phases of multilayer InSe. Besides ideal diode behaviors and the gate-tunable current rectification, the thermoelectric power is significantly enhanced in these junctions by more than three orders of magnitude compared with single-phase multilayer InSe, with the thermoelectric figure-of-merit approaching ∼1 at room temperature. Our results suggest that these significantly improved thermoelectric properties are not due to the 2D quantum confinement effects but instead are a consequence of the Schottky barrier at the junction interface, which leads to hot carrier transport and shifts the balance between thermally and field-driven currents. This "bulk" effect extends the advantages of van der Waals materials beyond the few-layer limit. Adopting such an approach of using energy barriers between van der Waals materials, where the interface states are minimal, is expected to enhance the thermoelectric performance in other 2D materials as well.

It is shown by an extensive benchmark on molecular energy data that the mathematical form of the damping function in DFT-D methods has only a minor impact on the quality of the results. For 12 different functionals, a standard "zero-damping" formula and rational damping to finite values for small interatomic distances according to Becke and Johnson (BJ-damping) has been tested. The same (DFT-D3) scheme for the computation of the dispersion coefficients is used. The BJ-damping requires one fit parameter more for each functional (three instead of two) but has the advantage of avoiding repulsive interatomic forces at shorter distances. With BJ-damping better results for nonbonded distances and more clear effects of intramolecular dispersion in four representative molecular structures are found. For the noncovalently-bonded structures in the S22 set, both schemes lead to very similar intermolecular distances. For noncovalent interaction energies BJ-damping performs slightly better but both variants can be recommended in general. The exception to this is Hartree-Fock that can be recommended only in the BJ-variant and which is then close to the accuracy of corrected GGAs for non-covalent interactions. According to the thermodynamic benchmarks BJ-damping is more accurate especially for medium-range electron correlation problems and only small and practically insignificant double-counting effects are observed. It seems to provide a physically correct short-range behavior of correlation/dispersion even with unmodified standard functionals. In any case, the differences between the two methods are much smaller than the overall dispersion effect and often also smaller than the influence of the underlying density functional.Copyright © 2011 Wiley Periodicals, Inc.