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1.
J Am Chem Soc ; 142(10): 4932-4943, 2020 Mar 11.
Artigo em Inglês | MEDLINE | ID: mdl-32079395

RESUMO

Covalent organic frameworks are an emerging class of porous crystalline organic materials that can be designed and synthesized from the bottom up. Despite progress made in synthesizing COFs of diverse topologies, the synthesis methods are often tedious and unscalable, hampering practical applications. Herein, we demonstrate a scalable, robust method of producing highly crystalline acylhydrazone two-dimensional (2D) COFs with diversified structures (six examples) under open and stirred conditions, with growth typically completed in only 30 min. Our strategy involves selecting molecular building blocks that have bond dipole moments with spatial orientations that favor antiparallel stacking and whose structure allows the restriction of intramolecular bond rotation (RIR) via intra- and interlayer hydrogen bonding. This method is widely applicable for hydrazide linkers containing various side-chain functionalities and topicities. By this strategy, the gram-scale synthesis of two highly crystalline COFs (up to 1.4 g yield) was obtained in a one-pot reaction within 30 min.

2.
ACS Nano ; 2020 Feb 18.
Artigo em Inglês | MEDLINE | ID: mdl-32049489

RESUMO

The breaking of multiple symmetries by periodic lattice distortion at a commensurate charge density wave (CDW) state is expected to give rise to intriguing interesting properties. However, accessing the commensurate CDW state on bulk TaS2 crystals typically requires cryogenic temperatures (77 K), which precludes practical applications. Here, we found that heteroepitaxial growth of a 2H-tantalum disulfide bilayer on a hexagonal-boron nitride (h-BN) substrate produces a robust commensurate CDW order at room temperature, characterized by a Moiré superlattice of 3 × 3 TaS2 on a 4 × 4 h-BN unit cell. The CDW order is confirmed by scanning transmission electron microscopy and Raman measurements. Theoretical calculations reveal that the stabilizing energy for the CDW phase of the monolayer and bilayer 2H-TaS2-on-h-BN substrates arises primarily from interfacial electrostatic interactions and, to a lesser extent, interfacial strain. Our work shows that engineering interfacial electrostatic interactions in an ultrathin van der Waals heterostructure constitutes an effective way to enhance CDW order in two-dimensional materials.

3.
Nat Commun ; 10(1): 3374, 2019 Jul 29.
Artigo em Inglês | MEDLINE | ID: mdl-31358744

RESUMO

Collective molecular physical properties can be enhanced from their intrinsic characteristics by templating at material interfaces. Here we report how a black phosphorous (BP) substrate concatenates a nearly-free-electron (NFE) like conduction band of a C60 monolayer. Scanning tunneling microscopy reveals the C60 lowest unoccupied molecular orbital (LUMO) band is strongly delocalized in two-dimensions, which is unprecedented for a molecular semiconductor. Experiment and theory show van der Waals forces between C60 and BP reduce the inter-C60 distance and cause mutual orientation, thereby optimizing the π-π wave function overlap and forming the NFE-like band. Electronic structure and carrier mobility calculations predict that the NFE band of C60 acquires an effective mass of 0.53-0.70 me (me is the mass of free electrons), and has carrier mobility of ~200 to 440 cm2V-1s-1. The substrate-mediated intermolecular van der Waals interactions provide a route to enhance charge delocalization in fullerenes and other organic semiconductors.

4.
ACS Appl Mater Interfaces ; 11(9): 9213-9222, 2019 Mar 06.
Artigo em Inglês | MEDLINE | ID: mdl-30740967

RESUMO

Layered black phosphorus (BP) has been expected to be a promising material for future electronic and optoelectronic applications since its discovery. However, the difficulty in mass fabricating layered air-stable BP severely obstructs its potential industry applications. Here, we report a new BP chemical modification method to implement all-solution-based mass production of layered air-stable BP. This method uses the combination of two electron-deficient reagents 2,2,6,6-tetramethylpiperidinyl- N-oxyl (TEMPO) and triphenylcarbenium tetrafluorobor ([Ph3C]BF4) to accomplish thinning and/or passivation of BP in organic solvent. The field-effect transistor and photodetection devices constructed from the chemically modified BP flakes exhibit enhanced performances with environmental stability up to 4 months. A proof-of-concept BP thin-film transistor fabricated through the all-solution-based exfoliation and modification displays an air-stable and a typical p-type transistor behavior. This all-solution-based method improves the prospects of BP for industry applications.

