Your browser doesn't support javascript.
loading
Mostrar: 20 | 50 | 100
Resultados 1 - 20 de 31
Filtrar
Mais filtros










Base de dados
Intervalo de ano de publicação
1.
Nano Lett ; 2020 Apr 21.
Artigo em Inglês | MEDLINE | ID: mdl-32267709

RESUMO

The electron beam (e-beam) in the scanning electron microscopy (SEM) provides an appealing mobile heating source for thermal metrology with spatial resolution of ∼1 nm, but the lack of systematic quantification of the e-beam heating power limits such application development. Here, we systemically study e-beam heating in LPCVD silicon nitride (SiNx) thin-films with thickness ranging from 200 to 500 nm from both experiments and complementary Monte Carlo simulations using the CASINO software package. There is good agreement about the thickness-dependent e-beam energy absorption of thin-film between modeling predictions and experiments. Using the absorption results, we then demonstrate adapting the e-beam as a quantitative heating source by measuring the thickness-dependent thermal conductivity of SiNx thin-films, with the results validated to within 7% by a separate Joule heating experiment. The results described here will open a new avenue for using SEM e-beams as a mobile heating source for advanced nanoscale thermal metrology development.

2.
J Phys Chem Lett ; 11(7): 2624-2629, 2020 Apr 02.
Artigo em Inglês | MEDLINE | ID: mdl-32191469

RESUMO

Mn2+ doping of lead halide perovskites has garnered recent interest because it produces stable orange luminescence in tandem with perovskite emission. Here, we observe enhanced Mn2+ luminescence at the edges of Mn2+-doped CsPbCl3 perovskite microplates and suggest an explanation for its origin using the high spatiotemporal resolution of time-resolved cathodoluminescence (TRCL) imaging. We reveal two luminescent decay components that we attribute to two different Mn2+ populations. While each component appears to be present both near the surface and in the bulk, the origin of the intensity variation stems from a higher proportion of the longer lifetime component near the perovskite surface. We suggest that this higher emission is caused by an increased probability of electron-hole recombination on Mn2+ near the perovskite surface due to an increased trap concentration there. This observation suggests that such surface features have yet untapped potential to enhance emissive properties via control of surface-to-volume ratio.

3.
Phys Rev Lett ; 123(7): 076801, 2019 Aug 16.
Artigo em Inglês | MEDLINE | ID: mdl-31491121

RESUMO

Structural defects in 2D materials offer an effective way to engineer new material functionalities beyond conventional doping. We report on the direct experimental correlation of the atomic and electronic structure of a sulfur vacancy in monolayer WS_{2} by a combination of CO-tip noncontact atomic force microscopy and scanning tunneling microscopy. Sulfur vacancies, which are absent in as-grown samples, were deliberately created by annealing in vacuum. Two energetically narrow unoccupied defect states followed by vibronic sidebands provide a unique fingerprint of this defect. Direct imaging of the defect orbitals, together with ab initio GW calculations, reveal that the large splitting of 252±4 meV between these defect states is induced by spin-orbit coupling.

