Metal and magnetic overlayers alter the surface of the topological insulator (TI) bismuth selenide (Bi$_2$Se$_3$) through proximity effects but also by changing the composition and chemical structure of the Bi$_2$Se$_3$ sub-surface. The interface between Bi$_2$Se$_3$ and Mn metal or manganese selenide was explored using x-ray photoelectron spectroscopy (XPS) revealing chemical and electronic changes at the interface. Depositing Mn metal on Bi$_2$Se$_3$ without an external source of Se shows unexpected bonding within the Mn layer due to Mn-Se bonding as Se diffuses out of the Bi$_2$Se$_3$ layer into the growing Mn film. The Se out-diffusion is further evidenced by changes in Bi core levels within the Bi$_2$Se$_3$ layers indicating primarily Bi-Bi bonding over Bi-Se bonding. No out-diffusion of Se occurred when excess Se is supplied with Mn, indicating the importance of supplying enough chalcogen atoms with deposited metals. However, Bi$_2$Se$_3$ core level photoelectrons exhibited a rigid chemical shift toward higher binding energy after depositing a monolayer of MnSe$_{2-x}$, indicating a dipole within the overlayer. Stoichiometry calculations indicated that the monolayer forms MnSe preferentially over the transition metal dichalcogenide (TMD) phase MnSe$_2$, providing a consistent picture of the dipole formation in which a plane of Se anions sits above Mn cations. This study shows that chemical diffusion and dipole formation are important for Mn-Bi$_2$Se$_3$ and MnSe$_{2-x}$-Bi$_2$Se$_3$ and should be considered carefully for TMD/TI interfaces more generally.
The application of new materials in nanotechnology opens new perspectives and enables ground-breaking innovations. Two-dimensional van der Waals materials and more specific, 2D chalcogenides are a promising class of new materials awaiting their usage in the semiconductor industry. However, the integration of van der Waals materials relying on industry-compatible manufacturing processes is still a major challenge. This is currently restricting the application of these new materials to the research laboratories environment only. The large-area and single-crystalline growth of van der Waals mater…
Defect-free epitaxial growth of 2D materials is one of the holy grails for a successful integration of van der Waals (vdW) materials in the semiconductor industry. The large-area (quasi-)vdW epitaxy of layered 2D chalcogenides is consequently carefully being researched since these materials hold very promising properties for future nanoelectronic applications. The formation of defects such as stacking faults like 60o twins and consequently 60o grain boundaries is still of major concern for the defect-free epitaxial growth of 2D chalcogenides. Although growth strategies to overcome the occurren…
Formation of femtosecond laser direct-written positive refractive index waveguides in Gallium Lanthanum Sulphide (GLS) glass is explained for the first time. Evidence of structural changes and ion migration are presented using Raman spectroscopy and electron probe microanalysis (EPMA), respectively. 2-D Raman spectra maps reveal a peak shift and full-width at half maximum variations in the symmetric vibrations of GaS4 main band. For the first time, the 2D map of the boson band was successfully used to identify and understand the material densification profile in a high refractive index glass w…
Novel materials with nontrivial electronic and photonic band topology are crucial for realizing novel devices with low power consumption and heat dissipation, and quantum computing free of decoherence. Here using first-principles approach, we predict a class of ternary transition metal chalcogenides (TTMC) MM'Te$_4$ exhibits dual topological characteristics: quantum spin Hall (QSH) insulators in their 2D monolayers and topological Weyl semimetals in their 3D noncentrosymmetric crystals upon van der Waals (vdW) stacking. Remarkably, we find that one can create and annihilate Weyl fermions, and …
Molecular Beam Epitaxy of Mn2In2Se5 van der Waals Layers Using Mn Intercalation
Two Dimensional Crystal Consortium Materials Innovation Platform, The Pennsylvania State University（二维晶体联盟材料创新平台，宾夕法尼亚州立大学）；Materials Research Institute, The Pennsylvania State University（材料研究所，宾夕法尼亚州立大学）；Department of Materials Science and Engineering, The Pennsylvania State University（材料科学与工程系，宾夕法尼亚州立大学）；Institute of Energy and the Environment, The Pennsylvania State University（能源与环境研究所，宾夕法尼亚州立大学）
Identifying Highly Deformable van der Waals Layered Chalcogenides with Superior Thermoelectric Performance Using Deformability Factors and Interpretable Machine Learning
Kinetically accessible 1D magnetic chains of transition-metal chalcogenides and halides on van der Waals surfaces
Key Laboratory of Quantum State Construction and Manipulation (Ministry of Education), Renmin University of China（中国人民大学量子态构建与操控教育部重点实验室）；College of Physics and Electronic Engineering, Center for Computational Sciences, Sichuan Normal University（四川师范大学物理电子工程学院计算科学中心）；College of Physics and Optoelectronic Engineering, Shenzhen University（深圳大学物理与光电工程学院）
