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1.
Adv Mater ; 34(3): e2106674, 2022 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-34738669

RESUMO

Defects are ubiquitous in 2D materials and can affect the structure and properties of the materials and also introduce new functionalities. Methods to adjust the structure and density of defects during bottom-up synthesis are required to control the growth of 2D materials with tailored optical and electronic properties. Here, the authors present an Au-assisted chemical vapor deposition approach to selectively form SW and S2W antisite defects, whereby one or two sulfur atoms substitute for a tungsten atom in WS2 monolayers. Guided by first-principles calculations, they describe a new method that can maintain tungsten-poor growth conditions relative to sulfur via the low solubility of W atoms in a gold/W alloy, thereby significantly reducing the formation energy of the antisite defects during the growth of WS2 . The atomic structure and composition of the antisite defects are unambiguously identified by Z-contrast scanning transmission electron microscopy and electron energy-loss spectroscopy, and their total concentration is statistically determined, with levels up to ≈5.0%. Scanning tunneling microscopy/spectroscopy measurements and first-principles calculations further verified these antisite defects and revealed the localized defect states in the bandgap of WS2 monolayers. This bottom-up synthesis method to form antisite defects should apply in the synthesis of other 2D materials.

2.
Nanomicro Lett ; 14(1): 2, 2021 Dec 02.
Artigo em Inglês | MEDLINE | ID: mdl-34859320

RESUMO

Engineering oxygen vacancy formation and distribution is a powerful route for controlling the oxygen sublattice evolution that affects diverse functional behavior. The controlling of the oxygen vacancy formation process is particularly important for inducing topotactic phase transitions that occur by transformation of the oxygen sublattice. Here we demonstrate an epitaxial nanocomposite approach for exploring the spatial control of topotactic phase transition from a pristine perovskite phase to an oxygen vacancy-ordered brownmillerite (BM) phase in a model oxide La0.7Sr0.3MnO3 (LSMO). Incorporating a minority phase NiO in LSMO films creates ultrahigh density of vertically aligned epitaxial interfaces that strongly influence the oxygen vacancy formation and distribution in LSMO. Combined structural characterizations reveal strong interactions between NiO and LSMO across the epitaxial interfaces leading to a topotactic phase transition in LSMO accompanied by significant morphology evolution in NiO. Using the NiO nominal ratio as a single control parameter, we obtain intermediate topotactic nanostructures with distinct distribution of the transformed LSMO-BM phase, which enables systematic tuning of magnetic and electrical transport properties. The use of self-assembled heterostructure interfaces by the epitaxial nanocomposite platform enables more versatile design of topotactic phase structures and correlated functionalities that are sensitive to oxygen vacancies.

3.
ACS Nano ; 15(5): 8638-8652, 2021 May 25.
Artigo em Inglês | MEDLINE | ID: mdl-33929816

RESUMO

Understanding the bottom-up synthesis of atomically thin two-dimensional (2D) crystals and heterostructures is important for the development of new processing strategies to assemble 2D heterostructures with desired functional properties. Here, we utilize in situ laser-heating within a transmission electron microscope (TEM) to understand the stages of crystallization and coalescence of amorphous precursors deposited by pulsed laser deposition (PLD) as they are guided by 2D crystalline substrates into van der Waals (vdW) epitaxial heterostructures. Amorphous clusters of tungsten selenide were deposited by PLD at room temperature onto graphene or MoSe2 monolayer crystals that were suspended on TEM grids. The precursors were then stepwise evolved into 2D heterostructures with pulsed laser heating treatments within the TEM. The lattice-matching provided by the MoSe2 substrate is shown to guide the formation of large-domain, heteroepitaxial vdW WSe2/MoSe2 bilayers both during the crystallization process via direct templating and after crystallization by assisting the coalescence of nanosized domains through nonclassical particle attachment processes including domain rotation and grain boundary migration. The favorable energetics for domain rotation induced by lattice matching with the substrate were understood from first-principles calculations. These in situ TEM studies of pulsed laser-driven nonequilibrium crystallization phenomena represent a transformational tool for the rapid exploration of synthesis and processing pathways that may occur on extremely different length and time scales and lend insight into the growth of 2D crystals by PLD and laser crystallization.

