Integration of Ultrathin Hafnium Oxide with a Clean van der Waals Interface for Two-Dimensional Sandwich Heterostructure Electronics.

Integrating high-κ dielectrics with a small equivalent oxide thickness (EOT) with two-dimensional (2D) semiconductors for low-power consumption van der Waals (vdW) heterostructure electronics remains challenging in meeting both interface quality and dielectric property requirements. Here, we demonstrate the integration of ultrathin amorphous HfOx sandwiched within vdW heterostructures by the selective thermal oxidation of HfSe2 precursors. The self-cleaning process ensures a high-quality interface with a low interface state density of 1011-1012 cm-2 eV-1. The synthesized HfOx displays excellent dielectric properties with an EOT of ∼1.5 nm, i.e., a high κ of ∼16, an ultralow leakage current of 10-6 A/cm2, and an impressively high breakdown field of 9.5 MV/cm. This facilitates low-power consumption vdW heterostructure MoS2 transistors, demonstrating steep switching with a low subthreshold swing of 61 mV/decade. This one-step integration of high-κ dielectrics into vdW sandwich heterostructures holds immense potential for developing low-power consumption 2D electronics while meeting comprehensive dielectric requirements.

Quasi-Zero-Dimensional Ferroelectric Polarization Charges-Coupled Resistance Switching with High-Current Density in Ultrascaled Semiconductors.

Ferroelectric memristors hold immense promise for advanced memory and neuromorphic computing. However, they face limitations due to low readout current density in conventional designs with low-conductive ferroelectric channels, especially at the nanoscale. Here, we report a ferroelectric-mediated memristor utilizing a 2D MoS2 nanoribbon channel with an ultrascaled cross-sectional area of <1000 nm2, defined by a ferroelectric BaTiO3 nanoribbon stacked on top. Strikingly, the Schottky barrier at the MoS2 contact can be effectively tuned by the charge transfers coupled with quasi-zero-dimensional polarization charges formed at the two ends of the nanoribbon, which results in distinctive resistance switching accompanied by multiple negative differential resistance showing the high-current density of >104 A/cm2. The associated space charges in BaTiO3 are minimized to ∼3.7% of the polarization charges, preserving nonvolatile polarization. This achievement establishes ferroelectric-mediated nanoscale semiconductor memristors with high readout current density as promising candidates for memory and highly energy-efficient in-memory computing applications.

A Light-Programmed Rewritable Lattice-Mediated Multistate Memory for High-Density Data Storage.

Mainstream non-volatile memory (NVM) devices based on floating gate structures or phase-change/ferroelectric materials face inherent limitations that compromise their suitability for long-term data storage. To address this challenge, a novel memory device based on light-programmed lattice engineering of thin rhenium disulfide (ReS2 ) flakes is proposed. By inducing sulfur vacancies in the ReS2 channel through light illumination, the device's electrical conductivity is modified accordingly and multiple conductance states for data storage therefore are generated. The device exhibits more than 128 distinct states with linearly increasing conductance, corresponding to a sevenfold increase in storage density. Through further optimization to achieve atomic-level precision in defect creation, it is possible to achieve even higher storage densities. These states are extremely stable in vacuum or inert ambient showing long retention of >10 years, while they can be erased upon exposure to the air. The ReS2 memory device can maintain its stability over multiple program-erase operation cycles and shows superior wavelength discrimination capability for incident light in the range of 405-785 nm. This device represents a significant contribution to NVM technology by offering the ability to store information in multistate memory and enabling filter-free color image recorder applications.

Reconfigurable Quasi-Nonvolatile Memory/Subthermionic FET Functions in Ferroelectric-2D Semiconductor vdW Architectures.

The functional reconfiguration of transistors and memory in homogenous ferroelectric devices offers significant opportunities for implementing the concepts of in-memory computing and logic-memory monolithic integration. Thus far, reconfiguration is realized through programmable doping profiles in the semiconductor channel using multiple-gate operation. This complex device architecture limits further scaling to match the overall chip requirements. Here, reconfigurable memory/transistor functionalities in a ferroelectric-gated van der Waals transistor by controlling the behavior of ferroelectric oxygen vacancies at the interface are demonstrated. Short- and long-term memory functions are demonstrated by modulating the border oxygen vacancy distribution and the associated charge dynamics. The quasi-nonvolatile long-term memory exhibits data retention of over 105 s and endurance of up to 5 × 105 cycles, verifying its applicability as a potential device platform for neuromorphic networks. More importantly, by modulating the ferroelectricity of the interfacial domains with the interactions of oxygen vacancies, a hysteresis-free logic transistor is realized with a subthermionic subthreshold swing down to 46 mV dec-1 , which resembles a negative-capacitance field-effect transistor. The new concept of achieving functional reconfiguration with prior device performance in a single-gate ferroelectric field-effect transistor is of great advantage in future integrated circuit applications.

