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1.
Artigo em Inglês | MEDLINE | ID: mdl-32374495

RESUMO

The energetic chemical reaction between Zn(NO3 )2 and Li is used to create a solid-state interface between Li metal and Li6.4 La3 Zr1.4 Ta0.6 O12 (LLZTO) electrolyte. This interlayer, composed of Zn, ZnLix alloy, Li3 N, Li2 O, and other species, possesses strong affinities with both Li metal and LLZTO and affords highly efficient conductive pathways for Li+ transport through the interface. The unique structure and properties of the interlayer lead to Li metal anodes with longer cycle life, higher efficiency, and better safety compared to the current best Li metal electrodes operating in liquid electrolytes while retaining comparable capacity, rate, and overpotential. All-solid-state Li||Li cells can operate at very demanding current-capacity conditions of 4 mA cm-2 -8 mAh cm-2 . Thousands of hours of continuous cycling are achieved at Coulombic efficiency >99.5 % without dendrite formation or side reactions with the electrolyte.

2.
Phys Rev Lett ; 124(3): 036102, 2020 Jan 24.
Artigo em Inglês | MEDLINE | ID: mdl-32031828

RESUMO

Large-scale, controlled fabrication of ordered phases is challenging at the nanoscale, yet highly demanded as their well-ordered structure and chemistry is the key for advanced functionality. Here, we demonstrate a general nanomolding process of ordered phases based on atomic diffusion. Resulting nanowires are single crystals and maintain their composition and structure throughout their length, which we explain by a self-ordering process originating from their narrow Gibbs free energy. The versatility, control, and precision of this thermomechanical nanomolding method of ordered phases provides new insights into single crystal growth and suggest itself as a technology to enable wide spread usage for nanoscale and quantum devices.

3.
ACS Nano ; 13(6): 6455-6460, 2019 Jun 25.
Artigo em Inglês | MEDLINE | ID: mdl-31141656

RESUMO

Tungsten ditelluride (WTe2) has many interesting properties such as its extremely large nonsaturating magnetoresistance and quantum spin Hall state in the monolayer limit. The anisotropic crystal structure of WTe2 can allow for isolation of particular crystal directions to study the predicted Weyl states or crystal-symmetry-dependent magnetoresistance when studied at limited dimensions. In particular, the recent demonstration of superconductivity in WTe2 monolayer suggests that realizing nanowire geometry for WTe2 may be important to investigate potential Majorana zero modes predicted in one-dimensional topological superconductors. In this work, we demonstrate a large-yield, low-temperature synthesis of WTe2 nanowires, an approximate one-dimensional system, by converting WO3 nanowires via tellurization. The nanowires are single crystalline and have a higher resistivity than WTe2 exfoliated flakes with similar thickness. The increased resistivity is attributed to increased scattering from imperfect surfaces and higher surface-to-volume ratios of the WTe2 nanowires. We demonstrate that the synthesis method is generalizable to other transition-metal dichalcogenides, laying the foundation for further study of this class of materials in the one-dimensional limit.

4.
Sci Rep ; 9(1): 7136, 2019 May 09.
Artigo em Inglês | MEDLINE | ID: mdl-31073200

RESUMO

Aluminum-based quasicrystals typically form across narrow composition ranges within binary to quaternary alloys, which makes their fabrication and characterization challenging. Here, we use combinatorial approaches together with fast characterization techniques to study a wide compositional range including known quasicrystal forming compositions. Specifically, we use magnetron co-sputtering to fabricate libraries of ~140 Al-Cu-Fe and ~300 Al-Cu-Fe-Cr alloys. The alloys compositions are measured through automated energy dispersive X-ray spectroscopy. Phase formation and thermal stability are investigated for different thermal processing conditions (as-sputtered and annealed at 400 °C, 520 °C and 600 °C for Al-Cu-Fe libraries; annealed at 600 °C for Al-Cu-Fe-Cr libraries) using automated X-ray diffraction and transmission electron microscopy. In both systems the compositional regions across which the quasicrystalline phase forms are identified. In particular, we demonstrate that the quasicrystalline phase forms across an unusually broad composition range in the Al-Cu-Fe-Cr system. Additionally, some of the considered alloys vitrify during sputtering, which also allows us to study their nucleation behavior. We find that phases with polytetrahedral symmetry, such as the icosahedral quasicrystal and the λ-Al13Fe4 phase, exhibit higher nucleation rates but lower growth rates, as compared to other phases with a lower degree of polytetrahedral order. Altogether, the here used combinatorial approach is powerful to identify compositional regions of quasicrystals.

