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.

Highly enhanced ferroelectricity in HfO2-based ferroelectric thin film by light ion bombardment.

Continuous advancement in nonvolatile and morphotropic beyond-Moore electronic devices requires integration of ferroelectric and semiconductor materials. The emergence of hafnium oxide (HfO2)-based ferroelectrics that are compatible with atomic-layer deposition has opened interesting and promising avenues of research. However, the origins of ferroelectricity and pathways to controlling it in HfO2 are still mysterious. We demonstrate that local helium (He) implantation can activate ferroelectricity in these materials. The possible competing mechanisms, including He ion-induced molar volume changes, vacancy redistribution, vacancy generation, and activation of vacancy mobility, are analyzed. These findings both reveal the origins of ferroelectricity in this system and open pathways for nanoengineered binary ferroelectrics.

Quantitative Local Probing of Polarization with Application on HfO2 -Based Thin Films.

Owing to their switchable spontaneous polarization, ferroelectric materials have been applied in various fields, such as information technologies, actuators, and sensors. In the last decade, as the characteristic sizes of both devices and materials have decreased significantly below the nanoscale, the development of appropriate characterization tools became essential. Recently, a technique based on conductive atomic force microscopy (AFM), called AFM-positive-up-negative-down (PUND), is employed for the direct measurement of ferroelectric polarization under the AFM tip. However, the main limitation of AFM-PUND is the low frequency (i.e., on the order of a few hertz) that is used to initiate ferroelectric hysteresis. A significantly higher frequency is required to increase the signal-to-noise ratio and the measurement efficiency. In this study, a novel method based on high-frequency AFM-PUND using continuous waveform and simultaneous signal acquisition of the switching current is presented, in which polarization-voltage hysteresis loops are obtained on a high-polarization BiFeO3 nanocapacitor at frequencies up to 100 kHz. The proposed method is comprehensively evaluated by measuring nanoscale polarization values of the emerging ferroelectric Hf0.5 Zr0.5 O2 under the AFM tip.

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.

Resonant Tunneling Spectroscopy to Probe the Giant Stark Effect in Atomically Thin Materials.

Each atomic layer in van der Waals heterostructures possesses a distinct electronic band structure that can be manipulated for unique device operations. In the precise device architecture, the subtle but critical band splits by the giant Stark effect between atomic layers, varied by the momentum of electrons and external electric fields in device operation, has not yet been demonstrated or applied to design original devices with the full potential of atomically thin materials. Here, resonant tunneling spectroscopy based on the negligible quantum capacitance of 2D semiconductors in resonant tunneling transistors is reported. The bandgaps and sub-band structures of various channel materials could be demonstrated by the new conceptual spectroscopy at the device scale without debatable quasiparticle effects. Moreover, the band splits by the giant Stark effect in the channel materials could be probed, overcoming the limitations of conventional optical, photoemission, and tunneling spectroscopy. The resonant tunneling spectroscopy reveals essential and practical information for novel device applications.

Wafer-Scale Synthesis of Reliable High-Mobility Molybdenum Disulfide Thin Films via Inhibitor-Utilizing Atomic Layer Deposition.

A reliable and rapid manufacturing process of molybdenum disulfide (MoS2 ) with atomic-scale thicknesses remains a fundamental challenge toward its successful incorporation into high-performance nanoelectronics. It is imperative to achieve rapid and scalable production of MoS2 exhibiting high carrier mobility and excellent on/off current ratios simultaneously. Herein, inhibitor-utilizing atomic layer deposition (iALD) is presented as a novel method to meet these requirements at the wafer scale. The kinetics of the chemisorption of Mo precursors in iALD is governed by the reaction energy and the steric hindrance of inhibitor molecules. By optimizing the inhibition of Mo precursor absorption, the nucleation on the substrate in the initial stage can be spontaneously tailored to produce iALD-MoS2 thin films with a significantly increased grain size and surface coverage (>620%). Moreover, highly crystalline iALD-MoS2 thin films, with thicknesses of only a few layers, excellent room temperature mobility (13.9 cm2 V-1 s-1 ), and on/off ratios (>108 ), employed as the channel material in field effect transistors on 6″ wafers, are successfully prepared.

Microscopic Origin of the Valley Hall Effect in Transition Metal Dichalcogenides Revealed by Wavelength-Dependent Mapping.

The band structure of many semiconducting monolayer transition metal dichalcogenides (TMDs) possesses two degenerate valleys with equal and opposite Berry curvature. It has been predicted that, when illuminated with circularly polarized light, interband transitions generate an unbalanced nonequilibrium population of electrons and holes in these valleys, resulting in a finite Hall voltage at zero magnetic field when a current flows through the system. This is the so-called valley Hall effect that has recently been observed experimentally. Here, we show that this effect is mediated by photogenerated neutral excitons and charged trions and not by interband transitions generating independent electrons and holes. We further demonstrate an experimental strategy, based on wavelength dependent spatial mapping of the Hall voltage, which allows the exciton and trion contributions to the valley Hall effect to be discriminated in the measurement. These results represent a significant step forward in our understanding of the microscopic origin of photoinduced valley Hall effect in semiconducting transition metal dichalcogenides and demonstrate experimentally that composite quasi-particles, such as trions, can also possess a finite Berry curvature.