4.
ACS Nano ; 15(3): 4504-4517, 2021 Mar 23.
Artigo em Inglês | MEDLINE | ID: mdl-33651582

RESUMO

Tailoring the grain boundaries (GBs) and twist angles between two-dimensional (2D) crystals are two crucial synthetic challenges to deterministically enable envisioned applications such as moiré excitons, emerging magnetism, or single-photon emission. Here, we reveal how twisted 2D bilayers can be synthesized from the collision and coalescence of two growing monolayer MoS2 crystals during chemical vapor deposition. The twisted bilayer (TB) moiré angles are found to preserve the misorientation angle (θ) of the colliding crystals. The shapes of the TB regions are rationalized by a kink propagation model that predicts the GB formed by the coalescing crystals. Optical spectroscopy measurements reveal a θ-dependent long-range strain in crystals with stitched grain boundaries and a sharp (θ > 20°) threshold for the appearance of TBs, which relieves this strain. Reactive molecular dynamics simulations explain this strain from the continued growth of the crystals during coalescence due to the insertion of atoms at unsaturated defects along the GB, a process that self-terminates when the defects become saturated. The simulations also reproduce atomic-resolution electron microscopy observations of faceting along the GB, which is shown to arise from the growth-induced long-range strain. These facets align with the axes of the colliding crystals to provide favorable nucleation sites for second-layer growth of a TB with twist angles that preserve the misorientation angle θ. This interplay between strain generation and aligned nucleation provides a synthetic pathway for the growth of TBs with deterministic angles.

5.
ACS Nano ; 15(2): 2858-2868, 2021 Feb 23.
Artigo em Inglês | MEDLINE | ID: mdl-33576605

RESUMO

Pulsed laser deposition (PLD) can be considered a powerful method for the growth of two-dimensional (2D) transition-metal dichalcogenides (TMDs) into van der Waals heterostructures. However, despite significant progress, the defects in 2D TMDs grown by PLD remain largely unknown and yet to be explored. Here, we combine atomic resolution images and first-principles calculations to reveal the atomic structure of defects, grains, and grain boundaries in mono- and bilayer MoS2 grown by PLD. We find that sulfur vacancies and MoS antisites are the predominant point defects in 2D MoS2. We predict that the aforementioned point defects are thermodynamically favorable under a Mo-rich/S-poor environment. The MoS2 monolayers are polycrystalline and feature nanometer size grains connected by a high density of grain boundaries. In particular, the coalescence of nanometer grains results in the formation of 180° mirror twin boundaries consisting of distinct 4- and 8-membered rings. We show that PLD synthesis of bilayer MoS2 results in various structural symmetries, including AA' and AB, but also turbostratic with characteristic moiré patterns. Moreover, we report on the experimental demonstration of an electron beam-driven transition between the AB and AA' stacking orientations in bilayer MoS2. These results provide a detailed insight into the atomic structure of monolayer MoS2 and the role of the grain boundaries on the growth of bilayer MoS2, which has importance for future applications in optoelectronics.

7.
Adv Mater ; 32(19): e1906238, 2020 May.
Artigo em Inglês | MEDLINE | ID: mdl-32173918

RESUMO

Two-dimensional (2D) palladium diselenide (PdSe2 ) has strong interlayer coupling and a puckered pentagonal structure, leading to remarkable layer-dependent electronic structures and highly anisotropic in-plane optical and electronic properties. However, the lack of high-quality, 2D PdSe2 crystals grown by bottom-up approaches limits the study of their exotic properties and practical applications. In this work, chemical vapor deposition growth of highly crystalline few-layer (≥2 layers) PdSe2 crystals on various substrates is reported. The high quality of the PdSe2 crystals is confirmed by low-frequency Raman spectroscopy, scanning transmission electron microscopy, and electrical characterization. In addition, strong in-plane optical anisotropy is demonstrated via polarized Raman spectroscopy and second-harmonic generation maps of the PdSe2 flakes. A theoretical model based on kinetic Wulff construction theory and density functional theory calculations is developed and described the observed evolution of "square-like" shaped PdSe2 crystals into rhombus due to the higher nucleation barriers for stable attachment on the (1,1) and (1,-1) edges, which results in their slower growth rates. Few-layer PdSe2 field-effect transistors reveal tunable ambipolar charge carrier conduction with an electron mobility up to ≈294 cm2 V-1 s-1 , which is comparable to that of exfoliated PdSe2 , indicating the promise of this anisotropic 2D material for electronics.

