Solution Adsorption Formation of a π‐Conjugated Polymer/Graphene Composite for High‐Performance Field‐Effect Transistors

Semiconducting polymers with π‐conjugated electronic structures have potential application in the large‐scale printable fabrication of high‐performance electronic and optoelectronic devices. However, owing to their poor environmental stability and high‐cost synthesis, polymer semiconductors possess limited device implementation. Here, an approach for constructing a π‐conjugated polymer/graphene composite material to circumvent these limitations is provided, and then this material is patterned into 1D arrays. Driven by the π–π interaction, several‐layer polymers can be adsorbed onto the graphene planes. The low consumption of the high‐cost semiconductor polymers and the mass production of graphene contribute to the low‐cost fabrication of the π‐conjugated polymer/graphene composite materials. Based on the π‐conjugated system, a reduced π–π stacking distance between graphene and the polymer can be achieved, yielding enhanced charge‐transport properties. Owing to the incorporation of graphene, the composite material shows improved thermal stability. More generally, it is believed that the construction of the π‐conjugated composite shows clear possibility of integrating organic molecules and 2D materials into microstructure arrays for property‐by‐design fabrication of functional devices with large area, low cost, and high efficiency.     

Dirac Semimetal Heterostructures: 3D Cd3As2 on 2D Graphene

Dirac semimetal is an emerging class of quantum matters, ranging from 2D category, such as, graphene and surface states of topological insulator to 3D category, for instance, Cd₃As₂ and Na₃Bi. As 3D Dirac semimetals typically possess Fermi‐arc surface states, the 2D–3D Dirac van der Waals heterostructures should be promising for future electronics. Here, graphene–Cd₃As₂ heterostructures are fabricated through direct layer‐by‐layer stacking. The electronic coupling results in a notable interlayer charge transfer, which enables us to modulate the Fermi level of graphene through Cd₃As₂. A planar graphene p–n–p junction is achieved by selective modification, which demonstrates quantized conductance plateaus. Moreover, compared with the bare graphene device, the graphene–Cd₃As₂ hybrid device presents large nonlocal signals near the Dirac point due to the charge transfer from the spin‐polarized surface states in the adjacent Cd₃As₂. The results enrich the family of van der Waals heterostructure and should inspire more studies on the application of Dirac/Weyl semimetals in spintronics.     

Coulomb Interaction Effect in Quantum Transport

We study the quantum Anderson model in the presence of the finite Coulomb interaction U using the t-matrix approximation. The energy of the d-electron level increases as Uln (U/πΔ) for strong Coulomb interaction U and finite level-width Δ. In the case of small U/Δ parameter this approximation gives the results from the perturbation theory. The spin susceptibility is calculated as a function of U and compared with the results obtained by renormalized perturbation approximation. The results can be used to study the effect of the finite Coulomb interaction in the quantum transport.     

Single‐Crystalline Nanobelts Composed of Transition Metal Ditellurides

Following the celebrated discovery of graphene, considerable attention has been directed toward the rich spectrum of properties offered by van der Waals crystals. However, studies have been largely limited to their 2D properties due to lack of 1D structures. Here, the growth of high‐yield, single‐crystalline 1D nanobelts composed of transition metal ditellurides at low temperatures (T ≤ 500 °C) and in short reaction times (t ≤ 10 min) via the use of tellurium‐rich eutectic metal alloys is reported. The synthesized semimetallic 1D products are highly pure, stoichiometric, structurally uniform, and free of defects, resulting in high electrical performances. Furthermore, complete compositional tuning of the ternary ditelluride nanobelts is achieved with suppressed phase separation, applicable to the creation of unprecedented low‐dimensional materials/devices. This approach may inspire new growth/fabrication strategies of 1D layered nanostructures, which may offer unique properties that are not available in other materials.     

