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Continuous advancement in nonvolatile and morphotropic beyond-Moore electronic devices requires integration of ferroelectric and semiconductor materials. The emergence of hafnium oxide (HfO 2 )–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 HfO 2 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.

Fluorite-structure ferroelectrics — in particular the orthorhombic phase of HfO2 — are of paramount interest to academia and industry because they show unprecedented scalability down to 1-nm-thick size and are compatible with Si electronics. However, their polarization switching is believed to be limited by the intrinsically high energy barrier of ferroelectric domain wall (DW) motions. Here, by unveiling a new topological class of DWs, we establish an atomic-scale mechanism of polarization switching in orthorhombic HfO2 that exhibits unexpectedly low energy barriers of DW motion (up to 35-fold lower than given by previous conjectures). These findings demonstrate that the nucleation-and-growth-based mechanism is feasible, challenging the commonly held view that the rapid growth of the oppositely polarized domain is impossible. Building on this insight, we describe a strategy to substantially reduce the coercive fields in HfO2-based ferroelectric devices. Our work is a crucial step towards understanding the polarization switching of HfO2, which could provide a means to solve the key problems associated with operation speed and endurance.

This study investigates, numerically, the spatial distribution of metastable helium (He*) in He/SiH4 capacitively coupled plasma (CCP) for the purpose of optimizing plasma density distributions. As a first step, we presented the results of a two-dimensional fluid model of He discharges, followed by those of He/SiH4 discharges to deposit hydrogenated amorphous silicon films, to investigate which factor dominates the coating uniformity. We retained our CCPs in the 300 mm wafer reactor used by the semiconductor industry in the recent past. Selected parameters, such as a sidewall gap (radial distance between the electrode edge and the sidewall), electrical condition of the sidewall, and position of the powered electrode, were considered. In addition, by increasing the gas pressure while varying the sidewall condition, we observed modification of the plasma distributions and, thus, the deposition rate profiles. According to the results, the shift in He* distributions was mainly due to the reduction in the electron mean free path under conditions of gas pressure higher than 100 Pa, as well as local perturbations in the ambipolar electric field due to the finite electrode structure. Small additions of SiH4 largely changed the He* density profile in the midplane of the discharge due to He* quenching. Furthermore, we found that the wide sidewall gap did not improve deposition uniformity against the expectation. This was because the excitation and ionization rate profiles were enhanced and localized only near the bottom electrode edge.

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, with 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 the ferroelectric memories from the history of conventional approaches to the future prospects. This article is protected by copyright. All rights reserved.

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 Hf0.5Zr0.5O2 under the AFM tip.

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 BiFeO

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.

In this work, we report sub-ns polarization switching in highly scaled 25 nm ferroelectric (FE) FinFET with Hf 0.5 Zr 0.5 O 2 (HZO) ferroelectric (FE)/SiO 2 dielectric (DE) gate stack for high performance CPU application for the first time. Observed limited endurance was attributed to the increase of trap density in the stack, which was quantitatively analyzed upon program/erase cycles by various methods including newly adopted low-frequency noise (LFN) characteristics for resolving spatial and energetic distribution of traps. In particular, we identified three different types of traps at FE/DE interface (D it_2 ) and SiO 2 /Si channel interface (D it_1 ) as well as in the bulk oxide (N ot ) of the HZO/SiO 2 gate stack of FE FinFETs. In addition, with the developed trap analysis, we investigated radiation-induced degradation of HZO/SiO 2 gate stack for application under harsh environments. Highly scaled and high performance FE FinFETs with enhanced endurance would provide a viable solution for future platform of low-power computing.

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.

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.