5.
Small ; 15(19): e1900078, 2019 May.
Artigo em Inglês | MEDLINE | ID: mdl-30957970

RESUMO

Using the MoS2 -WTe2 heterostructure as a model system combined with electrochemical microreactors and density function theory calculations, it is shown that heterostructured contacts enhance the hydrogen evolution reaction (HER) activity of monolayer MoS2 . Two possible mechanisms are suggested to explain this enhancement: efficient charge injection through large-area heterojunctions between MoS2 and WTe2 and effective screening of mirror charges due to the semimetallic nature of WTe2 . The dielectric screening effect is proven minor, probed by measuring the HER activity of monolayer MoS2 on various support substrates with dielectric constants ranging from 4 to 300. Thus, the enhanced HER is attributed to the increased charge injection into MoS2 through large-area heterojunctions. Based on this understanding, a MoS2 /WTe2 hybrid catalyst is fabricated with an HER overpotential of -140 mV at 10 mA cm-2 , a Tafel slope of 40 mV dec-1 , and long stability. These results demonstrate the importance of interfacial design in transition metal dichalcogenide HER catalysts. The microreactor platform presents an unambiguous approach to probe interfacial effects in various electrocatalytic reactions.

6.
Nat Commun ; 10(1): 915, 2019 02 22.
Artigo em Inglês | MEDLINE | ID: mdl-30796248

RESUMO

While common growth models assume a structure-less liquid composed of atomic flow units, structural ordering has been shown in liquid metals. Here, we conduct in situ transmission electron microscopy crystallization experiments on metallic glass nanorods, and show that structural ordering strongly affects crystal growth and is controlled by nanorod thermal history. Direct visualization reveals structural ordering as densely populated small clusters in a nanorod heated from the glass state, and similar behavior is found in molecular dynamics simulations of model metallic glasses. At the same growth temperature, the asymmetry in growth rate for rods that are heated versus cooled decreases with nanorod diameter and vanishes for very small rods. We hypothesize that structural ordering enhances crystal growth, in contrast to assumptions from common growth models. The asymmetric growth rate is attributed to the difference in the degree of the structural ordering, which is pronounced in the heated glass but sparse in the cooled liquid.

7.
J Am Chem Soc ; 140(15): 5241-5247, 2018 04 18.
Artigo em Inglês | MEDLINE | ID: mdl-29608305

RESUMO

Seeking earth-abundant electrocatalysts with high efficiency and durability has become the frontier of energy conversion research. Mixed-transition-metal (MTM)-based electrocatalysts, owing to the desirable electrical conductivity, synergistic effect of bimetal atoms, and structural stability, have recently emerged as new-generation hydrogen evolution reaction (HER) electrocatalysts. However, the correlation between anion species and their intrinsic electrocatalytic properties in MTM-based electrocatalysts is still not well understood. Here we present a novel approach to tuning the anion-dependent electrocatalytic characteristics in MTM-based catalyst for HER, using holey Ni/Co-based phosphides/selenides/oxides (Ni-Co-A, A = P, Se, O) as the model materials. The electrochemical results, combined with the electrical conductivity measurement and DFT calculation, reveal that P substitution could modulate the electron configuration, lower the hydrogen adsorption energy, and facilitate the desorption of hydrogen on the active sites in Ni-Co-A holey nanostructures, resulting in superior HER catalytic activity. Accordingly we fabricate the NCP holey nanosheet electrocatalyst for HER with an ultralow onset overpotential of nearly zero, an overpotential of 58 mV, and long-term durability, along with an applied potential of 1.56 V to boost overall water splitting at 10 mA cm-2, among the best electrocatalysts reported for non-noble-metal catalysts to date. This work not only presents a deeper understanding of the intrinsic HER electrocatalytic properties for MTM-based electrocatalyst with various anion species but also offers new insights to better design efficient and durable water-splitting electrocatalysts.

