Revival of Ferroelectric Memories Based on Emerging Fluorite-Structured Ferroelectrics.

Over the last few decades, the research on ferroelectric memories has been limited due to their dimensional scalability and incompatibility with complementary metal-oxide-semiconductor (CMOS) technology. The discovery of ferroelectricity in fluorite-structured oxides revived interest in the research on ferroelectric memories, by inducing nanoscale nonvolatility in state-of-the-art gate insulators by minute doping and thermal treatment. The potential of this approach has been demonstrated by the fabrication of sub-30 nm electronic devices. Nonetheless, to realize practical applications, various technical limitations, such as insufficient reliability including endurance, retention, and imprint, as well as large device-to-device-variation, require urgent solutions. Furthermore, such limitations should be considered based on targeting devices as well as applications. Various types of ferroelectric memories including ferroelectric random-access-memory, ferroelectric field-effect-transistor, and ferroelectric tunnel junction should be considered for classical nonvolatile memories as well as emerging neuromorphic computing and processing-in-memory. Therefore, from the viewpoint of materials science, this review covers the recent research focusing on ferroelectric memories from the history of conventional approaches to future prospects.

Unveiling the Origin of Robust Ferroelectricity in Sub-2 nm Hafnium Zirconium Oxide Films.

HfO2-based ferroelectrics are highly expected to lead the new paradigm of nanoelectronic devices owing to their unexpected ability to enhance ferroelectricity in the ultimate thickness scaling limit (≤2 nm). However, an understanding of its physical origin remains uncertain because its direct microstructural and chemical characterization in such a thickness regime is extremely challenging. Herein, we solve the mystery for the continuous retention of high ferroelectricity in an ultrathin hafnium zirconium oxide (HZO) film (∼2 nm) by unveiling the evolution of microstructures and crystallographic orientations using a combination of state-of-the-art structural analysis techniques beyond analytical limits and theoretical approaches. We demonstrate that the enhancement of ferroelectricity in ultrathin HZO films originates from textured grains with a preferred orientation along an unusual out-of-plane direction of (112). In principle, (112)-oriented grains can exhibit 62% greater net polarization than the randomly oriented grains observed in thicker samples (>4 nm). Our first-principles calculations prove that the hydroxyl adsorption during the deposition process can significantly reduce the surface energy of (112)-oriented films, thereby stabilizing the high-index facet of (112). This work provides new insights into the ultimate scaling of HfO2-based ferroelectrics, which may facilitate the design of future extremely small-scale logic and memory devices.

Carrier multiplication in van der Waals layered transition metal dichalcogenides.

Carrier multiplication (CM) is a process in which high-energy free carriers relax by generation of additional electron-hole pairs rather than by heat dissipation. CM is promising disruptive improvements in photovoltaic energy conversion and light detection technologies. Current state-of-the-art nanomaterials including quantum dots and carbon nanotubes have demonstrated CM, but are not satisfactory owing to high-energy-loss and inherent difficulties with carrier extraction. Here, we report CM in van der Waals (vdW) MoTe2 and WSe2 films, and find characteristics, commencing close to the energy conservation limit and reaching up to 99% CM conversion efficiency with the standard model. This is demonstrated by ultrafast optical spectroscopy with independent approaches, photo-induced absorption, photo-induced bleach, and carrier population dynamics. Combined with a high lateral conductivity and an optimal bandgap below 1 eV, these superior CM characteristics identify vdW materials as an attractive candidate material for highly efficient and mechanically flexible solar cells in the future.

Band Alignment and the Built-in Potential of Solids.

The built-in potential is of central importance to the understanding of many interfacial phenomena because it determines the band alignment at the interface. Despite its importance, its exact sign and magnitude have generally been recognized as ill-defined quantities for more than half a century. Here, we provide a common energy reference of bulk matter which leads to an unambiguous definition of the built-in potential and innate (i.e., bulk) band alignment. Further, we find that the built-in potential is explicitly determined by the bulk properties of the constituent materials when the system is in electronic equilibrium, while the interface plays a role only in the absence of equilibrium. Our quantitative theory enables a unified description of a variety of important properties of interfaces, ranging from work functions to Schottky barriers in electronic devices.

Quantum oscillation in carrier transport in two-dimensional junctions.

Two-dimensional (2D) junction devices have recently attracted considerable attention. Here, we show that most 2D junction structures, whether vertical or lateral, act as a lateral monolayer-bilayer-monolayer junction in their operation. In particular, a vertical structure cannot function as a vertical junction as having been widely believed in the literature. Due to a larger electrostatic screening, the bilayer region in the junction always has a smaller bandgap than its monolayer counterpart. As a result, a potential well, aside from the usual potential barrier, will form universally in the bilayer region to affect the hole or electron quantum transport in the form of transmission or reflection. Taking black phosphorus as an example, our calculations using a non-equilibrium Green function combined with density functional theory show a distinct oscillation in the transmission coefficient in a two-electrode prototypical device, and the results can be qualitatively understood using a simple quantum well model.

Traditional Semiconductors in the Two-Dimensional Limit.

Interest in two-dimensional materials has exploded in recent years. Not only are they studied due to their novel electronic properties, such as the emergent Dirac fermion in graphene, but also as a new paradigm in which stacking layers of distinct two-dimensional materials may enable different functionality or devices. Here, through first-principles theory, we reveal a large new class of two-dimensional materials which are derived from traditional III-V, II-VI, and I-VII semiconductors. It is found that in the ultrathin limit the great majority of traditional binary semiconductors studied (a series of 28 semiconductors) are not only kinetically stable in a two-dimensional double layer honeycomb structure, but more energetically stable than the truncated wurtzite or zinc-blende structures associated with three dimensional bulk. These findings both greatly increase the landscape of two-dimensional materials and also demonstrate that in the double layer honeycomb form, even ordinary semiconductors, such as GaAs, can exhibit exotic topological properties.