4.
ACS Nano ; 13(9): 10520-10534, 2019 Sep 24.
Artigo em Inglês | MEDLINE | ID: mdl-31393700

RESUMO

Control of impurity concentrations in semiconducting materials is essential to device technology. Because of their intrinsic confinement, the properties of two-dimensional semiconductors such as transition metal dichalcogenides (TMDs) are more sensitive to defects than traditional bulk materials. The technological adoption of TMDs is dependent on the mitigation of deleterious defects and guided incorporation of functional foreign atoms. The first step toward impurity control is the identification of defects and assessment of their electronic properties. Here, we present a comprehensive study of point defects in monolayer tungsten disulfide (WS2) grown by chemical vapor deposition using scanning tunneling microscopy/spectroscopy, CO-tip noncontact atomic force microscopy, Kelvin probe force spectroscopy, density functional theory, and tight-binding calculations. We observe four different substitutional defects: chromium (CrW) and molybdenum (MoW) at a tungsten site, oxygen at sulfur sites in both top and bottom layers (OS top/bottom), and two negatively charged defects (CD type I and CD type II). Their electronic fingerprints unambiguously corroborate the defect assignment and reveal the presence or absence of in-gap defect states. CrW forms three deep unoccupied defect states, two of which arise from spin-orbit splitting. The formation of such localized trap states for CrW differs from the MoW case and can be explained by their different d shell energetics and local strain, which we directly measured. Utilizing a tight-binding model the electronic spectra of the isolectronic substitutions OS and CrW are mimicked in the limit of a zero hopping term and infinite on-site energy at a S and W site, respectively. The abundant CDs are negatively charged, which leads to a significant band bending around the defect and a local increase of the contact potential difference. In addition, CD-rich domains larger than 100 nm are observed, causing a work function increase of 1.1 V. While most defects are electronically isolated, we also observed hybrid states formed between CrW dimers. The important role of charge localization, spin-orbit coupling, and strain for the formation of deep defect states observed at substitutional defects in WS2 as reported here will guide future efforts of targeted defect engineering and doping of TMDs.

5.
Nat Nanotechnol ; 14(5): 420-425, 2019 05.
Artigo em Inglês | MEDLINE | ID: mdl-30833691

RESUMO

Electron microscopy has been instrumental in our understanding of complex biological systems. Although electron microscopy reveals cellular morphology with nanoscale resolution, it does not provide information on the location of different types of proteins. An electron-microscopy-based bioimaging technology capable of localizing individual proteins and resolving protein-protein interactions with respect to cellular ultrastructure would provide important insights into the molecular biology of a cell. Here, we synthesize small lanthanide-doped nanoparticles and measure the absolute photon emission rate of individual nanoparticles resulting from a given electron excitation flux (cathodoluminescence). Our results suggest that the optimization of nanoparticle composition, synthesis protocols and electron imaging conditions can lead to sub-20-nm nanolabels that would enable high signal-to-noise localization of individual biomolecules within a cellular context. In ensemble measurements, these labels exhibit narrow spectra of nine distinct colours, so the imaging of biomolecules in a multicolour electron microscopy modality may be possible.


Assuntos
Corantes Fluorescentes/química , Microscopia Eletrônica de Transmissão , Nanopartículas/química
6.
J Chem Phys ; 149(15): 154305, 2018 Oct 21.
Artigo em Inglês | MEDLINE | ID: mdl-30342450

RESUMO

New photoresists are needed to advance extreme ultraviolet (EUV) lithography. The tailored design of efficient photoresists is enabled by a fundamental understanding of EUV induced chemistry. Processes that occur in the resist film after absorption of an EUV photon are discussed, and a new approach to study these processes on a fundamental level is described. The processes of photoabsorption, electron emission, and molecular fragmentation were studied experimentally in the gas-phase on analogs of the monomer units employed in chemically amplified EUV resists. To demonstrate the dependence of the EUV absorption cross section on selective light harvesting substituents, halogenated methylphenols were characterized employing the following techniques. Photoelectron spectroscopy was utilized to investigate kinetic energies and yield of electrons emitted by a molecule. The emission of Auger electrons was detected following photoionization in the case of iodo-methylphenol. Mass-spectrometry was used to deduce the molecular fragmentation pathways following electron emission and atomic relaxation. To gain insight on the interaction of emitted electrons with neutral molecules in a condensed film, the fragmentation pattern of neutral gas-phase molecules, interacting with an electron beam, was studied and observed to be similar to EUV photon fragmentation. Below the ionization threshold, electrons were confirmed to dissociate iodo-methylphenol by resonant electron attachment.