8.
ACS Nano ; 14(4): 3896-3906, 2020 Apr 28.
Artigo em Inglês | MEDLINE | ID: mdl-32150384

RESUMO

Atomically thin two-dimensional (2D) materials face significant energy barriers for synthesis and processing into functional metastable phases such as Janus structures. Here, the controllable implantation of hyperthermal species from pulsed laser deposition (PLD) plasmas is introduced as a top-down method to compositionally engineer 2D monolayers. The kinetic energies of Se clusters impinging on suspended monolayer WS2 crystals were controlled in the <10 eV/atom range with in situ plasma diagnostics to determine the thresholds for selective top layer replacement of sulfur by selenium for the formation of high quality WSSe Janus monolayers at low (300 °C) temperatures and bottom layer replacement for complete conversion to WSe2. Atomic-resolution electron microscopy and spectroscopy in tilted geometry confirm the WSSe Janus monolayer. Molecular dynamics simulations reveal that Se clusters implant to form disordered metastable alloy regions, which then recrystallize to form highly ordered structures, demonstrating low-energy implantation by PLD for the synthesis of 2D Janus layers and alloys of variable composition.

9.
Ultramicroscopy ; 209: 112842, 2020 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-31715387

RESUMO

Automated image recognition and analysis techniques were combined with liquid cell transmission electron microscopy to explore the oxidation kinetics of nanocrystalline Fe thin films in a water vapor environment. From in situ microscopy experiments, localized oxidation was observed to initiate in the film then propagate in an unsteady fashion, alternatingly arresting and progressing. The oxidation front propagation occurred via new oxidation sites initiating 10s of nm ahead of the existing front rather than through a continuous expansion mechanism. The oxidation rate was seen to be highly dependent on electron dose rate, with increasing electron dose rate accelerating the oxidation front propagation and increasing the density of oxidation initiation sites. The in situ experiments were also performed in diffraction space where it was seen that Fe2O3 was formed during oxidation. Coupling in situ microscopy with automated image analysis creates new opportunities for studying the early stages of localized corrosion by providing direct observation of oxidation propagation as well as quantification of the oxidation rates and rapid identification of byproducts.

10.
Sci Adv ; 5(5): eaav4028, 2019 May.
Artigo em Inglês | MEDLINE | ID: mdl-31172023

RESUMO

Two-dimensional (2D) crystal growth over substrate features is fundamentally guided by the Gauss-Bonnet theorem, which mandates that rigid, planar crystals cannot conform to surfaces with nonzero Gaussian curvature. Here, we reveal how topographic curvature of lithographically designed substrate features govern the strain and growth dynamics of triangular WS2 monolayer single crystals. Single crystals grow conformally without strain over deep trenches and other features with zero Gaussian curvature; however, features with nonzero Gaussian curvature can easily impart sufficient strain to initiate grain boundaries and fractured growth in different directions. Within a strain-tolerant regime, however, triangular single crystals can accommodate considerable (<1.1%) localized strain exerted by surface features that shift the bandgap up to 150 meV. Within this regime, the crystal growth accelerates in specific directions, which we describe using a growth model. These results present a previously unexplored strategy to strain-engineer the growth directions and optoelectronic properties of 2D crystals.

12.
J Am Chem Soc ; 141(22): 8928-8936, 2019 Jun 05.
Artigo em Inglês | MEDLINE | ID: mdl-31090414

RESUMO

The failure to achieve stable Ohmic contacts in two-dimensional material devices currently limits their promised performance and integration. Here we demonstrate that a phase transformation in a region of a layered semiconductor, PdSe2, can form a contiguous metallic Pd17Se15 phase, leading to the formation of seamless Ohmic contacts for field-effect transistors. This phase transition is driven by defects created by exposure to an argon plasma. Cross-sectional scanning transmission electron microscopy is combined with theoretical calculations to elucidate how plasma-induced Se vacancies mediate the phase transformation. The resulting Pd17Se15 phase is stable and shares the same native chemical bonds with the original PdSe2 phase, thereby forming an atomically sharp Pd17Se15/PdSe2 interface. These Pd17Se15 contacts exhibit a low contact resistance of ∼0.75 kΩ µm and Schottky barrier height of ∼3.3 meV, enabling nearly a 20-fold increase of carrier mobility in PdSe2 transistors compared to that of traditional Ti/Au contacts. This finding opens new possibilities in the development of better electrical contacts for practical applications of 2D materials.