8.
ACS Appl Mater Interfaces ; 10(22): 18805-18815, 2018 Jun 06.
Artigo em Inglês | MEDLINE | ID: mdl-29668253

RESUMO

Accomplishing acid-stable water oxidation is a critical matter for achieving both long-lasting water-splitting devices and other fuel-forming electro- and photocatalytic processes. Because water oxidation releases protons into the local electrolytic environment, it becomes increasingly acidic during device operation, which leads to corrosion of the photoactive component and hence loss in device performance and lifetime. In this work, we show that thin films of manganese-modified titania, (Ti,Mn)O x, topped with an iridium catalyst, can be used in a coating stabilization scheme for acid-stable water oxidation. We achieved a device lifetime of more than 100 h in pH = 0 acid. We successfully grew (Ti,Mn)O x coatings with uniform elemental distributions over a wide range of manganese compositions using atomic layer deposition (ALD), and using X-ray photoelectron spectroscopy, we show that (Ti,Mn)O x films grown in this manner give rise to closer-to-valence-band Fermi levels, which can be further tuned with annealing. In contrast to the normally n-type or intrinsic TiO2 coatings, annealed (Ti,Mn)O x films can make direct charge transfer to a Fe(CN)63-/4- redox couple dissolved in aqueous electrolytes. Using the Fe(CN)63-/4- redox, we further demonstrated anodic charge transfer through the (Ti,Mn)O x films to high work function metals, such as iridium and gold, which is not previously possible with ALD-grown TiO2. We correlated changes in the crystallinity (amorphous to rutile TiO2) and oxidation state (2+ to 3+) of the annealed (Ti,Mn)O x films to their hole conductivity and electrochemical stability in acid. Finally, by combining (Ti,Mn)O x coatings with iridium, an acid-stable water-oxidation anode, using acid-sensitive conductive fluorine-doped tin oxides, was achieved.

9.
Adv Mater ; 30(18): e1706076, 2018 May.
Artigo em Inglês | MEDLINE | ID: mdl-29573299

RESUMO

For the electrochemical hydrogen evolution reaction (HER), the electrical properties of catalysts can play an important role in influencing the overall catalytic activity. This is particularly important for semiconducting HER catalysts such as MoS2 , which has been extensively studied over the last decade. Herein, on-chip microreactors on two model catalysts, semiconducting MoS2 and semimetallic WTe2 , are employed to extract the effects of individual factors and study their relations with the HER catalytic activity. It is shown that electron injection at the catalyst/current collector interface and intralayer and interlayer charge transport within the catalyst can be more important than thermodynamic energy considerations. For WTe2 , the site-dependent activities and the relations of the pure thermodynamics to the overall activity are measured and established, as the microreactors allow precise measurements of the type and area of the catalytic sites. The approach presents opportunities to study electrochemical reactions systematically to help establish rational design principles for future electrocatalysts.

10.
Adv Mater ; 30(9)2018 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-29327386

RESUMO

Understanding and possibly recovering from the failure mechanisms of phase change memories (PCMs) are critical to improving their cycle life. Extensive electrical testing and postfailure electron microscopy analysis have shown that stuck-set failure can be recovered. Here, self-healing of novel confined PCM devices is directly shown by controlling the electromigration of the phase change material at the nanoscale. In contrast to the current mushroom PCM, the confined PCM has a metallic surfactant layer, which enables effective Joule heating to control the phase change material even in the presence of a large void. In situ transmission electron microscope movies show that the voltage polarity controls the direction of electromigration of the phase change material, which can be used to fill nanoscale voids that form during programing. Surprisingly, a single voltage pulse can induce dramatic migration of antimony (Sb) due to high current density in the PCM device. Based on the finding, self-healing of a large void inside a confined PCM device with a metallic liner is demonstrated for the first time.