5.
ACS Nano ; 13(2): 1885-1892, 2019 Feb 26.
Artigo em Inglês | MEDLINE | ID: mdl-30653300

RESUMO

Heterostructures of two-dimensional layered materials can be functionalized with exotic phenomena that are unpresented with each constituting component. The interface effect plays a key role in determining the electronic properties of the heterostructure, whose characterization requires a correlation with the morphology with atomic-scale precision. Here, we report an investigation on the electronic properties of few-layer Bi(110) films mediated by a NbSe2 substrate. By utilizing scanning tunneling microscopy and spectroscopy, we show a significant variation of the density of states at different Bi film thicknesses, resulting in an unusual superconducting proximity effect that deviates from the conventional monotonous decay behavior. Moreover, the electronic states of the Bi films are also prominently modulated by the Moiré pattern spatially. With first-principles calculations, we illuminate these findings as the results of covalent-like quasi-bonds formed at the Bi/NbSe2 interface, which profoundly alter the charge distributions in the Bi films. Our study indicates a viable way of modulating the electronic properties of ultrathin films by quasi-covalent interfacial couplings beyond conventional van der Waals interactions.

6.
Sci Adv ; 4(12): eaau6252, 2018 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-30555917

RESUMO

The edges of layered materials have unique properties that substantially differ from the body regions. In this work, we perform a systematic Raman study of the edges of various layered materials (MoS2, WS2, WSe2, PtS2, and black phosphorus). The Raman spectra of the edges feature newly observed forbidden Raman modes, which are originally undetectable from the body region. By selecting the edge type and the polarization directions of the incident and scattered light, all forbidden Raman modes are distinctly detected. Optical simulations show that the edges of layered materials drastically distort the electromagnetic fields of both the incident and scattered light, so that the light interacts with the edges in a distinct way, which differs from its interactions with the body regions.

7.
Nanoscale ; 10(47): 22263-22269, 2018 Dec 21.
Artigo em Inglês | MEDLINE | ID: mdl-30465580

RESUMO

Few-layer tellurium is an emerging quasi-one-dimensional layered material. The striking feature of Te is its presence as various few-layer allotropes (α-δ). Although these allotropes offer substantially different physical properties, only the α phase has been synthesized in neutral few-layers as it is so far the most stable few-layer form. Herein, we show that hole or electron doping could maintain a certain Te phase. The ß, α, γ and δ phases appear as the most stable forms of Te bilayer, in sequence, with bandgap variations over 1 eV. In Te trilayer, a novel metallic chiral α + δ phase emerges, leading to the appearance of chirality. Transitions among these phases, understood at the wavefunction level, are accompanied by the emergence or elimination of inversion centers (α-ß, α-γ, α-α + δ), structural anisotropy (α-γ, γ-δ) and chirality (α-α + δ), which could result in substantial changes in optical and other properties. In light of these findings, our work opens a new avenue for stabilizing different allotropes of layered materials; this is crucial for using their outstanding properties. This study also suggests the possibility of building mono-elemental electronic and optoelectronic heterostructures or devices, which are attractive for future applications in electronics.

8.
Sci Adv ; 3(9): e1701186, 2017 09.
Artigo em Inglês | MEDLINE | ID: mdl-28913429

RESUMO

Organic thin-film transistors (OTFTs) with high mobility and low contact resistance have been actively pursued as building blocks for low-cost organic electronics. In conventional solution-processed or vacuum-deposited OTFTs, due to interfacial defects and traps, the organic film has to reach a certain thickness for efficient charge transport. Using an ultimate monolayer of 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT) molecules as an OTFT channel, we demonstrate remarkable electrical characteristics, including intrinsic hole mobility over 30 cm2/Vs, Ohmic contact with 100 Ω · cm resistance, and band-like transport down to 150 K. Compared to conventional OTFTs, the main advantage of a monolayer channel is the direct, nondisruptive contact between the charge transport layer and metal leads, a feature that is vital for achieving low contact resistance and current saturation voltage. On the other hand, bilayer and thicker C8-BTBT OTFTs exhibit strong Schottky contact and much higher contact resistance but can be improved by inserting a doped graphene buffer layer. Our results suggest that highly crystalline molecular monolayers are promising form factors to build high-performance OTFTs and investigate device physics. They also allow us to precisely model how the molecular packing changes the transport and contact properties.

9.
Adv Mater ; 29(5)2017 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-27886410

RESUMO

The electrical and optical measurements, in combination with density functional theory calculations, show distinct layer-dependent semiconductor-to-semimetal evolution of 2D layered PtSe2 . The high room-temperature electron mobility and near-infrared photo-response, together with much better air-stability, make PtSe2 a versatile electronic 2D layered material.

10.
Nanoscale ; 8(15): 8324-32, 2016 Apr 21.
Artigo em Inglês | MEDLINE | ID: mdl-27035503

RESUMO

Anisotropic two-dimensional (2D) van der Waals (vdW) layered materials, with both scientific interest and application potential, offer one more dimension than isotropic 2D materials to tune their physical properties. Various physical properties of 2D multi-layer materials are modulated by varying their stacking orders owing to significant interlayer vdW coupling. Multilayer rhenium disulfide (ReS2), a representative anisotropic 2D material, was expected to be randomly stacked and lack interlayer coupling. Here, we demonstrate two stable stacking orders, namely isotropic-like (IS) and anisotropic-like (AI) N layer (NL, N > 1) ReS2 are revealed by ultralow- and high-frequency Raman spectroscopy, photoluminescence and first-principles density functional theory calculation. Two interlayer shear modes are observed in AI-NL-ReS2 while only one shear mode appears in IS-NL-ReS2, suggesting anisotropic- and isotropic-like stacking orders in IS- and AI-NL-ReS2, respectively. This explicit difference in the observed frequencies identifies an unexpected strong interlayer coupling in IS- and AI-NL-ReS2. Quantitatively, the force constants of them are found to be around 55-90% of those of multilayer MoS2. The revealed strong interlayer coupling and polytypism in multi-layer ReS2 may stimulate future studies on engineering physical properties of other anisotropic 2D materials by stacking orders.

