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1.
J Phys Chem Lett ; 11(15): 6273-6278, 2020 Aug 06.
Artigo em Inglês | MEDLINE | ID: mdl-32667205

RESUMO

The development of spin qubits for quantum technologies requires their protection from the main source of finite-temperature decoherence: atomic vibrations. Here we eliminate one of the main barriers to the progress in this field by providing a complete first-principles picture of spin relaxation that includes up to two-phonon processes. Our method is based on machine learning and electronic structure theory and makes the prediction of spin lifetime in realistic systems feasible. We study a prototypical vanadium-based molecular qubit and reveal that the spin lifetime at high temperature is limited by Raman processes due to a small number of THz intramolecular vibrations. These findings effectively change the conventional understanding of spin relaxation in this class of materials and open new avenues for the rational design of long-living spin systems.

2.
Sci Adv ; 5(9): eaax7163, 2019 09.
Artigo em Inglês | MEDLINE | ID: mdl-31598553

RESUMO

The coupling between electronic spins and lattice vibrations is fundamental for driving relaxation in magnetic materials. The debate over the nature of spin-phonon coupling dates back to the 1940s, but the role of spin-spin, spin-orbit, and hyperfine interactions has never been fully established. Here, we present a comprehensive study of the spin dynamics of a crystal of Vanadyl-based molecular qubits by means of first-order perturbation theory and first-principles calculations. We quantitatively determine the role of the Zeeman, hyperfine, and electronic spin dipolar interactions in the direct mechanism of spin relaxation. We show that, in a high magnetic field regime, the modulation of the Zeeman Hamiltonian by the intramolecular components of the acoustic phonons dominates the relaxation mechanism. In low fields, hyperfine coupling takes over, with the role of spin-spin dipolar interaction remaining the less important for the spin relaxation.

3.
Sci Rep ; 9(1): 11738, 2019 Aug 13.
Artigo em Inglês | MEDLINE | ID: mdl-31409846

RESUMO

Considerable attention has been drawn to the lead halide perovskites (LHPs) because of their outstanding optoelectronic characteristics. LHP nanosheets (NSs) grown from single crystalline lead halide possess advantages in device applications as they provide the possibility for control over morphology, composition, and crystallinity. Here, free-standing lead bromide (PbBr2) single-crystalline NSs with sizes up to one centimeter are synthesized from solution. These NSs can be converted to LHP while maintaining the NS morphology. We demonstrate that these perovskite NSs can be processed directly for fabrication of photodetector and laser arrays on a large scale. This strategy will allow high-yield synthesis of large-size perovskite NSs for functional devices in an integrated photonics platform.

4.
Nanoscale ; 11(27): 13117-13125, 2019 Jul 11.
Artigo em Inglês | MEDLINE | ID: mdl-31268079

RESUMO

Using graphene as electrodes provides an opportunity for fabricating stable single-molecule field-effect transistors (FETs) operating at room temperature. However, the role of the unique graphene band structure in charge transport of single-molecule devices is still not clear. Here we report the Dirac-cone induced electrostatic gating effects in single-molecule FETs with graphene electrodes and a solid-state local bottom gate. With the highest occupied molecular orbital (HOMO) as the dominating conduction channel and the graphene leads remaining intrinsic at zero gate voltage, electrostatic gating on the HOMO and the density of states of graphene at the negative gate polarity reinforces each other, resulting in an enhanced conductance modulation. In contrast, gating effects on the HOMO and the graphene states at the positive gate polarity are opposite. Depending on the gating efficiencies, the conductance can decrease, increase or remain almost unchanged when a more positive gate voltage is applied. Our observations can be well understood by a modified single-level model taking into account the linear dispersion of graphene near the Dirac point. Single-molecule FETs with Dirac-cone enhanced gating have shown high performances, with the modulation of a wide range of current over one order of magnitude. Our studies highlight the advantages of using graphene as an electrode material for molecular devices and pave the way for single-molecule FETs toward circuitry applications.