The identification of alternatives to the Lithium-ion battery architecture remains a crucial priority in the diversification of energy storage technologies. Accompanied by the low reduction potential of $\mathrm{Ca^{2+}/Ca}$, -2.87 V vs. SHE, metal-anode-based rechargeable Calcium (Ca) batteries appear competitive in terms of energy densities. However, the development of Ca-batteries lacks high-energy density intercalation cathode materials. Using first-principles methodologies, we screen a large chemical space for potential Ca-based cathode chemistries, with composition of $\mathrm{Ca_iTM_jZ_…
Materials with van der Waals-bonding are known to exhibit quantum confinement effect, in which the electronic bandgap of the three-dimensional (3D) realization of a material is lower than that of its two-dimensional (2D) counterpart. However, the possibility of an anomalous quantum confinement effect (AQCE) exists, where the bandgap trend is reversed. In this work, we computationally identify materials for which such AQCE occurs. Using density functional theory (DFT), we compute ~1000 OptB88vdW (semi-local functional), ~50 HSE06 and ~50 PBE0 (hybrid functional) bandgaps for bulk and their corr…
Semiconductor heterostructures are the fundamental platform for many important device applications such as lasers, light-emitting diodes, solar cells and high-electron-mobility transistors. Analogous to traditional heterostructures, layered transition metal dichalcogenide (TMDC) heterostructures can be designed and built by assembling individual single-layers into functional multilayer structures, but in principle with atomically sharp interfaces, no interdiffusion of atoms, digitally controlled layered components and no lattice parameter constraints. Nonetheless, the optoelectronic behavior o…
Tetradymite-structured chalcogenides such as bismuth telluride Bi_{2}Te_{3} are of significant interest for thermoelectric energy conversion and as topological insulators. Dislocations play a critical role during synthesis and processing of such materials and can strongly affect their functional properties. The dislocations between quintuple layers present special interest since their core structure is controlled by the van der Waals interactions between the layers. In this work, using atomic-resolution electron microscopy, we resolve the basal dislocation core structure in Bi_{2}Te_{3}, quant…
We predict a new family of robust two-dimensional (2D) topological insulators in van der Waals heterostructures comprising graphene and chalcogenides BiTeX (X=Cl, Br and I). The layered structures of both constituent materials produce a naturally smooth interface that is conducive to proximity induced new topological states. First principles calculations reveal intrinsic topologically nontrivial bulk energy gaps as large as 70-80 meV, which can be further enhanced up to 120 meV by compression. The strong spin-orbit coupling in BiTeX has a significant influence on the graphene Dirac states, res…
Poor electrical conductivity and large volume expansion during repeated charge and discharge is what has characterized many battery electrode materials in current use. This has led to 2D materials, specifically multi-layered 2D systems, being considered as alternatives. Among these 2D multi-layered systems are the graphene-based van der Waals heterostructures with transition metal di-chalcogenides (TMDCs) as one of the layers. Thus in this study, graphene-Hafnium disulphide (Gr-HfS$_2$) system, has been investigated as a prototype Gr-TMDC system for application as battery electrode. Density fu…
Ternary chalcogenides, having large crystalline unit cell and van der Waal stacking of layers, are expected to be poor thermal conductors and good thermoelectric (TE) materials. We are reporting that layered Bi4GeTe7, with alternating quintuplet-septuplet layers of Bi2Te3 and Bi2GeTe4, has an ultralow thermal conductivity, \k{appa}total 0.42 Wm-1K-1 because of high degree of anharmonicity as estimated from large Gruneisen parameter (γ 4.07) and low Debye temperature (θd 135 K). The electron dominated charge transport has been realized from the Seebeck coefficient, S - 82 uV/K, at 380 K, and Ha…
The van der Waals layered material CuInP2S6 features interesting functional behavior, including the existence of four uniaxial polarization states, polarization reversal against the electric field through Cu ion migration, a negative-capacitance regime, and reversible extraction of Cu ions. At the heart of these characteristics lies the high mobility of Cu ions, which also determines the spontaneous polarization. Therefore, Cu migration across the lattice results in unusual ferroelectric behavior. Here, we demonstrate how the interplay of polar and ionic properties provides a path to ionically…