11.
Adv Mater ; 28(12): 2399-407, 2016 Mar 23.
Artigo em Inglês | MEDLINE | ID: mdl-26833689

RESUMO

Platinum disulfide (PtS2 ), a new member of the group-10 transition-metal dichalcogenides, is studied experimentally and theoretically. The indirect bandgap of PtS2 can be drastically tuned from 1.6 eV (monolayer) to 0.25 eV (bulk counterpart), and the interlayer mechanical coupling is almost isotropic. It can be explained by strongly interlayer interaction from the pz orbital hybridization of S atoms.

12.
Nanoscale ; 8(5): 2740-50, 2016 Feb 07.
Artigo em Inglês | MEDLINE | ID: mdl-26763557

RESUMO

Stacking two-dimensional (2D) materials into multi-layers or heterostructures, known as van der Waals (vdW) epitaxy, is an essential degree of freedom for tuning their properties on demand. Few-layer black phosphorus (FLBP), a material with high potential for nano- and optoelectronics applications, appears to have interlayer couplings much stronger than graphene and other 2D systems. Indeed, these couplings call into question whether the stacking of FLBP can be governed only by vdW interactions, which is of crucial importance for epitaxy and property refinement. Here, we perform a theoretical investigation of the vibrational properties of FLBP, which reflect directly its interlayer coupling, by discussing six Raman-observable phonons, including three optical, one breathing and two shear modes. With increasing sample thickness, we find anomalous redshifts of the frequencies for each optical mode but a blueshift for the armchair shear mode. Our calculations also show splitting of the phonon branches, due to anomalous surface phenomena, and strong phonon-phonon coupling. By computing uniaxial stress effects, inter-atomic force constants and electron densities, we provide a compelling demonstration that these properties are the consequence of strong and highly directional interlayer interactions arising from the electronic hybridization of the lone electron-pairs of FLBP, rather than from vdW interactions. This exceptional interlayer coupling mechanism controls the stacking stability of BP layers and thus opens a new avenue beyond vdW epitaxy for understanding the design of 2D heterostructures.

13.
Phys Rev Lett ; 116(1): 016602, 2016 Jan 08.
Artigo em Inglês | MEDLINE | ID: mdl-26799035

RESUMO

One of the basic assumptions in organic field-effect transistors, the most fundamental device unit in organic electronics, is that charge transport occurs two dimensionally in the first few molecular layers near the dielectric interface. Although the mobility of bulk organic semiconductors has increased dramatically, direct probing of intrinsic charge transport in the two-dimensional limit has not been possible due to excessive disorders and traps in ultrathin organic thin films. Here, highly ordered single-crystalline mono- to tetralayer pentacene crystals are realized by van der Waals (vdW) epitaxy on hexagonal BN. We find that the charge transport is dominated by hopping in the first conductive layer, but transforms to bandlike in subsequent layers. Such an abrupt phase transition is attributed to strong modulation of the molecular packing by interfacial vdW interactions, as corroborated by quantitative structural characterization and density functional theory calculations. The structural modulation becomes negligible beyond the second conductive layer, leading to a mobility saturation thickness of only ∼3 nm. Highly ordered organic ultrathin films provide a platform for new physics and device structures (such as heterostructures and quantum wells) that are not possible in conventional bulk crystals.

14.
Nat Commun ; 5: 4475, 2014 Jul 21.
Artigo em Inglês | MEDLINE | ID: mdl-25042376

RESUMO

Two-dimensional crystals are emerging materials for nanoelectronics. Development of the field requires candidate systems with both a high carrier mobility and, in contrast to graphene, a sufficiently large electronic bandgap. Here we present a detailed theoretical investigation of the atomic and electronic structure of few-layer black phosphorus (BP) to predict its electrical and optical properties. This system has a direct bandgap, tunable from 1.51 eV for a monolayer to 0.59 eV for a five-layer sample. We predict that the mobilities are hole-dominated, rather high and highly anisotropic. The monolayer is exceptional in having an extremely high hole mobility (of order 10,000 cm(2) V(-1) s(-1)) and anomalous elastic properties which reverse the anisotropy. Light absorption spectra indicate linear dichroism between perpendicular in-plane directions, which allows optical determination of the crystalline orientation and optical activation of the anisotropic transport properties. These results make few-layer BP a promising candidate for future electronics.

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