Charge-Ferroelectric Transition in Ultrathin Na0.5 Bi4.5 Ti4 O15 Flakes Probed via a Dual-Gated Full van der Waals Transistor.

Ferroelectric field-effect transistors (FeFETs) have recently attracted enormous attention owing to their applications in nonvolatile memories and low-power logic electronics. However, the current mainstream thin-film-based ferroelectrics lack good compatibility with the emergent 2D van der Waals (vdW) heterostructures. In this work, the synthesis of thin ferroelectric Na0.5 Bi4.5 Ti4 O15 (NBIT) flakes by a molten-salt method is reported. With a dry-transferred NBIT flake serving as the top-gate dielectric, dual-gate molybdenum disulfide (MoS2 ) FeFETs are fabricated in a full vdW stacking structure. Barrier-free graphene contacts allow the investigation of intrinsic carrier transport of MoS2 governed by lattice scattering. Thanks to the high dielectric constant of ≈94 in NBIT, a metal to insulator transition with a high electron concentration of 3.0 × 1013 cm-2 is achieved in MoS2 under top-gate modulation. The electron field-effect mobility as high as 182 cm2 V-1 s-1 at 88 K is obtained. The as-fabricated MoS2 FeFET exhibits clockwise hysteresis transfer curves that originate from charge trapping/release with either top-gate or back-gate modulation. Interestingly, hysteresis behavior can be controlled from clockwise to counterclockwise using dual-gate. A multifunctional device utilizing this unique property of NBIT, which is switchable electrostatically between short-term memory and nonvolatile ferroelectric memory, is envisaged.

Self-Terminated Surface Monolayer Oxidation Induced Robust Degenerate Doping in MoTe2 for Low Contact Resistance.

We introduce an effective method to degenerately dope MoTe2 by oxidizing its surface into the p-dopant MoOx in oxygen plasma. As a self-terminated process, the oxidation is restricted only in the very top layer, therefore offering us an easy and efficient control. The degenerate p-doping with the hole concentration of 2.5 × 1013 cm-2 can be obtained by applying a ∼300 s O2 plasma treatment. Using the degenerately doped MoTe2, we demonstrate a record low contact resistance of 0.6 kΩ µm for MoTe2. Our measurement highlights an excellent stability for the plasma-doped MoTe2. The doped characteristics are robust with no significant degradation even after a one-year exposure to the air. The oxygen plasma doping technique is compatible with the conventional semiconductor processes, which can be utilized to realize high-performance MoTe2 field-effect transistors (FETs) or tunnel FETs in the future.

Quantum Dot Formation in Controllably Doped Graphene Nanoribbon.

We introduce the controllable doping from hydrogen silsesquioxane (HSQ) to graphene by changing its electron-beam exposure dose. Using HSQ as the dopant, a fine-resolution electron-beam resist allows us to selectively dope graphene with an extremely high spatial resolution of a few nanometers. Therefore, we can design and demonstrate the single quantum dot (QD)-like transport in the graphene nanoribbon (GNR) with the opening of the energy gap. Moreover, we suggest a rough geometric design rule in which a relatively short and wide GNR is required for observing the single QD-like transport. We envisage that this method can be utilized for other materials and for other applications, such as p-n junctions and tunnel field-effect transistors.

High-Pressure Synthesis, Crystal Structure, and Magnetic Properties of Sr2MnO3F: A New Member of Layered Perovskite Oxyfluorides.

We have successfully synthesized Sr2MnO3F, a new layered perovskite oxyfluoride with a n = 1 Ruddlesden-Popper-type structure using a high-pressure, high-temperature method. Structural refinements against synchrotron X-ray diffraction data collected from manganese oxyfluoride demonstrated that it crystallizes in a tetragonal cell with the space group I4/mmm, in which the Mn cation is located at the octahedral center position. This is in stark contrast to the related oxyhalides that have square-pyramidal coordination such as Sr2MO3X (M = Fe, Co, Ni; X = F, Cl) and Sr2MnO3Cl. There was no evidence of O/F site order, but close inspection of the anion environment centered at the Mn cation on the basis of bond-valence-sum calculation suggested preferential occupation of the apical sites by the F ion with one oxide ion in a random manner. Magnetic susceptibility and heat capacity measurements revealed an antiferromagnetic ordering at 133 K (=TN), which is much higher than that of the chloride analogue with corrugated MnO2 planes (TN = 80 K).

Local destruction of superconductivity by non-magnetic impurities in mesoscopic iron-based superconductors.