外尔半金属TaAs单晶的研究进展

外尔半金属是当两个自旋非简并能带在三维动量空间通过费米能级附近时,其低能准粒子激发具有外尔费米子的所有特征的一类材料体系。外尔费米子是狄拉克方程的无质量解,可以看作是在三维空间一对重叠在一起且具有相反手性的粒子。TaAs单晶作为一种非磁性的外尔半金属,在其中能够观测到外尔费米子,并产生许多奇异的物理现象,如费米弧、负磁阻效应、量子反常霍尔效应等,使其在发展新型电子器件和拓扑量子计算等领域有着重要应用潜力。介绍了外尔半金属的相关基础理论和重要实验,重点探讨了TaAs单晶生长相关的技术问题,分析了化学气相传输法的优缺点。     

Covalent Functionalization of Dipole‐Modulating Molecules on Trilayer Graphene: An Avenue for Graphene‐Interfaced Molecular Machines

The molecular dipole moment plays a significant role in governing important phenomena like molecular interactions, molecular configuration, and charge transfer, which are important in several electronic, electrochemical, and optoelectronic systems. Here, the effect of the change in the dipole moment of a tethered molecule on the carrier properties of (functionalized) trilayer graphene—a stack of three layers of sp²‐hybridized carbon atoms—is demonstrated. It is shown that, due to the high carrier confinement and large quantum capacitance, the trans‐to‐cis isomerisation of ‘covalently attached’ azobenzene molecules, with a change in dipole moment of 3D, leads to the generation of a high effective gating voltage. Consequently, 6 units of holes are produced per azobenzene molecule (hole density increases by 440 000 holes μm^?2). Based on Raman and X‐ray photoelectron spectroscopy data, a model is outlined for outer‐layer, azobenzene‐functionalized trilayer graphene with current modulation in the inner sp² matrix. Here, 0.097 V are applied by the isomerisation of the functionalized azobenzene. Further, the large measured quantum capacitance of 72.5 μF cm^?2 justifies the large Dirac point in the heavily doped system. The mechanism defining the effect of dipole modulation of covalently tethered molecules on graphene will enable future sensors and molecular‐machine interfaces with graphene.     

Asymmetric 3D Elastic–Plastic Strain‐Modulated Electron Energy Structure in Monolayer Graphene by Laser Shocking

Graphene has a great potential to replace silicon in prospective semiconductor industries due to its outstanding electronic and transport properties; nonetheless, its lack of energy bandgap is a substantial limitation for practical applications. To date, straining graphene to break its lattice symmetry is perhaps the most efficient approach toward realizing bandgap tunability in graphene. However, due to the weak lattice deformation induced by uniaxial or in‐plane shear strain, most strained graphene studies have yielded bandgaps <1 eV. In this work, a modulated inhomogeneous local asymmetric elastic–plastic straining is reported that utilizes GPa‐level laser shocking at a high strain rate (dε/dt) ≈ 10⁶–10⁷ s^?1, with excellent formability, inducing tunable bandgaps in graphene of up to 2.1 eV, as determined by scanning tunneling spectroscopy. High‐resolution imaging and Raman spectroscopy reveal strain‐induced modifications to the atomic and electronic structure in graphene and first‐principles simulations predict the measured bandgap openings. Laser shock modulation of semimetallic graphene to a semiconducting material with controllable bandgap has the potential to benefit the electronic and optoelectronic industries.     

Band Structure Perfection and Superconductivity in Type‐II Dirac Semimetal Ir1−xPtxTe2

The discovery of a new type‐II Dirac semimetal in Ir_1?xPt_xTe₂ with optimized band structure is described. Pt dopants protect the crystal structure holding the Dirac cones and tune the Fermi level close to the Dirac point. The type‐II Dirac dispersion in Ir_1?xPt_xTe₂ is confirmed by angle‐resolved photoemission spectroscopy and first‐principles calculations. Superconductivity is also observed and persists when the Fermi level aligns with the Dirac points. Ir_1?xPt_xTe₂ is an ideal platform for further studies on the exotic properties and potential applications of type‐II DSMs, and opens up a new route for the investigation of the possible topological superconductivity and Majorana physics.     

Fabrication of Millimeter‐Scale,Single‐Crystal One‐Third‐Hydrogenated Graphene with Anisotropic Electronic Properties

Periodically hydrogenated graphene is predicted to form new kinds of crystalline 2D materials such as graphane, graphone, and 2D C_xH_y, which exhibit unique electronic properties. Controlled synthesis of periodically hydrogenated graphene is needed for fundamental research and possible electronic applications. Only small patches of such materials have been grown so far, while the experimental fabrication of large‐scale, periodically hydrogenated graphene has remained challenging. In the present work, large‐scale, periodically hydrogenated graphene is fabricated on Ru(0001). The as‐fabricated hydrogenated graphene is highly ordered, with a √3 × √3/R30° period relative to the pristine graphene. As the ratio of hydrogen and carbon is 1:3, the periodically hydrogenated graphene is named “one‐third‐hydrogenated graphene” (OTHG). The area of OTHG is up to 16 mm². Density functional theory calculations demonstrate that the OTHG has two deformed Dirac cones along one high‐symmetry direction and a finite energy gap along the other directions at the Fermi energy, indicating strong anisotropic electrical properties. An efficient method is thus provided to produce large‐scale crystalline functionalized graphene with specially desired properties.     