The lattice thermal expansion and conductivity in bulk Mo and W-based transition metal dichalcogenides are investigated by means of density functional and Boltzmann transport theory calculations. To this end, a recent van der Waals density functional (vdW-DF-CX) is employed, which is shown to yield excellent agreement with reference data for the structural parameters. The calculated in-plane thermal conductivity compares well with experimental room temperature values, when phonon-phonon and isotopic scattering are included. To explain the behavior over the entire available temperature range on…
The naturally existing chalcogenide Bi2Se3 is topologically nontrivial due to the band inversion caused by strong spin-orbit coupling inside the bulk of the material. The surface states are spin polarized, protected by the time-inversion symmetry, and thus robust to the scattering caused by non-magnetic defects. A high purity topological insulator thin film can be easily grown via molecular beam epitaxy (MBE) on various substrates to enable novel electronics, optics, and spintronics applications. However, the unique surface state properties have historically been limited by the film quality, w…
Quasi-two-dimensional (2D) films of layered metal-chalcogenides have attractive optoelectronic properties. However, photonic applications of thin films may be limited owing to weak light absorption and surface effects leading to reduced quantum yield. Integration of 2D films in optical microcavities will permit these limitations to be overcome owing to modified light coupling with the films. Here we present tunable microcavities with embedded monolayer MoS2 or few monolayer GaSe films. We observe significant modification of spectral and temporal properties of photoluminescence (PL): PL is emit…
Two-dimensional (2D) materials have recently been the focus of extensive research. By following a similar trend as graphene, other 2D materials including transition metal dichalcogenides (MX2) and metal mono-chalcogenides (MX) show great potential for ultrathin nanoelectronic and optoelectronic devices. Despite the weak nature of interlayer forces in semiconducting MX materials, their electronic properties are highly dependent on the number of layers. Using scanning tunneling microscopy and spectroscopy (STM/STS), we demonstrate the tunability of the quasiparticle energy gap of few layered gal…
The synthesis of new materials with novel or useful properties is one of the most important drivers in the fields of condensed matter physics and materials science. Discoveries of this kind are especially significant when they point to promising future basic research and applications. Van der Waals bonded materials comprised of lower-dimensional building blocks have been shown to exhibit emergent properties when isolated in an atomically thin form1-8. Here, we report the discovery of a transition metal chalcogenide in a heretofore unknown segmented linear chain form, where basic building block…
Two-dimensional (2D) van der Waals semiconductors represent the thinnest, air stable semiconducting materials known. Their unique optical, electronic and mechanical properties hold great potential for harnessing them as key components in novel applications for electronics and optoelectronics. However, the charge transport behavior in 2D semiconductors is more susceptible to external surroundings (e.g. gaseous adsorbates from air and trapped charges in substrates) and their electronic performance is generally lower than corresponding bulk materials due to the fact that surface and bulk coincide…
By breaking the restrictions on traditional alloying strategy, the high entropy concept has promoted the exploration of the central area of phase space, thus broadening the horizon of alloy exploitation. This review highlights the marriage of the high entropy concept and van der Waals systems to form a new family of materials category, namely the high entropy van der Waals materials (HEX, HE = high entropy, X= anion clusters) and describe the current issues and next challenges. The design strategy for HEX has integrated the local feature (e.g., composition, spin, and valence states) of structu…
Half-metallic ferrimagnetism is crucial for spintronic applications with respect to ferromagnets due to the lower stray fields created by these materials. Studying the effect of defects in CrAs and related transition-metal chalcogenides and pnictides crystallizing in the zinc-blende structure, we reveal that the excess of the transition-metal atoms leads to half-metallic ferrimagnetism. The surplus of these atoms are antiferromagnetically coupled to the transition-metal atoms sitting at the perfect lattice sites. The needed condition to achieve half-metallic ferrimagnetism is to prevent the mi…
The electronic structure in unconventional superconductors holds a key to understand the momentum-dependent pairing interactions and the resulting superconducting gap function. In superconducting Fe-based chalcogenides, there have been controversial results regarding the importance of the $k_z$ dependence of the electronic dispersion, the gap structure and the pairing mechanisms of iron-based superconductivity. Here, we present a detailed investigation of the van der Waals interaction in FeSe and its interplay with magnetic disorder and real space structural properties. Using density functiona…