7.
Sci Rep ; 8(1): 5761, 2018 Apr 10.
Artigo em Inglês | MEDLINE | ID: mdl-29636534

RESUMO

We report visualizations of the bidirectional near-field optical transfer function for a waveguide-coupled plasmonic transducer as a metrology technique essential for successful development for mass-fabricated near-field devices. Plasmonic devices have revolutionized the observation of nanoscale phenomena, enabling optical excitation and readout from nanoscale regions of fabricated devices instead of as limited by optical diffraction. Visualizations of the plasmonic transducer modes were acquired both by local near-field excitation of the antenna on the front facet of a waveguide using the focused electron beam of a scanning electron microscope as a probe of the near-field cathodoluminescence during far-field collection from the back facet of the waveguide, and by local mapping of the optical near-field for the same antenna design using scattering scanning near-field optical microscopy as a probe of the near-field optical mode density for far-field light focused into the back facet of the waveguide. Strong agreement between both measurement types and numerical modeling was observed, indicating that the method enables crucial metrological comparisons of as fabricated device performance to as-modeled device expectations for heat-assisted magnetic recording heads, which can be extended to successful development of future near-field-on-chip devices such as optical processor interconnects.

8.
ACS Nano ; 11(10): 10583-10590, 2017 10 24.
Artigo em Inglês | MEDLINE | ID: mdl-28956598

RESUMO

In situ electron microscopy provides remarkably high spatial resolution, yet electron beam irradiation often damages soft materials and perturbs dynamic processes, requiring samples to be very robust. Here, we instead noninvasively image the dynamics of metal and polymer nanoparticles in a liquid environment with subdiffraction resolution using cathodoluminescence-activated imaging by resonant energy transfer (CLAIRE). In CLAIRE, a free-standing scintillator film serves as a nanoscale optical excitation source when excited by a low energy, focused electron beam. We capture the nanoscale dynamics of these particles translating along and desorbing from the scintillator surface and demonstrate 50 ms frame acquisition and a range of imaging of at least 20 nm from the scintillator surface. Furthermore, in contrast with in situ electron microscopy, CLAIRE provides spectral selectivity instead of relying on scattering alone. We also demonstrate through quantitative modeling that the CLAIRE signal from metal nanoparticles is impacted by multiplasmonic mode interferences. Our findings demonstrate that CLAIRE is a promising, noninvasive approach for super-resolution imaging for soft and fluid materials with high spatial and temporal resolution.

9.
Nanoscale ; 9(34): 12288-12294, 2017 Aug 31.
Artigo em Inglês | MEDLINE | ID: mdl-28809419

RESUMO

We report on the vibrational (Raman) spectrum and structural transformation of semiconducting pseudo-1D GaTe and ZrTe3 nanomaterials driven by ambient molecular interactions at the nanoscale by angle-resolved Raman spectroscopy, atomic force microscopy (AFM), and environmental X-ray photoelectron (XPS) measurements. The results show that tellurium containing pseudo-1D materials undergo drastic structural and physical changes within a week. During this process, new Raman peaks start to emerge and surface roughness increases substantially. Surprisingly, aged Raman spectra of GaTe, ZrTe3, and α-TeOx show striking similarities suggesting that oxidation of tellurium takes place. Careful, environmental tests reveal that the interaction between GaTe and H2O molecules forms Te-O bonds at the outermost layers of GaTe which leads to newly emerging Raman peaks, a much reduced Schottky junction current density, and an anisotropic to isotropic structural transition. These findings offer fresh interpretation of the aging mechanisms for these material systems, provide new interpretation of the Raman spectrum of aged GaTe which was previously presumed to be of the hexagonal phase, and introduce an anisotropic to isotropic transformation effect induced by molecular interactions on the surface.