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 band structure. 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 the thicknesses down to the ultimate atomic limit, providing the first demonstration of 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, upon decreasing their thickness. The superconducting properties change smoothly down to bilayers, and a pronounced reduction in TC and BC is found to occur when going from bilayers to monolayers, for which we discuss possible microscopic mechanisms. Finding that gate-induced superconductivity persists in individual monolayers, which form the basic building blocks of more sophisticated van der Waals heterostructures, opens new possibilities for the engineering of the electronic properties of materials at the atomic scale., Originally submitted version, in compliance with editorial regulations. Final version to appear in Nature Nanotechnology

Recent discovery of ferroelectricity from non-centrosymmetric orthorhombic phase (Pca21) of Hf/Zr oxides [1] has brought enormous research interests and activities because the material compatibility with CMOS process and its scalability to a few nm thickness, which have been critical issues for introducing perovskites ferroelectric (FE) materials in nanoscale devices. Physical concept of “negative capacitance” in FE materials when stacked with dielectrics (DE) has been proposed to enhance the total capacitance larger than that of DE only [2,3] and has been demonstrated in DE-FE stacks such as Al2O3/Hf0.5Zr0.5O2 or Ta2O5/Hf0.5Zr0.5O2 via transient measurement [4,5]. However, stacks with amorphous Al2O3 DE layer having relatively low dielectric constant were vulnerable to irreversible charge injection from electrodes into the DE-FE interface and thus hysteresis-free operation of the capacitor was only limited to short pulse condition below 1μs. Also Ta2O5 DE layer is often found to be defective and the film easily becomes leaky with repeated cycles. Here we propose novel DE-FE stack based on all crystallized Hf/Zr oxides where polymorphic Hf/Zr oxides have three dominant phases, monoclinic (P21/c), orthorhombic (Pca21), and tetragonal (P42/nmc) and by varying parameters such as Zr composition and thickness in initial amorphous film, the oxides can be crystallized in phase-selective way. We employ the tetragonal phase of Hf/Zr oxide for DE layer which possesses high-k value above 30 and wide bandgap about 5.4 eV ensuring low leakage current and further enabling thickness scaling. All crystallized DE-FE stacks were fabricated on bottom electrodes via atomic layer deposition of Hf/Zr oxides with compositional variation and subsequent metal deposition and post-metallization-annealing. Electrical data from capacitance vs. voltage and polarization vs. voltage measurements manifests an intermediate characteristic between ferroelectric and anti-ferroelectric ones due to multi-phase layers. Pulsed voltage measurements and structural analyses with XRD and selective area electron diffraction will be presented to assess the proposed stack for devices with enhanced capacitance. References [1] T. S. Boske, J.Muller, D. Brauhaus, U. Schroder, and U. Bottger, Applied Physics Letters 99, 102903 (2011). [2] S. Salahuddin, and S. Datta, Nano Letters 8, 2, 405-410 (2008). [3] H. W. Park, J. Roh, Y. B. Lee, and C. S. Hwang, Advanced Materials 31, 32, 1805266 (2019). [4] K. D. Kim, Y. J. Kim, M. H. Park, H. W. Park, Y. J. Kwon, Y. B. Lee, H. J. Kim, T. Moon, Y. H. Lee, S. D. Hyun, B. S. Kim, and C. S. Hwang, Advanced Functional Materials 29, 17, 1808228 (2019). [5] M. Hoffmann, F. P. G. Fengler, M. Herzig, T. Mittmann, B. Max, U. Schroeder, R. Negrea, P. Lucian, S. Slesazeck, and T. Micholajick, Nature 565, 464-467 (2019). Figure 1

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 non-equilibrium 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 photo-generated neutral excitons and charged trions, and not by inter-band 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 photo-induced 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., accepted for publication in Nano Letters

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.

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.

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.

A spin injection is achieved in a direct-contact cobalt$\ensuremath{-}$single-layer graphene nonlocal spin-valve system, overlaid with a top gate. The spin signal is retained even in bipolar configurations of graphene. Hanle spin-precession analysis demonstrates that proportionality between spin and momentum relaxation times, which supports the Elliot-Yafet-type spin relaxation, holds consistently only when the carrier-density dependence of the density of states is taken into account. The corresponding strong spin-orbit coupling ($\ensuremath{\sim}$10 meV) suggests that covalently bonded adsorbates, rather than charged impurities, govern the spin relaxation in diffusive graphene.

