We report the development and implementation of hybrid methods that combine quantum mechanics (QM) with molecular mechanics (MM) to theoretically characterize thiolated gold clusters. We use, as training systems, structures such as Au25(SCH2-R)18 and Au38(SCH2-R)24, which can be readily compared with recent crystallographic data. We envision that such an approach will lead to an accurate description of key structural and electronic signatures at a fraction of the cost of a full quantum chemical treatment. As an example, we demonstrate that calculations of the 1H and 13C NMR shielding constants with our proposed QM/MM model maintain the qualitative features of a full DFT calculation, with an order-of-magnitude increase in computational efficiency.
Monolayer AlB$_2$ is composed of two atomic layers: honeycomb borophene and triangular aluminum. In contrast with the bulk phase, monolayer AlB$_2$ is predicted to be a superconductor with a high critical temperature. Here, we demonstrate that monolayer AlB$_2$ can be synthesized on Al(111) via molecular beam epitaxy. Our theoretical calculations revealed that the monolayer AlB$_2$ hosts several Dirac cones along the $Γ$--M and $Γ$--K directions; these Dirac cones are protected by crystal symmetries and are thus resistant to external perturbations. The extraordinary electronic structure of the…
Two-dimensional (2D) half-metallic materials are of great interest for their promising applications in spintronics. Although numerous of 2D half-metals have been proposed theoretically, rarely of them can be synthesized experimentally. Here, exemplified by monolayer FeCl2, we show three mechanisms in such quantum magnets that would cause the metal-insulator transition by using first-principles calculations. In particular, half-metallicity, especially that protected by symmetry-induced degeneracies, predicted by the previous theoretical simulations could be destroyed by electron correlation, sp…
Materials can, in principle, be imaged at the level of individual atoms with aberration corrected transmission electron microscopy. However, such resolution can be attained only with very high electron doses. Consequently, radiation damage is often the limiting factor when characterizing sensitive materials. Here, we demonstrate a simple and effective method to increase the electron radiation tolerance of materials by using graphene as protective coating. This leads to an improvement of three orders of magnitude in the radiation tolerance of monolayer MoS2. Further on, we construct samples in …
Giant magnetization of polyalanine monolayers on gold observed in resent years along with unusual large spin selectivity, the potential of the film and its temperature dependence are all explained in the context of vacuum polarization at the gold-monolayer interface. The enhancement is directly related to the fine structure constant, and involves a change in basic physical parameters including changes in the permeability of the vacuum and in the local zero point energy of the gold monolayer interface. Formation of an ordered state by the self-assembly process and the interaction of the monolay…
The optical selection rules obeyed by two-dimensional materials with spin-valley coupling enable the selective excitation of carriers. We show that six members of the monolayer MA2Z4 (M = Mo and W; A = C, Si, and Ge; Z = N, P, and As) family are direct band-gap semiconductors with protected valley states and that circularly polarized infrared light can induce valley-selective inter-band transitions. Our optovalleytronic device demonstrates a close to 100% valley- and spin-polarized current under in-plane bias and circularly polarized infrared light, which can be exploited to encode, process, a…
The picosecond thermal response of a normal octadecanethiol self-assembled monolayer on a gold surface was studied using pump-probe, broadband-infrared, background-suppressed and vibrational sum frequency generation spectroscopy. The orientation fluctuations in response to flash heating were characterized from the intensity kinetics of the terminal methyl C-H stretching vibrations. An intensity decrease (5.7 +/- 1.3 ps) in the asymmetric modes indicated that stochastic processes of molecular conformations developed during multiple light-matter interactions. Including torsional diffusion into t…
The application of graphene in electronic devices requires large scale epitaxial growth. The presence of the substrate, however, usually reduces the charge carrier mobility considerably. We show that it is possible to decouple the partially sp3-hybridized first graphitic layer formed on the Si-terminated face of silicon carbide from the substrate by gold intercalation, leading to a completely sp2-hybridized graphene layer with improved electronic properties.