10.
J Chem Phys ; 146(16): 164106, 2017 Apr 28.
Artigo em Inglês | MEDLINE | ID: mdl-28456207

RESUMO

In order to increase computation power and efficiency, the semiconductor industry continually strives to reduce the size of features written using lithographic techniques. The planned switch to a shorter wavelength extreme ultraviolet (EUV) source presents a challenge for the associated photoresists, which in their current manifestation show much poorer photoabsorption cross sections for the same dose. Here we consider the critical role that an inner-shell electronic structure might play in enhancing photoabsorption cross sections, which one can control by the choice of substituent elements in the photoresist. In order to increase the EUV sensitivity of current photoresists, it is critical to consider the inner-shell atomic structure of the elements that compose the materials. We validate this hypothesis using a series of halogenated organic molecules, which all have similar valence structures, but differ in the character of their semi-core and deep valence levels. Using various implementations of time-dependent density functional theory, the absorption cross sections are computed for the model systems of CH3X, X = H, OH, F, Cl, Br, I, as well as a representative polymer fragment: 2-methyl-phenol and its halogenated analogues. Iodine has a particularly high cross section in the EUV range, which is due to delayed absorption by its 4d electrons. The computational results are compared to standard database values and experimental data when available. Generally we find that the states that dominate the EUV oscillator strength are generated by excitations of deep valence or semi-core electrons, which are primarily atomic-like and relatively insensitive to the specific molecular structure.

11.
Nano Lett ; 17(2): 1028-1033, 2017 02 08.
Artigo em Inglês | MEDLINE | ID: mdl-28134530

RESUMO

The distinct physical properties of hybrid organic-inorganic materials can lead to unexpected nonequilibrium phenomena that are difficult to characterize due to the broad range of length and time scales involved. For instance, mixed halide hybrid perovskites are promising materials for optoelectronics, yet bulk measurements suggest the halides reversibly phase separate upon photoexcitation. By combining nanoscale imaging and multiscale modeling, we find that the nature of halide demixing in these materials is distinct from macroscopic phase separation. We propose that the localized strain induced by a single photoexcited charge interacting with the soft, ionic lattice is sufficient to promote halide phase separation and nucleate a light-stabilized, low-bandgap, ∼8 nm iodide-rich cluster. The limited extent of this polaron is essential to promote demixing because by contrast bulk strain would simply be relaxed. Photoinduced phase separation is therefore a consequence of the unique electromechanical properties of this hybrid class of materials. Exploiting photoinduced phase separation and other nonequilibrium phenomena in hybrid materials more generally could expand applications in sensing, switching, memory, and energy storage.

12.
Nat Commun ; 7: 11924, 2016 06 21.
Artigo em Inglês | MEDLINE | ID: mdl-27323904

RESUMO

The sensitivity of semiconductor photodetectors is limited by photocarrier recombination during the carrier transport process. We developed a new photoactive material that reduces recombination by physically separating hole and electron charge carriers. This material has a specific detectivity (the ability to detect small signals) of 5 × 10(17) Jones, the highest reported in visible and infrared detectors at room temperature, and 4-5 orders of magnitude higher than that of commercial single-crystal silicon detectors. The material was fabricated by sintering chloride-capped CdTe nanocrystals into polycrystalline films, where Cl selectively segregates into grain boundaries acting as n-type dopants. Photogenerated electrons concentrate in and percolate along the grain boundaries-a network of energy valleys, while holes are confined in the grain interiors. This electrostatic field-assisted carrier separation and percolation mechanism enables an unprecedented photoconductive gain of 10(10) e(-) per photon, and allows for effective control of the device response speed by active carrier quenching.

13.
Adv Mater ; 27(38): 5693-719, 2015 Oct 14.
Artigo em Inglês | MEDLINE | ID: mdl-26332202

RESUMO

Reduced-dimensionality materials for photonic and optoelectronic applications including energy conversion, solid-state lighting, sensing, and information technology are undergoing rapid development. The search for novel materials based on reduced-dimensionality is driven by new physics. Understanding and optimizing material properties requires characterization at the relevant length scale, which is often below the diffraction limit. Three important material systems are chosen for review here, all of which are under investigation at the Molecular Foundry, to illustrate the current state of the art in nanoscale optical characterization: 2D semiconducting transition metal dichalcogenides; 1D semiconducting nanowires; and energy-transfer in assemblies of 0D semiconducting nanocrystals. For each system, the key optical properties, the principal experimental techniques, and important recent results are discussed. Applications and new developments in near-field optical microscopy and spectroscopy, scanning probe microscopy, and cathodoluminescence in the electron microscope are given detailed attention. Work done at the Molecular Foundry is placed in context within the fields under review. A discussion of emerging opportunities and directions for the future closes the review.