The determination of the pairing symmetry is one of the most crucial issues for the iron-based superconductors, for which various scenarios are discussed controversially. Non-magnetic impurity substitution is one of the most promising approaches to address the issue, because the pair-breaking mechanism from the non-magnetic impurities should be different for various models. Previous substitution experiments demonstrated that the non-magnetic zinc can suppress the superconductivity of various iron-based superconductors. Here we demonstrate the local destruction of superconductivity by non-magnetic zinc impurities in Ba0.5K0.5Fe2As2 by exploring phase-slip phenomena in a mesoscopic structure with 119 × 102 nm(2) cross-section. The impurities suppress superconductivity in a three-dimensional 'Swiss cheese'-like pattern with in-plane and out-of-plane characteristic lengths slightly below ∼1.34 nm. This causes the superconducting order parameter to vary along abundant narrow channels with effective cross-section of a few square nanometres. The local destruction of superconductivity can be related to Cooper pair breaking by non-magnetic impurities.

High-pressure synthesis, crystal structures, and magnetic properties of 5d double-perovskite oxides Ca2MgOsO6 and Sr2MgOsO6.

Double-perovskite oxides Ca2MgOsO6 and Sr2MgOsO6 have been synthesized under high-pressure and high-temperature conditions (6 GPa and 1500 °C). Their crystal structures and magnetic properties were studied by a synchrotron X-ray diffraction experiment and by magnetic susceptibility, specific heat, isothermal magnetization, and electrical resistivity measurements. Ca2MgOsO6 and Sr2MgOsO6 crystallized in monoclinic (P21/n) and tetragonal (I4/m) double-perovskite structures, respectively; the degree of order of the Os and Mg arrangement was 96% or higher. Although Ca2MgOsO6 and Sr2MgOsO6 are isoelectric, a magnetic-glass transition was observed for Ca2MgOsO6 at 19 K, while Sr2MgOsO6 showed an antiferromagnetic transition at 110 K. The antiferromagnetic-transition temperature is the highest in the family. A first-principles density functional approach revealed that Ca2MgOsO6 and Sr2MgOsO6 are likely to be antiferromagnetic Mott insulators in which the band gaps open, with Coulomb correlations of ∼1.8-3.0 eV. These compounds offer a better opportunity for the clarification of the basis of 5d magnetic sublattices, with regard to the possible use of perovskite-related oxides in multifunctional devices. The double-perovskite oxides Ca2MgOsO6 and Sr2MgOsO6 are likely to be Mott insulators with a magnetic-glass (MG) transition at ∼19 K and an antiferromagnetic (AFM) transition at ∼110 K, respectively. This AFM transition temperature is the highest among double-perovskite oxides containing single magnetic sublattices. Thus, these compounds offer valuable opportunities for studying the magnetic nature of 5d perovskite-related oxides, with regard to their possible use in multifunctional devices.

High-temperature ferrimagnetism driven by lattice distortion in double perovskite Ca2FeOsO6.

5d and 3d hybrid solid-state oxide Ca2FeOsO6 crystallizes into an ordered double-perovskite structure with a space group of P21/n with high-pressures and temperatures. Ca2FeOsO6 presents a long-range ferrimagnetic transition at a temperature of ~320 K (T(c)) and is not a band insulator, but is electrically insulating like the recently discovered Sr2CrOsO6 (T(c) ~725 K). The electronic stat of Ca2FeOsO6 is adjacent to a half-metallic state as well as that of Sr2CrOsO6. In addition, the high-T(c) ferrimagnetism was driven by lattice distortion, which was observed for the first time among double-perovskite oxides and represents complex interplays between spins and orbitals. Unlike conventional ferrite and garnet, the interplays likely play a pivotal role of the ferrimagnetism. A new class of 5d-3d hybrid ferrimagnetic insulators with high-T(c) is established to develop practically and scientifically useful spintronic materials.

High-pressure synthesis, crystal structure, and magnetic properties of KSbO3-type 5d oxides K0.84OsO3 and Bi2.93Os3O11.

5d Solid-state oxides K0.84OsO3 (Os5.16+; 5d2.84) and Bi2.93Os3O11 (Os4.40+; 5d3.60) were synthesized under high-pressure and high-temperature conditions (6 GPa and 1500-1700 °C). Their crystal structures were determined by synchrotron x-ray diffraction and their 5d electronic properties and tunnel-like structure motifs were investigated. A KSbO3-type structure with a space group of Im-3 and Pn-3 was determined for K0.84OsO3 and Bi2.93Os3O11, respectively. The magnetic and electronic transport properties of the polycrystalline compounds were compared with those obtained theoretically. It was revealed that the 5d tunnel-like structures are paramagnetic with metallic charge conduction at temperatures above 2 K. This was similar to what was observed for structurally relevant 5d oxides, including Bi3Re3O11 (Re4.33+; 5d2.66) and Ba2Ir3O9 (Ir4.66+; 5d4.33). The absence of long-range magnetic order seems to be common among 5d KSbO3-like oxides, regardless of the number of 5d electrons (between 2.6 and 4.3 per 5d atom).