5.
Inorg Chem ; 58(15): 10260-10268, 2019 Aug 05.
Artigo em Inglês | MEDLINE | ID: mdl-31343163

RESUMO

Paramagnetic molecules can show long spin-coherence times, which make them good candidates as quantum bits (qubits). Reducing the efficiency of the spin-phonon interaction is the primary challenge toward achieving long coherence times over a wide temperature range in soft molecular lattices. The lack of a microscopic understanding about the role of vibrations in spin relaxation strongly undermines the possibility of chemically designing better-performing molecular qubits. Here we report a first-principles characterization of the main mechanism contributing to the spin-phonon coupling for a class of vanadium(IV) molecular qubits. Post-Hartree-Fock and density functional theory methods are used to determine the effect of both intermolecular and intramolecular vibrations on modulation of the Zeeman energy for four molecules showing different coordination geometries and ligands. This comparative study provides the first insight into the role played by coordination geometry and ligand-field strength in determining the spin-lattice relaxation time of molecular qubits, opening an avenue to the rational design of new compounds.

6.
J Phys Chem A ; 123(33): 7323-7334, 2019 Aug 22.
Artigo em Inglês | MEDLINE | ID: mdl-31343887

RESUMO

Forecasting the structural stability of hybrid organic/inorganic compounds, where polyatomic molecules replace atoms, is a challenging task; the composition space is vast, and the reference structure for the organic molecules is ambiguously defined. In this work, we use a range of machine-learning algorithms, constructed from state-of-the-art density functional theory data, to conduct a systematic analysis on the likelihood of a given cation to be housed in the perovskite structure. In particular, we consider both ABC3 chalcogenide (I-V-VI3) and halide (I-II-VII3) perovskites. We find that the effective atomic radius and the number of lone pairs residing on the A-site cation are sufficient features to describe the perovskite phase stability. Thus, the presented machine-learning approach provides an efficient way to map the phase stability of the vast class of compounds, including situations where a cation mixture replaces a single A-site cation. This work demonstrates that advanced electronic structure theory combined with machine-learning analysis can provide an efficient strategy superior to the conventional trial-and-error approach in materials design.

7.
Sci Adv ; 5(5): eaaw2210, 2019 May.
Artigo em Inglês | MEDLINE | ID: mdl-31172029

RESUMO

Computational studies of chemical processes taking place over extended size and time scales are inaccessible by electronic structure theories and can be tackled only by atomistic models such as force fields. These have evolved over the years to describe the most diverse systems. However, as we improve the performance of a force field for a particular physical/chemical situation, we are also moving away from a unified description. Here, we demonstrate that a unified picture of the covalent bond is achievable within the framework of machine learning-based force fields. Ridge regression, together with a representation of the atomic environment in terms of bispectrum components, can be used to map a general potential energy surface for molecular systems at chemical accuracy. This protocol sets the ground for the generation of an accurate and universal class of potentials for both organic and organometallic compounds with no specific assumptions on the chemistry involved.

8.
Angew Chem Int Ed Engl ; 58(18): 6017-6021, 2019 04 23.
Artigo em Inglês | MEDLINE | ID: mdl-30866112

RESUMO

The mechanism of silver-oxygen and silver-sulfur reactions is revealed by means of molecular dynamics simulations, performed with reactive force fields purposely built and extensively tested against quantum-chemical results. Different reaction mechanisms and rates for Ag-O and Ag-S emerge. This study solves the long-lasting question why silver exposed to the environment is strongly vulnerable to sulfur corrosion (tarnishing) but hardly reacts with O2 , despite the thermodynamic prediction that both oxide and sulfide should form. The reliability of the simulation results is confirmed by the agreement with a multitude of experimental results from the literature.

9.
Nat Mater ; 18(5): 482-488, 2019 05.
Artigo em Inglês | MEDLINE | ID: mdl-30886399

RESUMO

In two-dimensional (2D) systems, high mobility is typically achieved in low-carrier-density semiconductors and semimetals. Here, we discover that the nanobelts of Weyl semimetal NbAs maintain a high mobility even in the presence of a high sheet carrier density. We develop a growth scheme to synthesize single crystalline NbAs nanobelts with tunable Fermi levels. Owing to a large surface-to-bulk ratio, we argue that a 2D surface state gives rise to the high sheet carrier density, even though the bulk Fermi level is located near the Weyl nodes. A surface sheet conductance up to 5-100 S per □ is realized, exceeding that of conventional 2D electron gases, quasi-2D metal films, and topological insulator surface states. Corroborated by theory, we attribute the origin of the ultrahigh conductance to the disorder-tolerant Fermi arcs. The evidenced low-dissipation property of Fermi arcs has implications for both fundamental study and potential electronic applications.