14.
Nat Commun ; 6: 7993, 2015 Aug 13.
Artigo em Inglês | MEDLINE | ID: mdl-26269394

RESUMO

Two-dimensional monolayer transition metal dichalcogenide semiconductors are ideal building blocks for atomically thin, flexible optoelectronic and catalytic devices. Although challenging for two-dimensional systems, sub-diffraction optical microscopy provides a nanoscale material understanding that is vital for optimizing their optoelectronic properties. Here we use the 'Campanile' nano-optical probe to spectroscopically image exciton recombination within monolayer MoS2 with sub-wavelength resolution (60 nm), at the length scale relevant to many critical optoelectronic processes. Synthetic monolayer MoS2 is found to be composed of two distinct optoelectronic regions: an interior, locally ordered but mesoscopically heterogeneous two-dimensional quantum well and an unexpected ∼300-nm wide, energetically disordered edge region. Further, grain boundaries are imaged with sufficient resolution to quantify local exciton-quenching phenomena, and complimentary nano-Auger microscopy reveals that the optically defective grain boundary and edge regions are sulfur deficient. The nanoscale structure-property relationships established here are critical for the interpretation of edge- and boundary-related phenomena and the development of next-generation two-dimensional optoelectronic devices.

15.
Adv Mater ; 27(38): 5813-9, 2015 Oct 14.
Artigo em Inglês | MEDLINE | ID: mdl-26079187

RESUMO

Extreme ultraviolet lithography (EUVL) is the leading technology for enabling miniaturization of computational components over the next decade. Next-generation resists will need to meet demanding performance criteria of 10 nm critical dimension, 1.2 nm line-edge roughness, and 20 mJ cm(-2) exposure dose. Here, the current state of the development of EUV resist materials is reviewed. First, pattern formation in resist materials is described and the Hansen solubility sphere (HSS) is used as a framework for understanding the pattern-development process. Then, recent progress in EUVL resist chemistry and characterization is discussed. Incremental advances are obtained by transferring chemically amplified resist materials developed for 193 nm lithography to EUV wavelengths. Significant advances will result from synthesizing high-absorbance resist materials using heavier atoms. In the framework of the HSS model, these materials have significant room for improvement and thus offer great promise as high-performance EUV resists for patterning of sub-10 nm features.

16.
Chem Sci ; 6(11): 6295-6304, 2015 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-30090247

RESUMO

Our understanding of structure and bonding in nanoscale materials is incomplete without knowledge of their surface structure. Needed are better surveying capabilities responsive not only to different atoms at the surface, but also their respective coordination environments. We report here that d-block organometallics, when placed at nanocrystal surfaces through heterometallic bonds, serve as molecular beacons broadcasting local surface structure in atomic detail. This unique ability stems from their elemental specificity and the sensitivity of their d-orbital level alignment to local coordination environment, which can be assessed spectroscopically. Re-surfacing cadmium and lead chalcogenide nanocrystals with iron- or ruthenium-based molecular beacons is readily accomplished with trimethylsilylated cyclopentadienyl metal carbonyls. For PbSe nanocrystals with iron-based beacons, we show how core-level X-ray spectroscopies and DFT calculations enrich our understanding of both charge and atomic reorganization at the surface when beacons are bound.