Real-Space Plasmon Imaging Reveals Modified Electronic Structure of Gold at the Monolayer Limit
CIC nanoGUNE BRTA；Chalmers University of Technology（查尔姆斯理工大学）；Linköping University（林雪平大学）；Max Planck Institute for Solid State Research（马克斯·普朗克固体研究所）；MAX IV Laboratory, Lund University（隆德大学 MAX IV 实验室）；Donostia International Physics Center（圣塞巴斯蒂安国际物理中心）；IKERBASQUE, Basque Foundation for Science（伊卡巴斯基克，巴斯克科学基金会）；Facultad de Ciencias Químicas, Universidad del País Vasco UPV-EHU（巴斯克国立大学 UPV-EHU 理学院化学系）；Department of Electricity and Electronics, University of the Basque Country (UPV/EHU)（巴斯克国立大学 (UPV/EHU) 电力与电子工程系）
Machine learning (ML) force fields are one of the most common applications of ML methods in the field of physical and chemical science. In the optimal case, they are able to reach accuracy close to the first principles methods with significantly lowered computational cost. However, often the training of the ML methods rely on full atomic structures alongside their potential energies, and applying the force information needs special modifications to standard algorithms. Here we apply distance-based ML methods to predict force norms and estimate the directions of the force vectors of the thiolat…
Nonsymmorphic space group symmetries can generate exotic band-crossings in topological metals and semimetals. Here, based on symmetry analysis and first-principles calculations, we reveal rich band-crossing features in the existing layered compounds Ta$_3$SiTe$_6$ and Nb$_3$SiTe$_6$, enabled by nonsymmorphic symmetries. We show that in the absence of spin-orbit coupling (SOC), these three-dimensional (3D) bulk materials possess accidental Dirac loops and essential fourfold nodal lines. In the presence of SOC, there emerges an hourglass Dirac loop---a fourfold degenerate nodal loop, on which ea…
The magnetic properties of a monolayer of Fe4 single molecule magnets grafted onto a Au (111) thin film have been investigated using low energy muon spin rotation. The properties of the monolayer are compared to bulk Fe4. We find that the magnetic properties in the monolayer are consistent with those measured in the bulk, strongly indicating that the single molecule magnet nature of Fe4 is preserved in a monolayer. However, differences in the temperature dependencies point to a small difference in their energy scale. We attribute this to a ~60% increase in the intramolecular magnetic interacti…
Monolayer WTe$_2$, a centrosymmetric transition metal dichacogenide, has recently been established as a quantum spin Hall insulator and found superconducting upon gating. Here we study the pairing symmetry and topological nature of superconducting WTe$_2$ with a microscopic model at mean-field level. Surprisingly, we find that the spin-triplet phases in our phase diagram all host Majorana modes localized on two opposite corners. Even when the conventional pairing is favored, we find that an intermediate in-plane magnetic field exceeding the Pauli limit stabilizes an unconventional equal-spin p…
Gold-mediated exfoliation of MoS2 has attracted considerable interest in the recent years. A strong interaction between MoS2 and Au facilitates preferential production of centimeter-sized monolayer MoS2 with near-unity yield and provides a heterostructure system noteworthy from a fundamental standpoint. However, little is known about the detailed nature of the MoS2-Au interaction and its evolution with the MoS2 thickness. Here, we identify specific vibrational and binding energy fingerprints of such strong interaction using Raman and X-ray photoelectron spectroscopy, which indicate substantial…
We present a study of quasi-free-standing monolayer graphene obtained by intercalation of Au atoms at the interface between the carbon buffer layer (Bu-L) and the silicon-terminated face (0001) of 4H-silicon carbide. Au intercalation is achieved by deposition of atomically thin Au on the Bu-L followed by annealing at 850 °C in an Argon atmosphere. We explore the intercalation of Au and decoupling of the Bu-L into quasi-free-standing monolayer graphene by surface science characterizations and electron transport in top-gated electronic devices. By gate-dependent magnetotransport we find that the…