Self-Aligned Multichannel Graphene Nanoribbon Transistor Arrays Fabricated at Wafer Scale.

We present a novel method for fabricating large-area field-effect transistors (FETs) based on densely packed multichannel graphene nanoribbon (GNR) arrays using advanced direct self-assembly (DSA) nanolithography. The design of our strategy focused on the efficient integration of the FET channel and using fab-compatible processes such as thermal annealing and chemical vapor deposition. We achieved linearly stacked DSA nanopattern arrays with sub-10 nm half-pitch critical dimensions (CD) by controlling the thickness of topographic Au confinement patterns. Excellent roughness values (∼10% of CD) were obtained, demonstrating the feasibility of integrating sub-10 nm GNRs into commercial semiconductor processes. Based on this facile process, FETs with such densely packed multichannel GNR arrays were successfully fabricated on 6 in. silicon wafers. With these high-quality GNR arrays, we achieved FETs showing the highest performance reported to date (an on-to-off ratio larger than 10(2)) for similar devices produced using conventional photolithography and block-copolymer lithography.

Gate-induced superconductivity in atomically thin MoS2 crystals.

When thinned down to the atomic scale, many layered van der Waals materials exhibit an interesting evolution of their electronic properties, whose main aspects can be accounted for by changes in the single-particle bandstructure. Phenomena driven by interactions are also observed, but identifying experimentally systematic trends in their thickness dependence is challenging. Here, we explore the evolution of gate-induced superconductivity in exfoliated MoS2 multilayers ranging from bulk-like to individual monolayers. We observe a clear transition for all thicknesses down to the ultimate atomic limit, providing the first demonstration of gate-induced superconductivity in atomically thin exfoliated crystals. Additionally, we characterize the superconducting state by measuring the critical temperature TC and magnetic field BC in a large number of multilayer devices while decreasing their thickness. We find that the superconducting properties exhibit a pronounced reduction in TC and BC when going from bilayers to monolayers, for which we discuss possible microscopic mechanisms.

Electrostatically induced superconductivity at the surface of WS2.

We investigate transport through ionic liquid gated field effect transistors (FETs) based on exfoliated crystals of semiconducting WS2. Upon electron accumulation, at surface densities close to, or just larger than, 10(14) cm(-2), transport exhibits metallic behavior with the surface resistivity decreasing pronouncedly upon cooling. A detailed characterization as a function of temperature and magnetic field clearly shows the occurrence of a gate-induced superconducting transition below a critical temperature Tc ≈ 4 K, a finding that represents the first demonstration of superconductivity in tungsten-based semiconducting transition metal dichalcogenides. We investigate the nature of superconductivity and find significant inhomogeneity, originating from the local detaching of the frozen ionic liquid from the WS2 surface. Despite the inhomogeneity, we find that in all cases where a fully developed zero resistance state is observed, different properties of the devices exhibit a behavior characteristic of a Berezinskii-Kosterlitz-Thouless transition, as it could be expected in view of the two-dimensional nature of the electrostatically accumulated electron system.

Mono- and bilayer WS2 light-emitting transistors.

We have realized ambipolar ionic liquid gated field-effect transistors based on WS2 mono- and bilayers, and investigated their opto-electronic response. A thorough characterization of the transport properties demonstrates the high quality of these devices for both electron and hole accumulation, which enables the quantitative determination of the band gap (Δ1L = 2.14 eV for monolayers and Δ2L = 1.82 eV for bilayers). It also enables the operation of the transistors in the ambipolar injection regime with electrons and holes injected simultaneously at the two opposite contacts of the devices in which we observe light emission from the FET channel. A quantitative analysis of the spectral properties of the emitted light, together with a comparison with the band gap values obtained from transport, show the internal consistency of our results and allow a quantitative estimate of the excitonic binding energies to be made. Our results demonstrate the power of ionic liquid gating in combination with nanoelectronic systems, as well as the compatibility of this technique with optical measurements on semiconducting transition metal dichalcogenides. These findings further open the way to the investigation of the optical properties of these systems in a carrier density range much broader than that explored until now.

Structures and properties of poly(3-alkylthiophene) thin-films fabricated though vapor-phase polymerization.

Organic semiconducting polymer thin-films of 3-hexylthiophene, 3-octylthiophene, 3-decylthiophene, containing highly oriented crystal were fabricated by gas-phase polymerization using the CVD technique. These poly(3-alkylthiophene) films had a crystallinity up to 80%, and possessed a Hall mobility up to 10 cm2/Vs. The degree of crystalinity and the mobility values increased as the alkyl chain length increased. The crystal structure of the polymers was composed of stacked layers constructed by a side-by-side arrangement of alkyl chains and in-plane pi-pi stacking. These thin films are capable of being applied to organic electronics as the active materials used in thin-film transistors and organic photovoltaic cells.