10.
Nano Lett ; 19(2): 1366-1370, 2019 02 13.
Artigo em Inglês | MEDLINE | ID: mdl-30648394

RESUMO

Inspired by recent experiments on the successful fabrication of monolayer Janus transition-metal dichalcogenides [ Lu , A.-Y. ; Nat. Nanotechnol. 2017 , 12 , ( 8 ), 744 and ferromagnetic VSe2 [ Bonilla , M. ; Nat. Nanotechnol. 2018 , 13 , ( 4 ), 289 ], we predict a highly stable room-temperature ferromagnetic Janus monolayer (VSSe) by density functional theory methods and further confirmed the stability by a global minimum search with the particle-swarm optimization method. The VSSe monolayer exhibits a large valley polarization due to the broken space- and time-reversal symmetry. Moreover, its low symmetry C3 v point group results in giant in-plane piezoelectric polarization. Most interestingly, a strain-driven 90° lattice rotation is found in the magnetic VSSe monolayer with an extremely high reversal strain (73%), indicating an intrinsic ferroelasticity. The combination of piezoelectricity and valley polarization make magnetic 2D Janus VSSe a tantalizing material for potential applications in nanoelectronics, optoelectronics, and valleytronics.

11.
Phys Chem Chem Phys ; 21(5): 2821, 2019 01 30.
Artigo em Inglês | MEDLINE | ID: mdl-30657154

RESUMO

Correction for 'Exploring new approaches towards the formability of mixed-ion perovskites by DFT and machine learning' by Heesoo Park et al., Phys. Chem. Chem. Phys., 2019, DOI: 10.1039/c8cp06528d.

12.
Nature ; 565(7739): 331-336, 2019 01.
Artigo em Inglês | MEDLINE | ID: mdl-30559378

RESUMO

Discovered decades ago, the quantum Hall effect remains one of the most studied phenomena in condensed matter physics and is relevant for research areas such as topological phases, strong electron correlations and quantum computing1-5. The quantized electron transport that is characteristic of the quantum Hall effect typically originates from chiral edge states-ballistic conducting channels that emerge when two-dimensional electron systems are subjected to large magnetic fields2. However, whether the quantum Hall effect can be extended to higher dimensions without simply stacking two-dimensional systems is unknown. Here we report evidence of a new type of quantum Hall effect, based on Weyl orbits in nanostructures of the three-dimensional topological semimetal Cd3As2. The Weyl orbits consist of Fermi arcs (open arc-like surface states) on opposite surfaces of the sample connected by one-dimensional chiral Landau levels along the magnetic field through the bulk6,7. This transport through the bulk results in an additional contribution (compared to stacked two-dimensional systems and which depends on the sample thickness) to the quantum phase of the Weyl orbit. Consequently, chiral states can emerge even in the bulk. To measure these quantum phase shifts and search for the associated chiral modes in the bulk, we conduct transport experiments using wedge-shaped Cd3As2 nanostructures with variable thickness. We find that the quantum Hall transport is strongly modulated by the sample thickness. The dependence of the Landau levels on the magnitude and direction of the magnetic field and on the sample thickness agrees with theoretical predictions based on the modified Lifshitz-Onsager relation for the Weyl orbits. Nanostructures of topological semimetals thus provide a way of exploring quantum Hall physics in three-dimensional materials with enhanced tunability.

13.
Phys Chem Chem Phys ; 21(3): 1078-1088, 2019 Jan 21.
Artigo em Inglês | MEDLINE | ID: mdl-30566133

RESUMO

Recent years have witnessed a growing effort in engineering and tuning the properties of hybrid halide perovskites as light absorbers. These have led to the successful enhancement of their stability, a feature that is often counterbalanced by a reduction of their power-conversion efficiency. In order to provide a systematic analysis of the structure-property relationships of this class of compounds we have performed density functional theory calculations exploring fully inorganic ABC3 chalcogenide (I-V-VI3), halide (I-II-VII3) and hybrid perovskites. Special attention has been given to structures featuring three-dimensional BC6 octahedral networks because of their efficient carrier transport properties. In particular we have carefully analyzed the role of BC6 octahedral deformations, rotations and tilts in the thermodynamic stability and optical properties of the compounds. By using machine learning algorithms we have estimated the relations between the octahedral deformation and the bandgap, and established a similarity map among all the calculated compounds.