13.
ACS Appl Mater Interfaces ; 11(19): 17979-17986, 2019 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-31021595

RESUMO

Ionic liquids (ILs) have been investigated extensively because of their unique ability to form the electric double layer (EDL), which induces high electrical field. For certain materials, low-temperature IL charging is needed to limit the electrochemical etching. Here, we report our investigation of the low-temperature charging dynamics in two widely used ILs-DEME-TF2N and C4mim-TF2N. Results show that the formation of the EDL at ∼220 K requires several hours relative to milliseconds at room temperature, and an equivalent voltage Ve is introduced as a measure of the EDL formation during the biasing process. The experimental observation is supported by molecular dynamics simulation, which shows that the dynamics are logically a function of gate voltage, time, and temperature. To demonstrate the importance of understanding the charging dynamics, a 140 nm thick FeSe0.5Te0.5 film was biased using the DEME IL, showing a tunable Tc between 18 and 35 K. Notably, this is the first observation of the tunability of the Tc in thick film FeSe0.5Te0.5 superconductors.

14.
Nanoscale ; 11(17): 8138-8149, 2019 Apr 25.
Artigo em Inglês | MEDLINE | ID: mdl-30788480

RESUMO

Photocatalytic hydrogen evolution from water has received enormous attention due to its ability to address a number of global environmental and energy-related issues. Here, we synthesize 2D/2D Ti3C2/g-C3N4 composites by electrostatic self-assembly technique and demonstrate their use as photocatalysts for hydrogen evolution under visible light irradiation. The optimized Ti3C2/g-C3N4 composite exhibited a 10 times higher photocatalytic hydrogen evolution performance (72.3 µmol h-1 gcat-1) than that of pristine g-C3N4 (7.1 µmol h-1 gcat-1). Such enhanced photocatalytic performance was due to the formation of 2D/2D heterojunctions in the Ti3C2/g-C3N4 composites. The intimate contact between the monolayer Ti3C2 and g-C3N4 nanosheets promotes the separation of photogenerated charge carriers at the Ti3C2/g-C3N4 interface. Furthermore, the ultrahigh conductivity of Ti3C2 and the Schottky junction formed between g-C3N4/MXene interfaces facilitate the photoinduced electron transfer and suppress the recombination with photogenerated holes. This work demonstrates that the 2D/2D Ti3C2/g-C3N4 composites are promising photocatalysts thanks to the ultrathin MXenes as efficient co-catalysts for photocatalytic hydrogen production.

15.
ACS Nano ; 13(2): 2481-2489, 2019 Feb 26.
Artigo em Inglês | MEDLINE | ID: mdl-30673215

RESUMO

Isotopes represent a degree of freedom that might be exploited to tune the physical properties of materials while preserving their chemical behaviors. Here, we demonstrate that the thermal properties of two-dimensional (2D) transition-metal dichalcogenides can be tailored through isotope engineering. Monolayer crystals of MoS2 were synthesized with isotopically pure 100Mo and 92Mo by chemical vapor deposition employing isotopically enriched molybdenum oxide precursors. The in-plane thermal conductivity of the 100MoS2 monolayers, measured using a non-destructive, optothermal Raman technique, is found to be enhanced by ∼50% compared with the MoS2 synthesized using mixed Mo isotopes from naturally occurring molybdenum oxide. The boost of thermal conductivity in isotopically pure MoS2 monolayers is attributed to the combined effects of reduced isotopic disorder and a reduction in defect-related scattering, consistent with observed stronger photoluminescence and longer exciton lifetime. These results shed light on the fundamentals of 2D nanoscale thermal transport important for the optimization of 2D electronic devices.

16.
Nano Lett ; 19(2): 1033-1038, 2019 02 13.
Artigo em Inglês | MEDLINE | ID: mdl-30673240

RESUMO

In classical morphotropic piezoelectric materials, rhombohedral and tetragonal phase variants can energetically compete to form a mixed phase regime with improved functional properties. While the discovery of morphotropic-like phases in multiferroic BiFeO3 films has broadened this definition, accessing these phase spaces is still typically accomplished through isovalent substitution or heteroepitaxial strain which do not allow for continuous modification of phase composition postsynthesis. Here, we show that it is possible to use low-energy helium implantation to tailor morphotropic phases of epitaxial BiFeO3 films postsynthesis in a continuous and iterative manner. Applying this strain doping approach to morphotropic films creates a new phase space based on internal and external lattice stress that can be seen as an analogue to temperature-composition phase diagrams of classical morphotropic ferroelectric systems.