Thermodynamics of the Frustrated 2D Hubbard Model

The thermodynamic properties of the quarter filled 2D Hubbard model extended by next-nearest-neighbor (NNN) hopping have been studied in an exact diagonalization method on a tilted square cluster. The NNN hopping interaction (i.e. frustration) is prominent at the low-temperature region. A positive (negative) diagonal hopping t′ favors (suppresses) double occupancy and hence decreases (increases) local moment. At higher temperatures thermal excitations favor the formation of doublans against the strong Coulomb repulsion U and the weak diagonal hopping, hence decreasing local moment. A two-peak structure is observed in the specific heat curves with the inclusion of negative NNN hopping. The low-T peak in specific heat is highly suppressed in comparison to the high-T peak. It has also been argued that t′ influences the ‘pseudogap’ energy scale. In the present case of quarter filling, a weak and short range antiferromagnetic order is present at very low temperatures, which is slightly suppressed (enhanced) by positive (negative) t′. The effect of t′ is more pronounced in the non-interacting limit.     

Tunable quantum Shubnikov-de Hass oscillations in antiferromagnetic topological semimetal Mn-doped Cd3As2

Three-dimensional Dirac semimetal Cd3As2 has been considered as an excellent candidate for applica-tions of electronic devices owing to its ultrahigh mobility and air-stability.However,current researches are focused mainly on the use of gate-voltage to control its carrier transport tunability,while the manipulation of transport properties by element-doping is quite limited.Here we report the tunable magneto-transport properties by adjusting Mn-doping in the Cd3As2 compound.We find that Mn-element doping has a strong influence on the Fermi level positions,and the Fermi energy approaches to Dirac point with higher Mn-doping.More importantly,the introduction of Mn atoms transforms dia-magnetic Cd3As2 to antiferromagnetic(Cd,Mn)3As2,which provides an approach to control topological protected Dirac materials by manipulating antiferromagnetic order parameters.The Shubnikov-de Hass oscillation originates from the surface states,and the Landau fan diagram yields a nontrivial Berry phase,indicating the existence of massless Dirac fermions in the(Cd1-xMnx)3As2 compounds.Our present results may pave a way for further investigating antiferromagnetic topological Dirac semimetal and expand the potential applications in optoelectronics and spintronics.     

Emergence of Pairing Interaction in the Hubbard Model in the Strong Coupling Limit

We implement the rotationally-invariant formulation of the two-dimensional Hubbard model, with nearest-neighbors hopping t, which allows for the analytic study of the system in the low-energy limit. Both U(1) and SU(2) gauge transformations are used to factorize the charge and spin contribution to the original electron operator in terms of the corresponding gauge fields. The Hubbard Coulomb energy U-term is then expressed in terms of quantum phase variables conjugate to the local charge and variable spin quantization axis, providing a useful representation of strongly correlated systems. It is shown that these gauge fields play a similar role as phonons in the BCS theory: they act as the “glue” for fermion pairing. By tracing out gauge degrees of freedom the form of paired states is established and the strength of the pairing potential is determined. It is found that the attractive pairing potential in the effective low-energy fermionic action is non-zero in a rather narrow range of U/t.     

Probing Defect‐Induced Midgap States in MoS2 Through Graphene–MoS2 Heterostructures

Crystalline defects in MoS₂ may induce midgap states, resulting in low carrier mobility. These midgap states are usually difficult to probe by conventional transport measurement. The quantum capacitance of single‐layer graphene is sensitive to defect‐induced states near the Dirac point, at which the density of states is extremely low. It is reported that the hexagonal‐boron nitride/graphene/MoS₂ sandwich structure facilitates the exploration of the properties of those midgap states in MoS₂. Comparative results of the quantum capacitance of pristine graphene indicate the presence of several midgap states with distinct features. Some of these states donate electrons while some states lead to localization of electrons. It is believed that these midgap states originate from intrinsic point defects such as sulfur vacancies, which have a significant impact on the property of the MoS₂/graphene interface. They are responsible for the contact problems of metal/MoS­₂ interfaces.     