14.
J Chem Inf Model ; 58(12): 2477-2490, 2018 12 24.
Artigo em Inglês | MEDLINE | ID: mdl-30188699

RESUMO

A priori prediction of phase stability of materials is a challenging practice, requiring knowledge of all energetically competing structures at formation conditions. Large materials repositories-housing properties of both experimental and hypothetical compounds-offer a path to prediction through the construction of informatics-based, ab initio phase diagrams. However, limited access to relevant data and software infrastructure has rendered thermodynamic characterizations largely peripheral, despite their continued success in dictating synthesizability. Herein, a new module is presented for autonomous thermodynamic stability analysis, implemented within the open-source, ab initio framework AFLOW. Powered by the AFLUX Search-API, AFLOW-CHULL leverages data of more than 1.8 million compounds characterized in the AFLOW.org repository, and can be employed locally from any UNIX-like computer. The module integrates a range of functionality: the identification of stable phases and equivalent structures, phase coexistence, measures for robust stability, and determination of decomposition reactions. As a proof of concept, thermodynamic characterizations have been performed for more than 1300 binary and ternary systems, enabling the identification of several candidate phases for synthesis based on their relative stability criterion-including 17 promising C15 b-type structures and 2 half-Heuslers. In addition to a full report included herein, an interactive, online web application has been developed showcasing the results of the analysis and is located at aflow.org/aflow-chull .


Assuntos
Informática , Software , Termodinâmica , Simulação por Computador , Descoberta de Drogas , Ciência dos Materiais , Modelos Químicos
15.
ACS Nano ; 12(7): 7185-7196, 2018 Jul 24.
Artigo em Inglês | MEDLINE | ID: mdl-29901987

RESUMO

The search for proximity-induced superconductivity in topological materials has generated widespread interest in the condensed matter physics community. The superconducting states inheriting nontrivial topology at interfaces are expected to exhibit exotic phenomena such as topological superconductivity and Majorana zero modes, which hold promise for applications in quantum computation. However, a practical realization of such hybrid structures based on topological semimetals and superconductors has hitherto been limited. Here, we report the strong proximity-induced superconductivity in type-II Weyl semimetal WTe2, in a van der Waals hybrid structure obtained by mechanically transferring NbSe2 onto various thicknesses of WTe2. When the WTe2 thickness ( tWTe2) reaches 21 nm, the superconducting transition occurs around the critical temperature ( Tc) of NbSe2 with a gap amplitude (Δp) of 0.38 meV and an unexpected ultralong proximity length ( lp) up to 7 µm. With the thicker 42 nm WTe2 layer, however, the proximity effect yields Tc ≈ 1.2 K, Δp = 0.07 meV, and a short lp of less than 1 µm. Our theoretical calculations, based on the Bogoliubov-de Gennes equations in the clean limit, predict that the induced superconducting gap is a sizable fraction of the NbSe2 superconducting one when tWTe2 is less than 30 nm and then decreases quickly as tWTe2 increases. This agrees qualitatively well with the experiments. Such observations form a basis in the search for superconducting phases in topological semimetals.

16.
J Chem Phys ; 148(18): 184703, 2018 May 14.
Artigo em Inglês | MEDLINE | ID: mdl-29764150

RESUMO

The relationship between the molecular structure and the electronic transport properties of molecular junctions based on thiol-terminated oligoethers, which are obtained by replacing every third methylene unit in the corresponding alkanethiols with an oxygen atom, is investigated by employing the non-equilibrium Green's function formalism combined with density functional theory. Our calculations show that the low-bias conductance depends strongly on the conformation of the oligoethers in the junction. Specifically, in the cases of trans-extended conformation, the oxygen-dominated transmission peaks are very sharp and well below the Fermi energy, EF, thus hardly affect the transmission around EF; the Au-S interface hybrid states couple with σ-bonds in the molecular backbone forming the conduction channel at EF, resulting in a conductance decay against the molecular length close to that for alkanethiols. By contrast, for junctions with oligoethers in helical conformations, some π-type oxygen orbitals coupling with the Au-S interface hybrid states contribute to the transmission around EF. The molecule-electrode electronic coupling is also enhanced at the non-thiol side due to the specific spatial orientation introduced by the twist of the molecular backbone. This leads to a much smaller conductance decay constant. Our findings highlight the important role of the molecular conformation of oligoethers in their electronic transport properties and are also helpful for the design of molecular wires with heteroatom-substituted alkanethiols.