17.
Nat Commun ; 9(1): 2051, 2018 05 24.
Artigo em Inglês | MEDLINE | ID: mdl-29795375

RESUMO

Exerting synthetic control over the edge structure and chemistry of two-dimensional (2D) materials is of critical importance to direct the magnetic, optical, electrical, and catalytic properties for specific applications. Here, we directly image the edge evolution of pores in Mo1-xW x Se2 monolayers via atomic-resolution in situ scanning transmission electron microscopy (STEM) and demonstrate that these edges can be structurally transformed to theoretically predicted metastable atomic configurations by thermal and chemical driving forces. Density functional theory calculations and ab initio molecular dynamics simulations explain the observed thermally induced structural evolution and exceptional stability of the four most commonly observed edges based on changing chemical potential during thermal annealing. The coupling of modeling and in situ STEM imaging in changing chemical environments demonstrated here provides a pathway for the predictive and controlled atomic scale manipulation of matter for the directed synthesis of edge configurations in Mo1-x W x Se2 to achieve desired functionality.

18.
Adv Mater ; 30(22): e1705801, 2018 May.
Artigo em Inglês | MEDLINE | ID: mdl-29660765

RESUMO

A fundamental understanding of the interplay between the microscopic structure and macroscopic optoelectronic properties of organic-inorganic hybrid perovskite materials is essential to design new materials and improve device performance. However, how exactly the organic cations affect the structural phase transition and optoelectronic properties of the materials is not well understood. Here, real-time, in situ temperature-dependent neutron/X-ray diffraction and photoluminescence (PL) measurements reveal a transformation of the organic cation CH3 NH3+ from order to disorder with increasing temperature in CH3 NH3 PbBr3 perovskites. The molecular-level order-to-disorder transformation of CH3 NH3+ not only leads to an anomalous increase in PL intensity, but also results in a multidomain to single-domain structural transition. This discovery establishes the important role that organic cation ordering has in dictating structural order and anomalous optoelectronic phenomenon in hybrid perovskites.

19.
ACS Appl Mater Interfaces ; 10(13): 11008-11017, 2018 Apr 04.
Artigo em Inglês | MEDLINE | ID: mdl-29528215

RESUMO

Simple and easily integrated design of flexible and transparent electrode materials affixed to polymer-based substrates hold great promise to have a revolutionary impact on the functionality and performance of energy storage devices for many future consumer electronics. Among these applications are touch sensors, roll-up displays, photovoltaic cells, health monitors, wireless sensors, and wearable communication devices. Here, we report an environmentally friendly, simple, and versatile approach to produce optically transparent and mechanically flexible all-solid-state supercapacitor devices. These supercapacitors were constructed on tin-doped indium oxide coated polyethylene terephthalate substrates by intercalation of a polymer-based gel electrolyte between two reduced graphene oxide (rGO) thin-film electrodes. The rGO electrodes were fabricated simply by drop-casting of graphene oxide (GO) films, followed by a novel low-temperature (≤250 °C) vacuum-assisted annealing approach for the in situ reduction of GO to rGO. A trade-off between the optical transparency and electrochemical performance is determined by the concentration of the GO in the initial dispersion, whereby the highest capacitance (∼650 µF cm-2) occurs at a relatively lower optical transmittance (24%). Notably, the all-solid-state supercapacitors demonstrated excellent mechanical flexibility with a capacity retention rate above 90% under various bending angles and cycles. These attributes underscore the potential of the present approach to provide a path toward the realization of thin-film-based supercapacitors as flexible and transparent energy storage devices for a variety of practical applications.

20.
ACS Appl Mater Interfaces ; 10(5): 4816-4823, 2018 Feb 07.
Artigo em Inglês | MEDLINE | ID: mdl-29322765

RESUMO

Proton-conducting perovskites have been widely studied because of their potential application as solid electrolytes in intermediate temperature solid oxide fuel cells. Structural and chemical heterogeneities can develop during synthesis, device fabrication, or service, which can profoundly affect proton transport. Here, we use time-resolved Kelvin probe force microscopy, scanning transmission electron microscopy, atom probe tomography, and density functional theory calculations to intentionally introduce Ba-deficient planar and spherical defects and link the resultant atomic structure with proton transport behavior in both stoichiometric and nonstoichiometric epitaxial, yttrium-doped barium zirconate thin films. The defects were intentionally induced through high-temperature annealing treatment, while maintaining the epitaxial single crystalline structure of the films, with an overall relaxation in the atomic structure. The annealed samples showed smaller magnitudes of local lattice distortions because of the formation of proton polarons, thereby leading to decreased proton-trapping effect. This resulted in a decrease in the activation energy for proton transport, leading to faster proton transport.

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