The electronic structure of two-dimensional (2D) materials are inherently prone to environmental perturbations, which may pose significant challenges to their applications in electronic or optoelectronic devices. A 2D material couples with its environment through two mechanisms: local chemical coupling and nonlocal dielectric screening effects. The local chemical coupling is often difficult to predict or control experimentally. Nonlocal dielectric screening, on the other hand, can be tuned by choosing the substrates or layer thickness in a controllable manner. Therefore, a compelling 2D electr…
Ultrastrong Au-Te bonding drives disorder in monolayer ZrTe$_5$ on gold
Hungarian Research Network, HUN-REN Centre for Energy Research, Institute of Technical Physics and Materials Science（匈牙利研究网络，HUN-REN能源研究中心，技术物理与材料科学研究所）；MTA - HUN-REN EK Lendület “Momentum” Topology in Nanomaterials Research Group（MTA-HUN-REN EK Lendulet“动量”纳米材料拓扑研究组）；Budapest University of Technology and Economics（布达佩斯技术与经济大学）；ELTE Eötvös Loránd University（罗兰大学）
Sub-10 nm continuous metal films are promising candidates for flexible and transparent nanophotonics and optoelectronics applications. In this Letter, we demonstrate that monolayer MoS2 is a perspective adhesion layer for the deposition of continuous conductive gold films with a thickness of only 3-4 nm. Optical properties of continuous ultrathin gold films deposited on two-dimensional MoS2 grown by chemical vapor deposition are investigated by spectroscopic ellipsometry over a wide wavelength range (300-3300 nm). Results show that optical losses in ultrathin films increase with decreasing thi…
We evidence the possibility for coherent electrical manipulation of the spin orientation of topologically protected edge states in a low-symmetry quantum spin Hall insulator. By using a combination of ab-initio simulations, symmetry-based modeling, and large-scale calculations of the spin Hall conductivity, it is shown that small electric fields can efficiently vary the spin textures of edge currents in monolayer 1T'-WTe2 by up to a 90-degree spin rotation, without jeopardizing their topological character. These findings suggest a new kind of gate-controllable spin-based device, topologically …
Structural phase transitions between semiconductors and topological insulators have rich applications in nanoelectronics but are rarely found in two-dimensional (2D) materials. In this work, by combining ab initio computations and evolutionary structure search, we investigate two stable 2D forms of gold(I) telluride (Au$_{2}$Te) with square symmetry, noted as s(I)- and s(II)-Au$_{2}$Te. s(II)-Au$_{2}$Te is the global minimum structure and is a room-temperature topological insulator. s(I)-Au$_{2}$Te is a direct-gap semiconductor with high carrier mobilities and unusual in-plane negative Poisson…
By means of the first-principles calculations and magnetic topological quantum chemistry, we demonstrate that the low energy physics in the checkerboard antiferromagnetic (AFM) monolayer FeSe, very close to an AFM topological insulator that hosts robust edge states, can be well captured by a double-degenerate fragile topologically flat band just below the Fermi level. The Wilson loop calculations identify that such fragile topology is protected by the $S_{4z}$ symmetry, which gives rise to an AFM higher-order topological insulator that support the bound state with fractional charge $e/2$ at th…
Emergent gold-induced interfacial magnetism in monolayer FePS$_3$
European Synchrotron Radiation Facility（欧洲同步辐射装置）；Université Grenoble Alpes, CNRS, Grenoble INP, Institut NEEL（格勒诺布尔阿尔卑斯大学、法国国家科学研究中心、格勒诺布尔理工学院、NEEL研究所）；Department of Physics Giuseppe Occhialini, University of Milano-Bicocca（米兰比可卡大学朱塞佩·奥基亚利尼物理系）；Université Grenoble Alpes, CEA, IRIG, MEM（格勒诺布尔阿尔卑斯大学、法国原子能和替代能源委员会、研究与信息技术部、材料与物理化学实验室）