17.
Sci Rep ; 8(1): 4779, 2018 Mar 19.
Artigo em Inglês | MEDLINE | ID: mdl-29556015

RESUMO

Recently magnetic tunnel junctions using two-dimensional MoS2 as nonmagnetic spacer have been fabricated, although their magnetoresistance has been reported to be quite low. This may be attributed to the use of permalloy electrodes, injecting current with a relatively small spin polarization. Here we evaluate the performance of MoS2-based tunnel junctions using Fe3Si Heusler alloy electrodes. Density functional theory and the non-equilibrium Green's function method are used to investigate the spin injection efficiency (SIE) and the magnetoresistance (MR) ratio as a function of the MoS2 thickness. We find a maximum MR of ~300% with a SIE of about 80% for spacers comprising between 3 and 5 MoS2 monolayers. Most importantly, both the SIE and the MR remain robust at finite bias, namely MR > 100% and SIE > 50% at 0.7 V. Our proposed materials stack thus demonstrates the possibility of developing a new generation of performing magnetic tunnel junctions with layered two-dimensional compounds as spacers.

18.
Phys Chem Chem Phys ; 20(6): 4277-4286, 2018 Feb 07.
Artigo em Inglês | MEDLINE | ID: mdl-29364993

RESUMO

Ag and Sn are the major components of solder alloys adopted to assemble printed circuit boards. The qualities that make them the alloys of choice for the modern electronic industry are related to their physical and chemical properties. For corrosion resistance and solderability, surface properties are particularly important. Yet, atomic-level information about the surfaces of these alloys is not known. Here we fill this gap by presenting an extensive ab initio investigation of composition, energetics, structure and reactivity of Ag-Sn alloy surfaces. The structure and stability of various surfaces is evaluated, and the main factors determining the energetics of surface formation are uncovered. Oxygen and sulphur chemisorptions are studied and discussed in the framework of corrosion tendency, an important issue for printed circuit boards. Adsorption energy trends are rationalized based on the analysis of structural and electronic features.

19.
Chemphyschem ; 19(6): 703-714, 2018 Mar 19.
Artigo em Inglês | MEDLINE | ID: mdl-29144015

RESUMO

In the quest for nontoxic and stable perovskites for solar cells, we have conducted a systematic study of the effect of chalcogen content in oxychalcogenide perovskite by using DFT and quasi-particle perturbation theory. We explored the changes in the electronic structure due to the substitution of O atoms in NaNbO3 and NaTaO3 perovskite structures with various chalcogens (S, Se, Te) at different concentrations. Interestingly, the introduction of the chalcogen atoms resulted in a drastic reduction in the electronic band gap, which made some of the compounds fall within the visible range of the solar spectrum. In addition, our analysis of the electronic structure shows that the optical transition becomes direct as a result of the strong hybridization between the orbitals of the transition metal and those of the chalcogen ion, in contrast to the indirect band feature of NaNbO3 and NaTaO3 . We identified candidates with a high theoretical solar conversion efficiency that approached the Shockley-Queisser limit, which makes them suitable for thin-film solar cell applications. The present work serves as a guideline for experimental efforts by identifying the chalcogen content that should be targeted during the synthetic route of thermodynamically stable and strongly photoactive absorbers for oxychalcogenide perovskites in thin-film solar cells.

20.
Nat Commun ; 8(1): 1272, 2017 11 02.
Artigo em Inglês | MEDLINE | ID: mdl-29097658

RESUMO

Owing to the coupling between open Fermi arcs on opposite surfaces, topological Dirac semimetals exhibit a new type of cyclotron orbit in the surface states known as Weyl orbit. Here, by lowering the carrier density in Cd3As2 nanoplates, we observe a crossover from multiple-frequency to single-frequency Shubnikov-de Haas (SdH) oscillations when subjected to out-of-plane magnetic field, indicating the dominant role of surface transport. With the increase of magnetic field, the SdH oscillations further develop into quantum Hall state with non-vanishing longitudinal resistance. By tracking the oscillation frequency and Hall plateau, we observe a Zeeman-related splitting and extract the Landau level index as well as sub-band number. Different from conventional two-dimensional systems, this unique quantum Hall effect may be related to the quantized version of Weyl orbits. Our results call for further investigations into the exotic quantum Hall states in the low-dimensional structure of topological semimetals.

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