Correlated electron systems on a honeycomb lattice have emerged as a fertile playground to explore exotic electronic phenomena. Theoretical and experimental work has appeared to realize novel behavior, including quantum Hall effects and valleytronics, mainly focusing on van der Waals compounds, such as graphene, chalcogenides, and halides. In this article, we review our theoretical study on perovskite transition-metal oxides (TMOs) as an alternative system to realize such exotic phenomena. We demonstrate that novel quantum Hall effects and related phenomena associated with the honeycomb struct…
It was generally assumed that weak van der Waals interactions exist between neighboring layers in the two-dimensional group-IV chalcogenides. Using PbSe as a prototypal example, however, we find additional strong coupling between the Pb-Pb layers, as evidenced by detailed analysis of the differential charge density. The coupling resembles covalent-like bond and exhibits strong harmonicity around the equilibrium distance, which can be fine tuned to obviously reduce the phonon thermal conductivity but slightly change the electronic transport of PbSe. As a consequence, a maximum ZT value of 2.5 c…
Two-dimensional (2D) crystals have renewed opportunities in design and assembly of artificial lattices without the constraints of epitaxy. However, the lack of thickness control in exfoliated van der Waals (vdW) layers prevents realization of repeat units with high fidelity. Recent availability of uniform, wafer-scale samples permits engineering of both electronic and optical dispersions in stacks of disparate 2D layers with multiple repeating units. We present optical dispersion engineering in a superlattice structure comprised of alternating layers of 2D excitonic chalcogenides and dielectri…
Understanding the electronic transport properties of layered, van der Waals transition metal halides (TMHs) and chalcogenides is a highly active research topic today. Of particular interest is the evolution of those properties with changing thickness as the 2D limit is approached. Here, we present the electrical conductivity of exfoliated single crystals of the TMH, cluster magnet, Nb3Cl8, over a wide range of thicknesses both with and without hexagonal boron nitride (hBN) encapsulation. The conductivity is found to increase by more than three orders of magnitude when the thickness is decrease…
Orbital mixing and strong Hund's coupling stabilize spin order in van der Waals ferromagnet CrI3
Technische Universität Berlin（柏林工业大学）；Fritz Haber Institute of the Max Planck Society（马克斯·普朗克学会弗里茨·哈伯研究所）；Vinča Institute of Nuclear Sciences - National Institute of the Republic of Serbia, University of Belgrade（贝尔格莱德大学文查核科学研究所）；ESRF, The European Synchrotron（欧洲同步辐射装置）；Politecnico di Milano（米兰理工大学）；Consiglio Nazionale delle Ricerche CNR-IOM, Unità di Trieste（国家研究委员会CNR-IOM的里雅斯特分部）；University of Milan-Bicocca（米兰比可卡大学）；Consiglio Nazionale delle Ricerche CNR-SPIN, c/o Università degli Studi ‘G. D’Annunzio’（国家研究委员会CNR-SPIN，挂靠阿布鲁佐大学）
Tunable Nanostructuring for van der Waals Materials
XPANCEO；King’s College London（伦敦国王学院）；University of Chemistry and Technology Prague（布拉格化工大学）；Aix-Marseille Université（艾克斯-马赛大学）；Leibniz Universität Hannover（汉诺威莱布尼茨大学）；The University of Manchester（曼彻斯特大学）；National Graphene Institute（国家石墨烯研究所）；National University of Singapore（新加坡国立大学）；Chongqing 2D Materials Institute（重庆二维材料研究院）
Plasmonics currently faces the problem of seemingly inevitable optical losses occurring in the metallic components that challenges the implementation of essentially any application. In this work we show that Ohmic losses are reduced in certain layered metals, such as the transition metal dichalcogenide TaS$_2$, due to an extraordinarily small density of states for scattering in the near-IR originating from their special electronic band structure. Based on this observation we propose a new class of band structure engineered van der Waals layered metals composed of hexagonal transition metal cha…
Moiré-induced symmetry breaking of charge order in van der Waals heterostructures
Donostia International Physics Center (DIPC)（圣塞巴斯蒂安国际物理中心）；Institute of Theoretical Physics, University of Hamburg（汉堡大学理论物理研究所）；Department of Physics, Indian Institute of Science Education and Research Bhopal（博帕尔印度科学教育研究系物理系）；The Hamburg Centre for Ultrafast Imaging（汉堡超快成像中心）；Centro de Física de Materiales (CSIC-UPV/EHU)（材料物理中心（西班牙国家科研委员会-巴斯克国立大学/巴斯克国立理工大学））；Max Planck Institute for the Structure and Dynamics of Matter（马克斯·普朗克物质结构与动力学研究所）；Yusuf Hamied Department of Chemistry, University of Cambridge（剑桥大学尤瑟夫·哈米德化学系）；Dept. Polymers and Advanced Materials, University of the Basque Country (UPV/EHU)（巴斯克国立大学（UPV/EHU）聚合物与先进材料系）；Ikerbasque, Basque Foundation for Science（伊克拉巴斯科，巴斯克科学基金会）