In this paper we demonstrated the thermal Atomic Layer Deposition (ALD) growth at 250 °C of highly homogeneous and ultra-thin ($\approx$ 3.6 nm) $Al_2O_3$ films with excellent insulating properties directly onto a monolayer (1L) $MoS_2$ membrane exfoliated on gold. Differently than in the case of 1L $MoS_2$ supported by a common insulating substrate ($Al_2O_3/Si$), a better nucleation process of the high-k film was observed on the 1L $MoS_2/Au$ system since the ALD early stages. Atomic force microscopy analyses showed a $\approx 50\%$ $Al_2O_3$ surface coverage just after 10 ALD cycles, its in…
We have investigated the radical functionalization of gold surfaces with a derivative of the perchlorotriphenylmethyl (PTM) radical, using two methods: by chemisorption from the radical solution and by on surface chemical derivatization from a precursor. We have investigated the obtained self-assembled monolayers by photon-energy dependent X-ray photoelectron spectroscopy. Our results show that the molecules were successfully anchored on the surfaces. The monolayers are characterized by air and beam stability unprecedented for films of organic radicals. Over very long beam exposure we observed…
Ultrathick MA$_2$N$_4$(M'N) Intercalated Monolayers with Sublayer-Protected Fermi Surface Conduction States: Interconnect and Metal Contact Applications
Growth of two-dimensional van der Waals layered single-crystal (SC) films is highly desired to manifest intrinsic material sciences and unprecedented devices for industrial applications. While wafer-scale SC hexagonal boron nitride film has been successfully grown, an ideal growth platform for diatomic transition metal dichalcogenide (TMdC) film has not been established to date. Here, we report the SC growth of TMdC monolayers in a centimeter scale via atomic sawtooth gold surface as a universal growth template. Atomic tooth-gullet surface is constructed by the one-step solidification of liqui…
Gold-assisted mechanical exfoliation currently represents a promising method to separate ultra-large (cm-scale) transition metal dichalcogenides (TMDs) monolayers (1L) with excellent electronic and optical properties from the parent van der Waals (vdW) crystals. The strong interaction between $Au$ and chalcogen atoms is the key to achieve this nearly perfect 1L exfoliation yield. On the other hand, it may affect significantly the doping and strain of 1L TMDs in contact with Au. In this paper, we systematically investigated the morphology, strain, doping, and electrical properties of large area…
Using ab-initio computational techniques on crystal determined clusters, we report on the similarities and differences of Al$_{50}$(C$_5$(CH$_3)_5)_{12}$, Ga$_{23}$(N(Si(CH$_3)_{3}$)$_{2}$)$_{11}$, and Au$_{102}$(SC$_7$O$_2$H$_5$)$_{44}$ ligand-protected clusters. Each of the ligand-protected clusters in this study show the similar stable character which can be described via a electronic shell model. We show here that the same type of analysis leads consistently to derive a superatomic electronic counting rule, independently of the metal and ligand compositions. One can define the cluster core…
The Au25(SR)18- cluster is a new member in the superatom family which features a centered icosahedral shell (Au13) protected by six RS(AuSR)2 motifs (RS- being a alkylthiolate group). Here we show that this superatom can be magnetically doped by replacing the center Au atom with Cr, Mn, or Fe. We find that Cr and Mn-doped clusters have an optimized magnetic moment of 5 Bohr magnetons while the Fe-doped cluster has an optimized magnetic moment of 3 Bohr magnetons. Although the dopant atom's local magnetic moment makes a major contribution to the total moment, the icosahedral Au12 shell is also …
We have studied the excitonic properties of exfoliated tungsten diselenide (WSe$_2$) monolayers transferred to gold substrates using the tunneling current in a Scanning Tunneling Microscope (STM) operated in air to excite the light emission locally. In obtained spectra, emission energies are independent of the applied bias voltage and resemble photoluminescence (PL) results, indicating that, in both cases, the light emission is due to neutral and charged exciton recombination. Interestingly, the electron injection rate, that is, the tunneling current, can be used to control the ratio of charge…