17.
Nano Lett ; 14(12): 6767-73, 2014 Dec 10.
Artigo em Inglês | MEDLINE | ID: mdl-25390285

RESUMO

In this work, we demonstrate that catalyst composition can be used to direct the crystallographic growth axis of GaN nanowires. By adjusting the ratio of gold to nickel in a bimetallic catalyst, we achieved selective growth of dense, uniform nanowire arrays along two nonpolar directions. A gold-rich catalyst resulted in single-crystalline nanowire growth along the ⟨11̅00⟩ or m axis, whereas a nickel-rich catalyst resulted in nanowire growth along the ⟨112̅0⟩ or a axis. The same growth control was demonstrated on two different epitaxial substrates. Using proper conditions, many of the nanowires were observed to switch direction midgrowth, resulting in monolithic single-crystal structures with segments of two distinct orientations. Cathodoluminescence spectra revealed significant differences in the optical properties of these nanowire segments, which we attribute to the electronic structures of their semipolar {112̅2} or {11̅01} sidewalls.

18.
Nat Commun ; 5: 3252, 2014.
Artigo em Inglês | MEDLINE | ID: mdl-24500082

RESUMO

Semiconducting transition metal dichalcogenides consist of monolayers held together by weak forces where the layers are electronically and vibrationally coupled. Isolated monolayers show changes in electronic structure and lattice vibration energies, including a transition from indirect to direct bandgap. Here we present a new member of the family, rhenium disulphide (ReS2), where such variation is absent and bulk behaves as electronically and vibrationally decoupled monolayers stacked together. From bulk to monolayers, ReS2 remains direct bandgap and its Raman spectrum shows no dependence on the number of layers. Interlayer decoupling is further demonstrated by the insensitivity of the optical absorption and Raman spectrum to interlayer distance modulated by hydrostatic pressure. Theoretical calculations attribute the decoupling to Peierls distortion of the 1T structure of ReS2, which prevents ordered stacking and minimizes the interlayer overlap of wavefunctions. Such vanishing interlayer coupling enables probing of two-dimensional-like systems without the need for monolayers.

19.
Nat Commun ; 5: 3082, 2014.
Artigo em Inglês | MEDLINE | ID: mdl-24448414

RESUMO

It has been more than a decade since the experimental demonstration that the thermal conductivity of carbon nanotubes can exceed that of diamond, which has the highest thermal conductivity among naturally occurring materials. In spite of tremendous promise as a thermal material, results have been disappointing for practical thermal systems and applications based on nanotubes. The main culprit for the dramatic shortfall in the performance of nanotubes in practical systems is high thermal interface resistance between them and other components because of weak adhesion at the interface. Here we report a sixfold reduction in the thermal interface resistance between metal surfaces and vertically aligned multiwall carbon nanotube arrays by bridging the interface with short, covalently bonded organic molecules. These results are also significant for single and multilayer graphene applications, since graphene faces similar limitations in practical systems.

20.
ACS Nano ; 7(11): 10397-404, 2013 Nov 26.
Artigo em Inglês | MEDLINE | ID: mdl-24156282

RESUMO

Demand for visualizing nanoscale dynamics in biological and advanced materials continues to drive the development of subdiffraction optical probes. While many strategies employ scanning tips for this purpose, we instead exploit a focused electron beam to create scannable nanoscale optical excitations in an epitaxially grown thin-film of cerium-doped yttrium aluminum perovskite, whose cathodoluminescence response is bright, robust, and spatially resolved to 18 nm. We also demonstrate lithographic patterning of the film's luminescence at the nanoscale. We anticipate that converting these films into free-standing membranes will yield a powerful near-field optical microscopy without the complication of mechanical scanning.


Assuntos
Eletrodos , Luminescência , Óptica e Fotônica/métodos , Alumínio/química , Cério/química , Elétrons , Desenho de Equipamento , Lasers , Teste de Materiais , Método de Monte Carlo , Nanopartículas/química , Nanoestruturas/química , Nanotecnologia/métodos , Propriedades de Superfície
SELEÇÃO DE REFERÊNCIAS
DETALHE DA PESQUISA