Direct transformation of crystalline MoO3_3 into few-layers MoS2_2

We fabricate large-area atomically thin MoS$_2$ layers through the direct transformation of crystalline molybdenum MoS$_2$ (MoO$_3$) by sulfurization at relatively low temperatures. The obtained MoS2 sheets are polycrystalline (~10-20 nm single-crystal domain size) with areas of up to 300x300 um$^2$ with 2-4 layers in thickness and show a marked p-type behaviour. The synthesized films are characterized by a combination of complementary techniques: Raman spectroscopy, X-ray diffraction, transmission electron microscopy and electronic transport measurements.Comment: 6 figures in main text, 2 figures in supp. inf

Formation of titanium monoxide (001) single-crystalline thin film induced by ion bombardment of titanium dioxide (110)

© 2015 Macmillan Publishers Limited. All rights reserved. A plethora of technological applications justify why titanium dioxide is probably the most studied oxide, and an optimal exploitation of its properties quite frequently requires a controlled modification of the surface. Low-energy ion bombardment is one of the most extended techniques for this purpose and has been recently used in titanium oxides, among other applications, to favour resistive switching mechanisms or to form transparent conductive layers. Surfaces modified in this way are frequently described as reduced and defective, with a high density of oxygen vacancies. Here we show, at variance with this view, that high ion doses on rutile titanium dioxide (110) induce its transformation into a nanometric and single-crystalline titanium monoxide (001) thin film with rocksalt structure. The discovery of this ability may pave the way to new technical applications of ion bombardment not previously reported, which can be used to fabricate heterostructures and interfaces.Peer Reviewe

Hexagonal Hybrid Bismuthene by Molecular Interface Engineering

High-quality devices based on layered heterostructures are typically built from materials obtained by complex solid-state physical approaches or laborious mechanical exfoliation and transfer. Meanwhile, wet-chemically synthesized materials commonly suffer from surface residuals and intrinsic defects. Here, we synthesize using an unprecedented colloidal photocatalyzed, one-pot redox reaction a few-layers bismuth hybrid of “electronic grade” structural quality. Intriguingly, the material presents a sulfur-alkyl-functionalized reconstructed surface that prevents it from oxidation and leads to a tuned electronic structure that results from the altered arrangement of the surface. The metallic behavior of the hybrid is supported by ab initio predictions and room temperature transport measurements of individual nanoflakes. Our findings indicate how surface reconstructions in two-dimensional (2D) systems can promote unexpected properties that can pave the way to new functionalities and devices. Moreover, this scalable synthetic process opens new avenues for applications in plasmonics or electronic (and spintronic) device fabrication. Beyond electronics, this 2D hybrid material may be of interest in organic catalysis, biomedicine, or energy storage and conversion.This work has been supported by the European Union (ERC-2018-StG 804110-2D-PnictoChem & and ERC Proof of Concept Grant 101101079-2D4H2 to G.A.; ERC-2021-StG 101042680 2D-SMARTiES awarded to J.J.B.), the Spanish MICINN (PID2019-111742GA-I00, PID2020–115100GB–I00, MRR/PDC2022-133997-I00, TED2021-131347B-I00, and Excellence Unit María de Maeztu CEX2019-000919-M), and the Generalitat Valenciana (CIDEGENT/2018/001, CIDEGENT/2018/005, and CDEIGENT/2019/022). Financial support by Severo Ochoa centre of excellence program (CEX2021–001230–S) is gratefully acknowledged. M.K. and H.B.W. acknowledge support by the Deutsche Forschungsgemeinschaft (DFG), under Projektnummer 182849149 (SFB 953, projects B08 and B13). Electron microscopy work carried out at UCM (M.V., G.S.S.) sponsored by MICINN PID2021-122980OB-C51 and Comunidad de Madrid MAD2D-CM-UCM3. G.S.S. acknowledges financial support from Spanish MCI Grant Nos. RTI2018-099054-J-I00 (MCI/AEI/FEDER, UE) and IJC2018-038164-I. C.D. and Y.M.E. thank the cluster of excellence 3DMM2O funded by DFG under Germany’s Excellence Strategy – 2082/1 – 390761711 for financial support. The authors thank Lukas Grünwald and Erich Müller for helpful discussions. A.M.R. thanks the Spanish MIU (Grant No FPU21/04195). A.S.-D. thanks the Universidad de Valencia, for an ‘Atracción del talento’ predoctoral grant. F.G.-P. thanks ITQ, UPV–CSIC for concession of a contract (PAID 01-18)

Combining Freestanding Ferroelectric Perovskite Oxides with Two-Dimensional Semiconductors for High Performance Transistors