To explore new materials for the realization of the quantum anomalous Hall effect (QAHE), we studied electronic, magnetic and topological properties of transition-metal phthalocyanine (TMPc) monolayers in a square lattice. Many of them have large topologically nontrivial band gaps and integer Chern numbers. In particular, the Fermi level of MoPc lies right in the band gap (Eg=8.1 meV) and has large magnetic anisotropy energy (MAE=2.0 meV per Mo atom) and a Curie temperature of 16 K, showing its usefulness for applications. The presence of topologically protected edge state in a MoPc nanoribbon…
Geometry, electronic structure, and magnetic properties of methylthiolate-stabilized Au$_{25}$L$_{18}$ and MnAu$_{24}$L$_{18}$ (L = SCH$_3$) clusters adsorbed on noble-metal (111) surfaces have been investigated by using spin-polarized density functional theory computations. The interaction between the cluster and the surface is found to be mediated by charge transfer mainly from or into the ligand monolayer. The electronic properties of the 13-atom metal core remain in all cases rather undisturbed as compared to the isolated clusters in gas phase. The Au$_{25}$L$_{18}$ cluster retains a clear…
A grand unified model (GUM) has been proposed recently to understand structure anatomy and evolution of liganded gold clusters. In this work, besidesthe two types of elementary blocks (triangular Au3(2e) and tetrahedral Au4(2e)), we introduce a secondary block, namely, the icosahedral Au13 with 8e valence electrons, noted as Au13(8e). Using this secondary block, structural anatomy and evolution of a special group of liganded gold nanoclusters containing icosahedral Au13 motifs can be conveniently analyzed. In addition, a new ligand-protected cluster Au49(PR3)10(SR)15Cl2 is predicted to exhibit…
Quadratic band crossing points (QBCPs) and quantum anomalous Hall effect (QAHE) have attracted the attention of both theoretical and experimental researchers in recent years. Based on first-principle calculations, we find that the FeB$_2$ monolayer is a nonmagnetic semimetal with QBCPs at $K$. Through symmetry analysis and $\mathbf{k}\cdot\mathbf{p}$ invariant theory, we find that the QBCP is not protected by rotation symmetry and consists of two Dirac points with same chirality (Berry phase of $2π$). Once introducing Coulomb interactions, we find that there is a spontaneous-time-reversal-brea…
The intriguing properties, especially Dirac physics in graphene, have inspired the pursuit of two-dimensional materials in honeycomb structure. Here we achieved a monolayer transition metal monochalcogenide AgTe on Ag(111) by tellurization of the substrate. High-resolution scanning tunneling microscopy, combined with low-energy electron diffraction, angle-resolved photoemission spectroscopy, and density functional theory calculations, demonstrates the planar honeycomb structure of AgTe. The first principle calculations further reveal that, protected by the in-plane mirror reflection symmetry, …
We report one-pot chemical vapor deposition (CVD) growth of large-area Janus SeMoS monolayers, with the asymmetric top (Se) and bottom (S) chalcogen atomic planes with respect to the central transition metal (Mo) atoms. The formation of these two-dimensional semiconductor monolayers takes place upon the thermodynamic equilibrium-driven exchange of the bottom Se atoms of the initially grown MoSe2 single crystals on gold foils with S atoms. The growth process is characterized by complementary experimental techniques including Raman and X-ray photoelectron spectroscopy and the growth mechanisms a…
Quantum spin Hall (QSH) materials are two-dimensional systems exhibiting insulating bulk and helical edge states simultaneously. A QSH insulator processes topologically non-trivial edge states protected by time-reversal symmetry, so that electrons can propagate unscattered. Realization of such topological phases enables promising applications in spintronics, dissipationless transport and quantum computations. Presently, realization of such QSH-based devices are limited to complicated heterostructures. Monolayer 1T'-WTe2 was predicted to be semimetallic QSH materials, though with a negative ban…
