Exfoliation of two-dimensional (2D) nanosheets from three-dimensional (3D) non-layered, non-van der Waals crystals represents an emerging strategy for materials engineering that could significantly increase the library of 2D materials. Yet, the exfoliation mechanism in which nanosheets are derived from crystals that are not intrinsically layered remains unclear. Here, we show that planar defects in the starting 3D boron material promote the exfoliation of 2D boron sheets-by combining liquid-phase exfoliation, aberration-corrected scanning transmission electron microscopy, Raman spectroscopy, and density functional theory calculations.
View Article and Find Full Text PDFvan der Waals heterojunctions based on transition-metal dichalcogenides (TMDs) offer advanced strategies for manipulating light-emitting and light-harvesting behaviors. A crucial factor determining the light-material interaction is in the band alignment at the heterojunction interface, particularly the distinctions between type-I and type-II alignments. However, altering the band alignment from one type to another without changing the constituent materials is exceptionally difficult.
View Article and Find Full Text PDFThe defect emission from h-BN at 1.55 eV is interesting as it enables optical readout of spins. It is necessary to identify the nature of the relevant point defects for its controlled introduction.
View Article and Find Full Text PDFACS Appl Mater Interfaces
November 2022
Designing the next generation of high-resolution displays requires high pixel density per area and small pixel sizes without compromising the optical quality. Quantum dots (QDs) have been demonstrated as a promising material system for down-conversion of blue emission as they provide pure colors on the wide color gamut. However, for high color-conversion efficiency, the required QD film thickness has not been compatible with small pixel sizes.
View Article and Find Full Text PDFExtraordinary optoelectronic properties of van der Waals (vdW) heterostructures can be tuned via strain caused by mechanical deformation. Here, we demonstrate strong and localized luminescence in the ultraviolet region from interface bubbles between stacked multilayers of hexagonal boron nitride (hBN). Compared to bubbles in stacked monolayers, bubbles formed by stacking vdW multilayers show distinct mechanical behavior.
View Article and Find Full Text PDFStructural, electronic, and chemical nanoscale modifications of transition metal dichalcogenide monolayers alter their optical properties. A key missing element for complete control is a direct spatial correlation of optical response to nanoscale modifications due to the large gap in spatial resolution between optical spectroscopy and nanometer-resolved techniques. Here, we bridge this gap by obtaining nanometer-resolved optical properties using electron spectroscopy at cryogenic temperatures, specifically electron energy loss spectroscopy for absorption and cathodoluminescence for emission, which are then directly correlated to chemical and structural information.
View Article and Find Full Text PDFControl of materials properties has been the driving force of modern technologies. So far, materials properties have been modulated by their composition, structure, and size. Here, by using cathodoluminescence in a scanning transmission electron microscope, we show that the optical properties of stacked, >100 nm thick hexagonal boron nitride (hBN) films can be continuously tuned by their relative twist angles.
View Article and Find Full Text PDFTwo-dimensional (2D) transition-metal dichalcogenides (TMDCs) have been explored for many optoelectronic applications. Most of these applications require them to be on insulating substrates. However, for many fundamental property characterizations, such as mapping surface potential or conductance, insulating substrates are nonideal as they lead to charging and doping effects or impose the inhomogeneity of their charge environment on the atomically thin 2D layers.
View Article and Find Full Text PDFACS Appl Mater Interfaces
July 2019
Oxidation is a scalable process for introducing nanopores in two-dimensional transitional metal dichalcogenides (TMDs) for membrane applications. The nanopore density is determined by the areal density of their nucleation sites; understanding the nature of the defects and their control would enable tailoring of TMD membranes for targeted applications. In this work, we show that the nanopore distribution is dramatically different in strained and unstrained MoS crystals.
View Article and Find Full Text PDFLow carrier mobility and lifetime in semiconductor polymers are some of the main challenges facing the field of organic photovoltaics (OPV) in the quest for efficient devices with high current density. Finding novel strategies such as device structure engineering is a key pathway toward addressing this issue. In this work, the light absorption and carrier collection of OPV devices are improved by employment of ZnO nanowire (NW) arrays with an optimum NW length (50 nm) and antireflection (AR) film with nanocone structure.
View Article and Find Full Text PDFTwo-dimensional (2D) transition metal dichalcogenides can be alloyed by substitution at the metal atom site with negligible effect on lattice strain, but with significant influence on optical and electrical properties. In this work, we establish the relationship between composition and optical properties of the MoWS alloy by investigating the effect of continuously-varying composition on photoluminescence intensity. We developed a new process for growth of two-dimensional MoWS alloys that span nearly the full composition range along a single crystal, thus avoiding any sample-related heterogeneities.
View Article and Find Full Text PDFHydrogen embrittlement (HE) causes sudden, costly failures of metal components across a wide range of industries. Yet, despite over a century of research, the physical mechanisms of HE are too poorly understood to predict HE-induced failures with confidence. We use non-destructive, synchrotron-based techniques to investigate the relationship between the crystallographic character of grain boundaries and their susceptibility to hydrogen-assisted fracture in a nickel superalloy.
View Article and Find Full Text PDFLead sulfide quantum dots (PbS QDs) are an attractive material system for the development of low-cost photovoltaics (PV) due to their ease of processing and stability in air, with certified power conversion efficiencies exceeding 11%. However, even the best PbS QD PV devices are limited by diffusive transport, as the optical absorption length exceeds the minority carrier diffusion length. Understanding minority carrier transport in these devices will therefore be critical for future efficiency improvement.