11.
Adv Mater ; 30(6)2018 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-29314276

RESUMO

Black phosphorus (BP) has recently attracted significant attention due to its exceptional physical properties. Currently, high-quality few-layer and thin-film BP are produced primarily by mechanical exfoliation, limiting their potential in future applications. Here, the synthesis of highly crystalline thin-film BP on 5 mm sapphire substrates by conversion from red to black phosphorus at 700 °C and 1.5 GPa is demonstrated. The synthesized ≈50 nm thick BP thin films are polycrystalline with a crystal domain size ranging from 40 to 70 µm long, as indicated by Raman mapping and infrared extinction spectroscopy. At room temperature, field-effect mobility of the synthesized BP thin film is found to be around 160 cm2 V-1 s-1 along armchair direction and reaches up to about 200 cm2 V-1 s-1 at around 90 K. Moreover, red phosphorus (RP) covered by exfoliated hexagonal boron nitride (hBN) before conversion shows atomically sharp hBN/BP interface and perfectly layered BP after the conversion. This demonstration represents a critical step toward the future realization of large scale, high-quality BP devices and circuits.

12.
Nat Commun ; 8(1): 1980, 2017 12 07.
Artigo em Inglês | MEDLINE | ID: mdl-29215011

RESUMO

Many physical phenomena deviate from their established frameworks when the system approaches relevant length scales governing the phenomena. In crystallization, the relevant length scales are the nucleation length set by the nucleus size and density, and the growth length set by diffusion fields. Here we observe unexpected crystallization phenomena at the nanoscale, using metallic glass (MG) nanorods and in situ transmission electron microscopy. The asymmetry between critical heating and cooling rates disappears for small MG nanorods. Strikingly, an apparent single crystalline phase with its composition similar to the glass composition is observed for very small rods, in contrast to bulk samples. We attribute this to the lack of nuclei in small MG nanorods that approach the nucleation length, thus coined the term, nucleus starvation. By controlling the MG nanorod diameter and crystallization kinetics, we can tune the number of nuclei in a nanorod, thereby tailoring the resulting crystallization phases.

13.
Nano Lett ; 17(10): 6273-6279, 2017 10 11.
Artigo em Inglês | MEDLINE | ID: mdl-28873318

RESUMO

Two-dimensional (2D) energy materials have shown the promising electrochemical characteristics for lithium ion storage. However, the decreased active surfaces and the sluggish charge/mass transport for beyond-lithium ion storage that has potential for large-scale energy storage systems, such as sodium or potassium ion storage, caused by the irreversible restacking of 2D materials during electrode processing remain a major challenge. Here we develop a general interlayer engineering strategy to address the above-mentioned challenges by using 2D ultrathin vanadyl phosphate (VOPO4) nanosheets as a model material for challenging sodium ion storage. Via controlled intercalation of organic molecules, such as triethylene glycol and tetrahydrofuran, the sodium ion transport in VOPO4 nanosheets has been significantly improved. In addition to advanced characterization including X-ray diffraction, high-resolution transmission electron microscopy, and X-ray absorption fine structure to characterize the interlayer and the chemical bonding/configuration between the organic intercalants and the VOPO4 host layers, density functional theory calculations are also performed to understand the diffusion behavior of sodium ions in the pure and TEG intercalated VOPO4 nanosheets. Because of the expanded interlayer spacing in combination with the decreased energy barriers for sodium ion diffusion, intercalated VOPO4 nanosheets show much improved sodium ion transport kinetics and greatly enhanced rate capability and cycling stability for sodium ion storage. Our results afford deeper understanding of the interlayer-engineering strategy to improve the sodium ion storage performance of the VOPO4 nanosheets. Our results may also shed light on possible multivalent-ion based energy storage such as Mg2+ and Al3+.