The Accelerating World of Graphdiynes

Graphdiyne (GDY), a 2D allotrope of graphene, is first synthesized in 2010 and has attracted attention as a new low‐dimensional carbon material. This work surveys the literature on GDYs. The history of GDYs is summarized, including their relationship with 2D graphyne carbons and yearly publication trends. GDY is a molecule‐based nanosheet woven from a molecular monomer, hexaethynylbenzene; thus, it is synthesized by bottom‐up approaches, which allow rich variation via monomer design. The GDY family and the synthetic procedures are also described. Highly developed π‐conjugated electronic structures are common important features in GDY and graphene; however, the coexistence of sp and sp² carbons differentiates GDY from graphene. This difference gives rise to unique physical properties, such as high conductivity and large carrier mobility. Next, the theoretical and experimental studies of these properties are described in detail. A wide variety of applications are proposed for GDYs, including electrocatalysts and energy devices, which exploit the carbon‐rich nature, porous framework, and expanded π‐electron system of these compounds. Finally, potential uses are discussed.     

First-Principles Investigation of Electronic Structure Features of TbOFeAs Compound

We report a theoretical investigation on the electronic and magnetic properties of rare-earth pnictide parent compound, such as TbOFeAs. Employing first-principles method supplemented by the local spin density approximation (LSDA), we discuss the electronic structure with the incorporation of the role of Coulomb on-site repulsion (U) of Tb 4f states as well as the spin-orbit (SO) coupling on the magnetic and nonmagnetic phases. For ferromagnetic (FM) and antiferromagnetic (AFM) phases, we have determined the spin and orbital magnetic moments of Tb ions and confer the significance of the spin-orbit interaction of Tb 4f states in this parent compound. In the FM state, the reduction of Fe moment is about a factor of 3.5 with respect to AFM configuration. The most energetically favorable state is AFM configuration. Our theoretical findings surmise that the magnetic moments on Fe sites carry an AFM order. Based on LSDA + U + SO approximation, we infer that the Tb magnetic moments also carry an AFM order, albeit the spin Tb sites in TbO layer possess the same orientation as the Fe spins in FeAs layer. With the incorporation of on-site Coulomb repulsion and spin-orbit interaction in AFM state, the Fe 3d states are large near the Fermi level and this phase is illustrating a metallic behavior. Moreover, the Fermi surface topology and nesting features are presented.     

Functionalization of low-dimensional honeycomb germanium with 3d transition-metal atoms

The energetics, electronic and magnetic properties of 3d transition-metal (TM) atoms adsorbed low-dimensional Ge honeycomb structures have been systematically investigated from the spin-polarized density-functional theory calculations. For the two-dimensional Ge honeycomb structure, all TM atoms considered prefer to adsorb on the hollow site of the buckled hexagon in both single-sided and double-sided adsorption cases, with binding energies ranging between 3.27 and 5.92 eV. Upon adsorption, the semimetallic 2D honeycomb Ge can change to either ferromagnetic or antiferromagnetic metals depending on both TM species and coverage density. For the one-dimensional structure, we found binding of TM atoms to hollow site of the edge hexagon yields the minimum energy state for all TM species considered and in all three AGeNRs examined which belong to different families. Depending on ribbon width, adsorbed TM species and adsorption concentration, most of the TM decorated AGeNRs can either be metals or semiconductors with ferromagnetic or antiferromagnetic spin alignment, except for Co-adsorbed ones which remain to be nonmagnetic. Interestingly, Cr or Mn adsorption can make certain AGeNRs to be half-metallic with a 100% spin-polarization at Fermi level which can be good candidates for future application in spintronic fields. Furthermore, the effect of the on-site Coulomb interaction on the stability of these half-metallic ribbons is also considered by performing L(S)DA + U calculations, and the results show that the half-metallic ground state of the Cr-adsorbed ribbons is more robust than that of the Mn-adsorbed one.     