In this study, we determined the chiral direction of the quantum-Hall (QH) edge states in graphene by adopting simple two-terminal conductance measurements while grounding different edge positions of the sample. The edge state with a smaller filling factor is found to more strongly interact with the electric contacts. This simple method can be conveniently used to investigate the chirality of the QH edge state with zero filling factor in graphene, which is important to understand the symmetry breaking sequence in high magnetic fields ($\gtrsim$25 T)., Comment: 3 pages, 3 figures. Appeared in APL

One of the points at issue with closed-loop-type interferometers is beating in the Aharonov-Bohm (AB) oscillations. Recent observations suggest the possibility that the beating results from the Berry-phase pickup by the conducting electrons in materials with the strong spin-orbit interaction (SOI). In this study, we also observed beats in the AB oscillations in a gate-defined closed-loop interferometer fabricated on a GaAs/Al{sub 0.3}Ga{sub 0.7}As two-dimensional electron-gas heterostructure. Since this heterostructure has very small SOI, the picture of the Berry-phase pickup is ruled out. The observation of beats in this study, with the controllability of forming a single transverse subband mode in both arms of our gate-defined interferometer, also rules out the often-claimed multiple transverse subband effect. It is observed that nodes of the beats with an h/2e period exhibit a parabolic distribution for varying the side gate. These results are shown to be well interpreted, without resorting to the SOI effect, by the existence of two-dimensional multiple longitudinal modes in a single transverse subband. The Fourier spectrum of measured conductance, despite showing multiple h/e peaks with the magnetic-field dependence that are very similar to that from strong-SOI materials, can also be interpreted as the two-dimensional multiple-longitudinal-modes effect.

A consistent approach in forming the 0.7 structure by using a quantum dot rather than a quantum point contact is demonstrated. With this scheme, it was possible to tune on and off the 0.7 structure. The 0.7 structure continuously evolved into a normal integer conductance plateau by varying the tuning condition. Unlike the conventional 0.7 plateau, the new 0.7 structure was observed even at low electron temperatures down to $100\phantom{\rule{0.3em}{0ex}}\mathrm{mK}$, with unprecedented flatness. From our results, it is concluded that electron interference should be taken into consideration to explain the 0.7 structure.

Improved conductive poly(3,4-ethylenedioxy thiophene) (PEDOT) electrode films were made through hybridization with charged gold nanoparticles. The conductivity of these hybrid films increased more than seven times than the value for the PEDOT alone. The optimized films show a sheet resistance value down to 85 ohm·sq−1 at 85% transparency when PEDOT was hybridized with gold particles of 12 nm diameter, and the organic light-emitting diode devices deposited on these electrodes show a performance equivalent to that of devices based on a conventional indium tin oxide electrode.

We investigate transport through ionic liquid gated field effect transistors (FETs) based on exfoliated crystals of semiconducting WS$_2$. 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 $T_c \approx 4$ 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 WS$_2$ 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., 18 pages, 4 figures; Nano Letters (2015)

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 ({\Delta}1L = 2.14 eV for monolayers and {\Delta}2L = 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., Comment: 22 pages, 6 figures, Nano Letters (2014)

We perform scanning photocurrent microscopy on WS2 ionic liquid-gated field effect transistors exhibiting high-quality ambipolar transport. By properly biasing the gate electrode, we can invert the sign of the photocurrent showing that the minority photocarriers are either electrons or holes. Both in the electron- and hole-doping regimes the photocurrent decays exponentially as a function of the distance between the illumination spot and the nearest contact, in agreement with a two-terminal Schottky-barrier device model. This allows us to compare the value and the doping dependence of the diffusion length of the minority electrons and holes on a same sample. Interestingly, the diffusion length of the minority carriers is several times larger in the hole accumulation regime than in the electron accumulation regime, pointing out an electron-hole asymmetry in WS2. (C) 2014 AIP Publishing LLC.