14.
ACS Appl Mater Interfaces ; 9(27): 23175-23180, 2017 Jul 12.
Artigo em Inglês | MEDLINE | ID: mdl-28631485

RESUMO

Recent renewed interest in layered transition metal dichalcogenides stems from the exotic electronic phases predicted and observed in the single- and few-layer limit. Realizing these electronic phases requires preserving the desired transport properties down to a monolayer, which is challenging. Surface oxides are known to impart Fermi level pinning or degrade the mobility on a number of different systems, including transition metal dichalcogenides and black phosphorus. Semimetallic WTe2 exhibits large magnetoresistance due to electron-hole compensation; thus, Fermi level pinning in thin WTe2 flakes could break the electron-hole balance and suppress the large magnetoresistance. We show that WTe2 develops an ∼2 nm thick amorphous surface oxide, which shifts the Fermi level by ∼300 meV at the WTe2 surface. We also observe a dramatic suppression of the magnetoresistance for thin flakes. However, due to the semimetallic nature of WTe2, the effects of Fermi level pinning are well screened and are not the dominant cause for the suppression of magnetoresistance, supported by fitting a two-band model to the transport data, which showed the electron and hole carrier densities are balanced down to ∼13 nm. However, the fitting shows a significant decrease of the mobilities of both electrons and holes. We attribute this to the disorder introduced by the amorphous surface oxide layer. Thus, the decrease of mobility is the dominant factor in the suppression of magnetoresistance for thin WTe2 flakes. Our study highlights the critical need to investigate often unanticipated and sometimes unavoidable extrinsic surface effects on the transport properties of layered dichalcogenides and other 2D materials.

15.
ACS Nano ; 11(7): 7156-7163, 2017 07 25.
Artigo em Inglês | MEDLINE | ID: mdl-28656774

RESUMO

Excitatory and inhibitory postsynaptic potentials are the two fundamental categories of synaptic responses underlying the diverse functionalities of the mammalian nervous system. Recent advances in neuroscience have revealed the co-release of both glutamate and GABA neurotransmitters from a single axon terminal in neurons at the ventral tegmental area that can result in the reconfiguration of the postsynaptic potentials between excitatory and inhibitory effects. The ability to mimic such features of the biological synapses in semiconductor devices, which is lacking in the conventional field effect transistor-type and memristor-type artificial synaptic devices, can enhance the functionalities and versatility of neuromorphic electronic systems in performing tasks such as image recognition, learning, and cognition. Here, we demonstrate an artificial synaptic device concept, an ambipolar junction synaptic devices, which utilizes the tunable electronic properties of the heterojunction between two layered semiconductor materials black phosphorus and tin selenide to mimic the different states of the synaptic connection and, hence, realize the dynamic reconfigurability between excitatory and inhibitory postsynaptic effects. The resulting device relies only on the electrical biases at either the presynaptic or the postsynaptic terminal to facilitate such dynamic reconfigurability. It is distinctively different from the conventional heterosynaptic device in terms of both its operational characteristics and biological equivalence. Key properties of the synapses such as potentiation and depression and spike-timing-dependent plasticity are mimicked in the device for both the excitatory and inhibitory response modes. The device offers reconfiguration properties with the potential to enable useful functionalities in hardware-based artificial neural network.


Assuntos
Materiais Biomiméticos/química , Técnicas Biossensoriais/instrumentação , Fósforo/química , Compostos de Selênio/química , Semicondutores , Sinapses/química , Estanho/química , Potenciais de Ação , Elétrons , Desenho de Equipamento
16.
Nat Commun ; 8: 14474, 2017 04 19.
Artigo em Inglês | MEDLINE | ID: mdl-28422160

RESUMO

Recently rediscovered black phosphorus is a layered semiconductor with promising electronic and photonic properties. Dynamic control of its bandgap can allow for the exploration of new physical phenomena. However, theoretical investigations and photoemission spectroscopy experiments indicate that in its few-layer form, an exceedingly large electric field in the order of several volts per nanometre is required to effectively tune its bandgap, making the direct electrical control unfeasible. Here we reveal the unique thickness-dependent bandgap tuning properties in intrinsic black phosphorus, arising from the strong interlayer electronic-state coupling. Furthermore, leveraging a 10 nm-thick black phosphorus, we continuously tune its bandgap from ∼300 to below 50 meV, using a moderate displacement field up to 1.1 V nm-1. Such dynamic tuning of bandgap may not only extend the operational wavelength range of tunable black phosphorus photonic devices, but also pave the way for the investigation of electrically tunable topological insulators and semimetals.