Linear Dichroism and Nondestructive Crystalline Identification of Anisotropic Semimetal Few‐Layer MoTe2

Semimetal 1T′ MoTe₂ crystals have attracted tremendous attention owing to their anisotropic optical properties, Weyl semimetal, phase transition, and so on. However, the complex refractive indices (n‐ik) of the anisotropic semimetal 1T′ MoTe₂ still are not revealed yet, which is important to applications such as polarized wide spectrum detectors, polarized surface plasmonics, and nonlinear optics. Here, the linear dichroism of as‐grown trilayer 1T′ MoTe₂ single crystals is investigated. Trilayer 1T′ MoTe₂ shows obvious anisotropic optical absorption due to the intraband transition of d_z² orbits for Mo atoms and p_x orbits for Te atoms. The anisotropic complex refractive indices of few‐layer 1T′ MoTe₂ are experimentally obtained for the first time by using the Pinier equation analysis. Based on the linear dichroism of 1T′ MoTe₂, angle‐resolved polarized optical microscopy is developed to visualize the grain boundary and identify the crystal orientation of 1T′ MoTe₂ crystals, which is also an excellent tool toward the investigation of the optical absorption properties in the visible range for anisotropic 2D transition metal chalcogenides. This work provides a universal and nondestructive method to identify the crystal orientation of anisotropic 2D materials, which opens up an opportunity to investigate the optical application of anisotropic semimetal 2D materials.     

25th Anniversary Article: High‐Mobility Hole and Electron Transport Conjugated Polymers: How Structure Defines Function

The structural organization of three different families of semicrystalline π‐conjugated polymers is reported (poly(3‐hexylthiophene) (P3HT), poly[2,6‐(4,4‐bis‐alkyl‐4H‐cyclopenta‐[2,1‐b;3,4‐b0]‐dithiophene)‐alt‐4,7‐(2,1,3‐benzothiadiazole)](cyclopentadithiophene‐benzothiadiazole) (CDT‐BTZ) and poly(N,N"‐bis‐2‐octyldodecylnaphtalene‐1,4,5,8‐bis‐dicarboximide‐2,6‐diyl‐alt‐5,5–2,2‐bithiophene (P(NDI2OD‐T2))). These have triggered significant interest for their remarkable charge‐transport properties. By performing molecular mechanics/dynamics simulations with carefully re‐parameterized force fields, it is illustrated in particular how the supramolecular organization of these conjugated polymers is driven by an interplay between the length and nature of the conjugated monomer unit and the packing of their alkyl side chains, and to what extent it impacts the charge‐carrier mobility, as monitored by quantum‐chemical calculations of the intermolecular hopping transfer integrals. This Progress Report is concluded by providing generic guidelines for the design of materials with enhanced degrees of supramolecular organization.     

Patterning nanoroads and quantum dots on fluorinated graphene

Using ab initio methods we have investigated the fluorination of graphene and find that different stoichiometric phases can be formed without a nucleation barrier, with the complete “2D-Teflon” CF phase being thermodynamically most stable. The fluorinated graphene is an insulator and turns out to be a perfect matrix-host for patterning nanoroads and quantum dots of pristine graphene. The electronic and magnetic properties of the nanoroads can be tuned by varying the edge orientation and width. The energy gaps between the highest occupied and lowest unoccupied molecular orbitals (HOMO-LUMO) of quantum dots are size-dependent and show a confinement typical of Dirac fermions. Furthermore, we study the effect of different basic coverage of F on graphene (with stoichiometries CF and C₄F) on the band gaps, and show the suitability of these materials to host quantum dots of graphene with unique electronic properties.     

In Situ Electrochemical Synthesis and Deposition of Discotic Hexa‐peri‐hexabenzocoronene Molecules on Electrodes: Self‐Assembled Structure,Redox Properties,and Application for Supercapacitor

Discotic hexa‐peri‐hexabenzocoronene (HBC) molecules are synthesized by electrochemical cyclodehydrogenation reaction and in situ self‐assembled to π‐electronic, discrete nanofibular objects with an average diameter about 70 nm, which are deposited directly onto the electrode. The nanofibers consist of columnar arrays of the π‐stacked HBC molecules and the intercolumnar distance is determined to be 1.19 nm by X‐ray diffraction, which corresponds well to the distance of 1.1 nm observed by high‐resolution transmitting electron microscopy. The diameter of the molecular columns matches the size of the discotic HBC molecule indicating face‐to‐face π‐stacking of HBC units in the column. The HBC nanofibers on electrode are redox active, and the nanosized columnar structures provide a huge surface area, which is a great benefit for the charging/discharging process, delivering excellent capacitance of 155 F g^?1. The described electrochemical deposition method shows great advantage for self‐assembling the family of insoluble and structurally designable graphene‐like nano materials, which constitutes an important step toward molecular electronics.