Long-Range Lattice Engineering of MoTe2 by a 2D Electride.

Doping two-dimensional (2D) semiconductors beyond their degenerate levels provides the opportunity to investigate extreme carrier density-driven superconductivity and phase transition in 2D systems. Chemical functionalization and the ionic gating have achieved the high doping density, but their effective ranges have been limited to ∼1 nm, which restricts the use of highly doped 2D semiconductors. Here, we report on electron diffusion from the 2D electride [Ca2N]+·e- to MoTe2 over a distance of 100 nm from the contact interface, generating an electron doping density higher than 1.6 × 1014 cm-2 and a lattice symmetry change of MoTe2 as a consequence of the extreme doping. The long-range lattice symmetry change, suggesting a length scale surpassing the depletion width of conventional metal-semiconductor junctions, was a consequence of the low work function (2.6 eV) with highly mobile anionic electron layers of [Ca2N]+·e-. The combination of 2D electrides and layered materials yields a novel material design in terms of doping and lattice engineering.

Tuning Dirac points by strain in MoX2 nanoribbons (X = S, Se, Te) with a 1T' structure.

For practical applications of two-dimensional topological insulators, large band gaps and Dirac states within the band gap are desirable because they allow for device operation at room temperature and quantum transport without dissipation. Based on first-principles density functional calculations, we report the tunability of the electronic structure by strain engineering in quasi-one-dimensional nanoribbons of transition metal dichalcogenides with a 1T' structure, MoX2 with X = (S, Se, Te). We find that both the band gaps and Dirac points in 1T'-MoX2 can be engineered by applying an external strain, thereby leading to a single Dirac cone within the bulk band gap. Considering the gap size and the location of the Dirac point, we suggest that, among 1T'-MoX2 nanoribbons, MoSe2 is the most suitable candidate for quantum spin Hall (QSH) devices.

DEVICE TECHNOLOGY. Phase patterning for ohmic homojunction contact in MoTe2.

Artificial van der Waals heterostructures with two-dimensional (2D) atomic crystals are promising as an active channel or as a buffer contact layer for next-generation devices. However, genuine 2D heterostructure devices remain limited because of impurity-involved transfer process and metastable and inhomogeneous heterostructure formation. We used laser-induced phase patterning, a polymorph engineering, to fabricate an ohmic heterophase homojunction between semiconducting hexagonal (2H) and metallic monoclinic (1T') molybdenum ditelluride (MoTe2) that is stable up to 300°C and increases the carrier mobility of the MoTe2 transistor by a factor of about 50, while retaining a high on/off current ratio of 10(6). In situ scanning transmission electron microscopy results combined with theoretical calculations reveal that the Te vacancy triggers the local phase transition in MoTe2, achieving a true 2D device with an ohmic contact.

Universal Conductance Fluctuation in Two-Dimensional Topological Insulators.

Despite considerable interest in two-dimensional (2D) topological insulators (TIs), a fundamental question still remains open how mesoscopic conductance fluctuations in 2D TIs are affected by spin-orbit interaction (SOI). Here, we investigate the effect of SOI on the universal conductance fluctuation (UCF) in disordered 2D TIs. Although 2D TI exhibits UCF like any metallic systems, the amplitude of these fluctuations is distinguished from that of conventional spin-orbit coupled 2D materials. Especially, in 2D systems with mirror symmetry, spin-flip scattering is forbidden even in the presence of strong intrinsic SOI, hence increasing the amplitude of the UCF by a factor of √2 compared with extrinsic SOI that breaks mirror symmetry. We propose an easy way to experimentally observe the existence of such spin-flip scattering in 2D materials. Our findings provide a key to understanding the emergence of a new universal behavior in 2D TIs.

Bandgap Widening of Phase Quilted, 2D MoS2 by Oxidative Intercalation.

Controllable bandgap widening from 1.8 to 2.6 eV is reported from oxidized MoS2 sheets that are composed of quilted phases of various MoSxOy flakes. The exfoliated flakes have large size (≥100 µm × 100 µm) sheets with average thickness of 1.7 nm. Remarkably, fine reversible tuning of the bandgap is achieved by postprocessing sulfurization of the MoSxOy sheets.

Effect of dimensionality on the localization behavior in hydrogenated graphene systems.

Recently, several experiments have shown that graphene exhibits a metal-to-insulator transition by hydrogenation. Here we theoretically study the transport properties of hydrogenated graphene and graphene nanoribbons (GNRs), focusing on the conductance fluctuation behavior in the localized regime. Using a simple model for the conductance distribution in the quasi-localized regime where the conventional theory fails, we derive the modified single parameter scaling (SPS) relations for quasi-one-dimensional (Q1D) GNRs as well as two-dimensional (2D) graphene. We show that, as the dimensional crossover occurs from 2D to Q1D, the shape of the conductance distribution evolves from a positively skewed distribution to a log-normal distribution. We predict that GNRs with widths much larger than the localization lengths do not behave as a Q1D system. Our results provide fundamental insights into the dimensionality change not only in graphene, but also in general mesoscopic systems in the localized regime.