Based on first-principles calculations and tight-binding model analysis, we propose monolayer graphdiyne as a candidate material for a two-dimensional higher-order topological insulator protected by inversion symmetry. Despite the absence of chiral symmetry, the higher-order topology of monolayer graphdiyne is manifested in the filling anomaly and charge accumulation at two corners. Although its low energy band structure can be properly described by the tight-binding Hamiltonian constructed by using only the $p_z$ orbital of each atom, the corresponding bulk band topology is trivial. The nontr…
The search for new quantum spin Hall (QSH) phase and effective manipulations of their edge states are very important for both fundamental sciences and practical applications. Here, we use first-principles calculations to study the strain-driven topological phase transition of two-dimensional (2D) arsenene monolayer. We find that the band gap of arsenene decreases with increasing strain and changes from indirect to direct, and then the s-p band inversion takes place at Γ point as the tensile strain is larger than 11.14%, which lead to a nontrivially topological state. A single pair of topologic…
Using density functional theory calculations and the Greens's function formalism, we report the existence of magnetic edge states with a non-collinear spin texture present on different edges of the 1T' phase of the three monolayer transition metal dichalcogenides (TMDs): MoS$_2$, MoTe$_2$ and WTe$_2$. The magnetic states are gapless and accompanied by a spontaneous breaking of the time-reversal symmetry. This may have an impact on the prospects of utilizing WTe$_2$ as a quantum spin Hall insulator. It has previously been suggested that the topologically protected edge states of the 1T' TMDs co…
Gold intercalation between the buffer layer and a graphene monolayer of epitaxial graphene on SiC(0001) leads to the formation of quasi free standing small aggregates of clusters. Angle Resolved Photoemission Spectroscopy measurements reveal that these clusters preserve the linear dispersion of the graphene quasiparticles and surprisingly increase their Fermi velocity. They also strongly modify the band structure of graphene around the Van Hove singularities (VHs) by a strong extension without charge transfer. This result gives a new insight on the role of the intercalant in the renormalizatio…
Quantum spin Hall (QSH) insulators possess edge states that are topologically protected from backscattering. However, known QSH materials (e.g. HgTe/CdTe and InAs/GaSb quantum wells) exhibit very small energy gap and only work at low temperature, hindering their applications for room temperature devices. Based on the first-principles calculations, we predict a novel family of QSH insulators in monolayer tantalum carbide halide TaCX (X = Cl, Br, and I) with unique rectangular lattice and large direct energy gaps larger than 0.2 eV, accurately, 0.23$-$0.36 eV. The mechanism for 2D QSH effect in …
Transition metal dichalcogenide monolayers such as MoSe2,MoS2 and WSe2 are direct bandgap semiconductors with original optoelectronic and spin-valley properties. Here we report spectrally sharp, spatially localized emission in monolayer MoSe2. We find this quantum dot like emission in samples exfoliated onto gold substrates and also suspended flakes. Spatial mapping shows a correlation between the location of emitters and the existence of wrinkles (strained regions) in the flake. We tune the emission properties in magnetic and electric fields applied perpendicular to the monolayer plane. We ex…
Nontrivial band topology combined with magnetic ordering can produce quantum anomalous Hall insulator (QAHI), which may lead to advances in device concepts. Here, through first-principles calculations, stable monolayer $\mathrm{Fe_2Br_2}$ is predicted as a room-temperature large-gap high-Chern-number QAHI by using generalized gradient approximation plus $U$ (GGA+$U$) approach. The large gap is due to correlation-enhanced spin-orbit coupling (SOC) effect of Fe atoms, which equates with artificially increasing the strength of SOC without electronic correlation. Out-of-plane magnetic anisotropy i…