View Article and Find Full Text PDFMacromol Rapid Commun
June 2017
Novel structures comprised of GaAs nanowire arrays conformally coated with conducting polymers (poly(3,4-ethylenedioxythiophene) (PEDOT) or poly(3,4-ethylenedioxythiophene-co-3-thiophene acetic acid) display both sensitivity and selectivity to a variety of volatile organic chemicals. A key feature is room temperature operation, so that neither a heater nor the power it would consume, is required. It is a distinct difference from traditional metal oxide sensors, which typically require elevated operational temperature.
View Article and Find Full Text PDFAs novel absorber materials are developed and screened for their photovoltaic (PV) properties, the challenge remains to reproducibly test promising candidates for high-performing PV devices. Many early-stage devices are prone to device shunting due to pinholes in the absorber layer, producing "false-negative" results. Here, we demonstrate a device engineering solution toward a robust device architecture, using a two-step absorber deposition approach.
View Article and Find Full Text PDFControlled growth of two-dimensional transition metal dichalcogenide (TMD) lateral heterostructures would enable on-demand tuning of electronic and optoelectronic properties in this new class of materials. Prior to this work, compositional modulations in lateral TMD heterostructures have been considered to depend solely on the growth chronology. We show that in-plane diffusion can play a significant role in the chemical vapor deposition of MoS2/WS2 lateral heterostructures leading to a variety of nontrivial structures whose composition does not necessarily follow the growth order.
View Article and Find Full Text PDFThe concept of a neutral hole-transporting polymer is realized for the first time, by integrating patterned Cl(-) -doped poly(3,4-dimethoxythiophene) thin films into organic solar cells through a vacuum-based polymer vapor printing technique. Due to this novel polymer's neutrality, high transparency, good conductivity, and appropriate energy levels, the solar-cell efficiency and lifetime are significantly enhanced.
View Article and Find Full Text PDFVarious electron and hole transport layers have been used to develop high-efficiency perovskite solar cells. To achieve low-temperature solution processing of perovskite solar cells, organic n-type materials are employed to replace the metal oxide electron transport layer (ETL). Although PCBM (phenyl-C61-butyric acid methyl ester) has been widely used for this application, its morphological instability in films (i.
View Article and Find Full Text PDFDespite the recent astronomical success of organic-inorganic perovskite solar cells (PSCs), the impact of microscale film inhomogeneities on device performance remains poorly understood. In this work, we study CH3NH3PbI3 perovskite films using cathodoluminescence in scanning transmission electron microscopy and show that localized regions with increased cathodoluminescence intensity correspond to iodide-enriched regions. These observations constitute direct evidence that nanoscale stoichiometric variations produce corresponding inhomogeneities in film cathodoluminescence intensity.
View Article and Find Full Text PDFMetallic nanoparticles can be used to enhance optical absorption or emission in semiconductors, thanks to a strong interaction of collective excitations of free charges (plasmons) with electromagnetic fields. Herein we present direct imaging at the nanoscale of plasmon-exciton coupling in Au/ZnO nanostructures by combining scanning transmission electron energy loss and cathodoluminescence spectroscopy and mapping. The Au nanoparticles (~30 nm in diameter) are grown in-situ on ZnO nanotetrapods by means of a photochemical process without the need of binding agents or capping molecules, resulting in clean interfaces.
View Article and Find Full Text PDFHydrothermally synthesized ZnO nanowire arrays are critical components in a range of nanostructured semiconductor devices. The device performance is governed by relevant nanowire morphological parameters that cannot be fully controlled during bulk hydrothermal synthesis due to its transient nature. Here, we maintain homeostatic zinc concentration, pH, and temperature by employing continuous flow synthesis and demonstrate independent tailoring of nanowire array dimensions including areal density, length, and diameter on device-relevant length scales.
View Article and Find Full Text PDFWe report the nanoscale quantification of strain in GaAs/GaAsP core-shell nanowires. By tracking the shifting of higher-order Laue zone (HOLZ) lines in convergent beam electron diffraction patterns, we observe unique variations in HOLZ line separation along different facets of the core-shell structure, demonstrating the nonuniform strain fields created by the heterointerface. Furthermore, through the use of continuum mechanical modeling and Bloch wave analysis we calculate expected HOLZ line shift behavior, which are directly matched to experimental results.
View Article and Find Full Text PDFDiameter-modulated nanowires can be used to impart unique properties to nanowire-based devices. Here, diameter modulation along Au-seeded GaAs nanowires was achieved by varying the flux of the III and V precursors during growth. Furthermore, three different types of [111]B-oriented nanowires were observed to display distinct differences in diameter modulation, growth rate, and cross-sectional shape.
View Article and Find Full Text PDFIII-nitride based nanorods and nanowires offer great potential for optoelectronic applications such as light emitting diodes or nanolasers. We report nanoscale optical studies of InGaN/GaN nanodisk-in-rod heterostructures to quantify uniformity of light emission on the ensemble level, as well as the emission characteristics from individual InGaN nanodisks. Despite the high overall luminescence efficiency, spectral and intensity inhomogeneities were observed and directly correlated to the compositional variations among nanodisks and to the presence of structural defect, respectively.
View Article and Find Full Text PDFHydrogen embrittlement (HE) causes engineering alloys to fracture unexpectedly, often at considerable economic or environmental cost. Inaccurate predictions of component lifetimes arise from inadequate understanding of how alloy microstructure affects HE. Here we investigate hydrogen-assisted fracture of a Ni-base superalloy and identify coherent twin boundaries (CTBs) as the microstructural features most susceptible to crack initiation.
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