[EN] We demonstrate the fabrication of field-effect transistors based on single-layer MoS2 and a thin layer of BaTiO3 (BTO) dielectric, isolated from its parent epitaxial template substrate. Thin BTO provides an ultrahigh-κ gate dielectric effectively screening Coulomb scattering centers. These devices show mobilities substantially larger than those obtained with standard SiO2 dielectrics and comparable with values obtained with hexagonal boron nitride, a dielectric employed for fabrication of high-performance two-dimensional (2D) based devices. Moreover, the ferroelectric character of BTO induces a robust hysteresis of the current vs gate voltage characteristics, attributed to it polarization switching. This hysteresis is strongly suppressed when the device is warmed up above the tetragonal-to-cubic transition temperature of BTO that leads to a ferroelectric-to-paraelectric transition. This hysteretic behavior is attractive for applications in memory storage devices. Our results open the door to the integration of a large family of complex oxides exhibiting strongly correlated physics in 2D-based devices.European Research Council (ERC) through the project 2DTOPSENSE (GA 755655) European Union’sHorizon 2020 research and innovation program (Graphene Core2-Graphenebased disruptive technologies and Grant Agreement 881603 Graphene Core3-Graphene-based disruptive technologies) EU FLAG-ERA through the project To2Dox (JTC-2019-009) Comunidad de Madrid through the project CAIRO-CM project (Y2020/NMT-6661) Spanish Ministry of Science and Innovation through the projects PID2020-118078RBI00 RTI2018-099054-J-I00 and IJC2018-038164-I, PRE2018-084818 Key Research and Development Program of Shaanxi (Program No.2021KW-02).Peer reviewe

Direct visualization of local electromagnetic field structures by scanning transmission electron microscopy

Published as part of the Accounts of Chemical Research special issue “Direct Visualization of Chemical and Self-Assembly Processes with Transmission Electron Microscopy”.ConspectusThe functional properties of materials and devices are critically determined by the electromagnetic field structures formed inside them, especially at nanointerface and surface regions, because such structures are strongly associated with the dynamics of electrons, holes and ions. To understand the fundamental origin of many exotic properties in modern materials and devices, it is essential to directly characterize local electromagnetic field structures at such defect regions, even down to atomic dimensions. In recent years, rapid progress in the development of high-speed area detectors for aberration-corrected scanning transmission electron microscopy (STEM) with sub-angstrom spatial resolution has opened new possibilities to directly image such electromagnetic field structures at very high-resolution.In this Account, we give an overview of our recent development of differential phase contrast (DPC) microscopy for aberration-corrected STEM and its application to many materials problems. In recent years, we have developed segmented-type STEM detectors which divide the detector plane into 16 segments and enable simultaneous imaging of 16 STEM images which are sensitive to the positions and angles of transmitted/scattered electrons on the detector plane. These detectors also have atomic-resolution imaging capability. Using these segmented-type STEM detectors, we show DPC STEM imaging to be a very powerful tool for directly imaging local electromagnetic field structures in materials and devices in real space. For example, DPC STEM can clearly visualize the local electric field variation due to the abrupt potential change across a p-n junction in a GaAs semiconductor, which cannot be observed by normal in-focus bright-field or annular type dark-field STEM imaging modes. DPC STEM is also very effective for imaging magnetic field structures in magnetic materials, such as magnetic domains and skyrmions. Moreover, real-time imaging of electromagnetic field structures can now be realized through very fast data acquisition, processing, and reconstruction algorithms. If we use DPC STEM for atomic-resolution imaging using a sub-angstrom size electron probe, it has been shown that we can directly observe the atomic electric field inside atoms within crystals and even inside single atoms, the field between the atomic nucleus and the surrounding electron cloud, which possesses information about the atomic species, local chemical bonding and charge redistribution between bonded atoms. This possibility may open an alternative way for directly visualizing atoms and nanostructures, that is, seeing atoms as an entity of electromagnetic fields that reflect the intra- and interatomic electronic structures. In this Account, the current status of aberration-corrected DPC STEM is highlighted, along with some applications in real material and device studies.This work was supported by the SENTAN and PRESTO (JPMJPR11C5), JST and the JSPS KAKENHI Grant Number JP26289234 and JP17H01316. A part of this work was supported by Grant-in-Aid for Scientific Research on Innovative Areas “Nano Informatics” (JP25106003). A part of this work was conducted in Research Hub for Advanced Nano Characterization, the University of Tokyo, under the support of “Nanotechnology Platform” (Project No.12024046) by MEXT, Japan. This research was supported under the Discovery Projects funding scheme of the Australian Research Council (Project No. DP160102338)