17.
ACS Appl Mater Interfaces ; 9(16): 14088-14092, 2017 Apr 26.
Artigo em Inglês | MEDLINE | ID: mdl-28361536

RESUMO

We have demonstrated growing uniform and purely nitrogen polar semipolar (202̅1̅) GaN epilayers on 2 in. patterned sapphire substrates. The as-grown surface of (202̅1̅) GaN is composed of two stable facets: (101̅0) and (101̅1̅). A chemical mechanical polishing process was further used to planarize the surface with a final surface root-mean-square roughness of less than 1.5 nm over an area of 10 × 10 µm2. InGaN light-emitting diodes were grown on a polished (202̅1̅) GaN/sapphire template with an electroluminescence emission at around 490 nm. Our work exhibits the potential to produce high-quality nitrogen-polar semipolar GaN templates and optoelectronic devices on large-area sapphire substrates with economical feasibility.

18.
Proc Natl Acad Sci U S A ; 114(14): 3578-3583, 2017 04 04.
Artigo em Inglês | MEDLINE | ID: mdl-28320950

RESUMO

Lithium-sulfur batteries (Li-S batteries) have attracted intense interest because of their high specific capacity and low cost, although they are still hindered by severe capacity loss upon cycling caused by the soluble lithium polysulfide intermediates. Although many structure innovations at the material and device levels have been explored for the ultimate goal of realizing long cycle life of Li-S batteries, it remains a major challenge to achieve stable cycling while avoiding energy and power density compromises caused by the introduction of significant dead weight/volume and increased electrochemical resistance. Here we introduce an ultrathin composite film consisting of naphthalimide-functionalized poly(amidoamine) dendrimers and graphene oxide nanosheets as a cycling stabilizer. Combining the dendrimer structure that can confine polysulfide intermediates chemically and physically together with the graphene oxide that renders the film robust and thin (<1% of the thickness of the active sulfur layer), the composite film is designed to enable stable cycling of sulfur cathodes without compromising the energy and power densities. Our sulfur electrodes coated with the composite film exhibit very good cycling stability, together with high sulfur content, large areal capacity, and improved power rate.

19.
Nano Lett ; 17(3): 2057-2063, 2017 03 08.
Artigo em Inglês | MEDLINE | ID: mdl-28186769

RESUMO

Rational design of multicomponent material structures with strong interfacial interactions enabling enhanced electrocatalysis represents an attractive but underdeveloped paradigm for creating better catalysts for important electrochemical energy conversion reactions. In this work, we report metal-phosphide core-shell nanostructures as a new model electrocatalyst material system where the surface electronic states of the shell phosphide and its interactions with reaction intermediates can be effectively influenced by the core metal to achieve higher catalytic activity. The strategy is demonstrated by the design and synthesis of iron-iron phosphide (Fe@FeP) core-shell nanoparticles on carbon nanotubes (CNTs) where we find that the electronic interactions between the metal and the phosphide components increase the binding strength of hydrogen adatoms toward the optimum. As a consequence, the Fe@FeP/CNT material exhibits exceptional catalytic activity for the hydrogen evolution reaction, only requiring overpotentials of 53-110 mV to reach catalytic current densities of 10-100 mA cm-2.

20.
Adv Mater ; 28(25): 4991-7, 2016 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-27119423

RESUMO

The first black-phosphorus synaptic device is demonstrated, which offers intrinsic anisotropy in its synaptic characteristics directly resulting from its low crystalline symmetry. Key features of biological synapses, such as long-term plasticity with heterogeneity, including long-term potentiation/depression and spike-timing-dependent plasticity, are mimicked. This demonstration represents an important step toward introducing intrinsic heterogeneity to artificial neuromorphic systems.

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