Excitons at the interface of 2D TMDs and molecular semiconductors.

Van der Waals heterostructures (vdWHs) of vertically stacked two-dimensional (2D) atomic crystals have been used to elicit intriguing phenomena stemming from strong electronic correlations, magnetic textures, and interlayer excitons spawned at the heterointerface. However, vdWHs comprised of heterointerfaces between these 2D atomic crystal lattices and molecular assemblies are emerging as equally intriguing platforms supporting properties to be harnessed for photovoltaic energy conversion, photodetection, spin-selective charge injection, and quantum emission. In this perspective, we summarize recent research examining exciton dynamics in heterostructures between semiconducting 2D transition metal dichalcogenides and molecular organic semiconductors. We discuss methods for assembly of these heterostructures, the nature of interlayer or charge-transfer excitons at transition-metal dichalcogenide (TMD)-molecule interfaces, explicit exciton transfer between organics and TMDs, and other interfacial phenomena driven by the merger of these two material classes. We also suggest key new research directions extending the remit of these 2D atomic-molecular lattice heterointerfaces into the domains of condensed matter physics, quantum sensing, and energy conversion.

Controlling Morphology and Excitonic Disorder in Monolayer WSe2 Grown by Salt-Assisted CVD Methods.

Chemical synthesis is a compelling alternative to top-down fabrication for controlling the size, shape, and composition of two-dimensional (2D) crystals. Precision tuning of the 2D crystal structure has broad implications for the discovery of new phenomena and the reliable implementation of these materials in optoelectronic, photovoltaic, and quantum devices. However, precise and predictable manipulation of the edge structure in 2D crystals through gas-phase synthesis is still a formidable challenge. Here, we demonstrate a salt-assisted low-pressure chemical vapor deposition method that enables tuning W metal flux during growth of 2D WSe2 monolayers and, thereby, direct control of their edge structure and optical properties. The degree of structural disorder in 2D WSe2 is a direct function of the W metal flux, which is controlled by adjusting the mass ratio of WO3 to NaCl. This edge disorder then couples to excitonic disorder, which manifests as broadened and spatially varying emission profiles. Our work links synthetic parameters with analyses of material morphology and optical properties to provide a unified understanding of intrinsic limits and opportunities in synthetic 2D materials.

Photon Upconversion in a Vapor Deposited 2D Inorganic-Organic Semiconductor Heterostructure.

Energy transfer processes may be engineered in van der Waals heterostructures by taking advantage of the atomically abrupt, Å-scale, and topologically tailorable interfaces within them. Here, we prepare heterostructures comprised of 2D WSe2 monolayers interfaced with dibenzotetraphenylperiflanthene (DBP)-doped rubrene, an organic semiconductor capable of triplet fusion. We fabricate these heterostructures entirely through vapor deposition methods. Time-resolved and steady-state photoluminescence measurements reveal rapid subnanosecond quenching of WSe2 emission by rubrene and fluorescence from guest DBP molecules at 612 nm (λexc = 730 nm), thus providing clear evidence of photon upconversion. The dependence of the upconversion emission on excitation intensity is consistent with a triplet fusion mechanism, and maximum efficiency (linear regime) of this process occurs at threshold intensities as low as 110 mW/cm2, which is comparable to the integrated solar irradiance. This study highlights the potential for advanced optoelectronic applications employing vdWHs which leverage strongly bound excitons in monolayer TMDs and organic semiconductors.

Graphene and Beyond: Recent Advances in Two-Dimensional Materials Synthesis, Properties, and Devices.

Since the isolation of graphene in 2004, two-dimensional (2D) materials research has rapidly evolved into an entire subdiscipline in the physical sciences with a wide range of emergent applications. The unique 2D structure offers an open canvas to tailor and functionalize 2D materials through layer number, defects, morphology, moiré pattern, strain, and other control knobs. Through this review, we aim to highlight the most recent discoveries in the following topics: theory-guided synthesis for enhanced control of 2D morphologies, quality, yield, as well as insights toward novel 2D materials; defect engineering to control and understand the role of various defects, including in situ and ex situ methods; and properties and applications that are related to moiré engineering, strain engineering, and artificial intelligence. Finally, we also provide our perspective on the challenges and opportunities in this fascinating field.

Structural and electronic switching of a single crystal 2D metal-organic framework prepared by chemical vapor deposition.

The incorporation of metal-organic frameworks into advanced devices remains a desirable goal, but progress is hindered by difficulties in preparing large crystalline metal-organic framework films with suitable electronic performance. We demonstrate the direct growth of large-area, high quality, and phase pure single metal-organic framework crystals through chemical vapor deposition of a dimolybdenum paddlewheel precursor, Mo2(INA)4. These exceptionally uniform, high quality crystals cover areas up to 8600 µm2 and can be grown down to thicknesses of 30 nm. Moreover, scanning tunneling microscopy indicates that the Mo2(INA)4 clusters assemble into a two-dimensional, single-layer framework. Devices are readily fabricated from single vapor-phase grown crystals and exhibit reversible 8-fold changes in conductivity upon illumination at modest powers. Moreover, we identify vapor-induced single crystal transitions that are reversible and responsible for 30-fold changes in conductivity of the metal-organic framework as monitored by in situ device measurements. Gas-phase methods, including chemical vapor deposition, show broader promise for the preparation of high-quality molecular frameworks, and may enable their integration into devices, including detectors and actuators.

Progress and Prospects in Transition-Metal Dichalcogenide Research Beyond 2D.

This review discusses recent advances and future research priorities in the transition-metal dichalcogenide (TMD) field. While the community has witnessed tremendous advances through research conducted on two-dimensional (2D) TMD crystals, it is vital to seek new research opportunities beyond developed areas. To this end, in this review we focus principally on articulating areas of need in the preparation and analysis of TMD crystals encompassing dimensionalities and morphologies beyond 2D. Ultimately, the development of new synthetic methods to control key structural features of low-dimensional TMD crystals (e.g., dimensionality, morphology, and phase) will afford access to a broader range of breakthrough properties for this intriguing material class. We begin with a brief overview of the evolution of 2D TMD research, discussing both the synthetic methods that have enabled the preparation of these materials and the manifold properties they possess. We focus the bulk of our review on discussion of recent advances associated with 1D TMD crystals, which are often referred to as TMD nanoribbons, and include a discussion of recent efforts in 0D systems. We discuss synthetic strategies that have been developed to prepare such beyond 2D crystals and highlight their unique physical and chemical properties. After reviewing the host of analytical tools available for characterization of TMD materials, we identify future analytical instrumentation needs. We conclude with a discussion of the prospects of beyond 2D TMD crystals in optoelectronics, catalysis, and quantum information science.

Substrate-directed synthesis of MoS2 nanocrystals with tunable dimensionality and optical properties.

Two-dimensional transition-metal dichalcogenide (TMD) crystals are a versatile platform for optoelectronic, catalytic and quantum device studies. However, the ability to tailor their physical properties through explicit synthetic control of their morphology and dimensionality is a major challenge. Here we demonstrate a gas-phase synthesis method that substantially transforms the structure and dimensionality of TMD crystals without lithography. Synthesis of MoS2 on Si(001) surfaces pre-treated with phosphine yields high-aspect-ratio nanoribbons of uniform width. We systematically control the width of these nanoribbons between 50 and 430 nm by varying the total phosphine dosage during the surface treatment step. Aberration-corrected electron microscopy reveals that the nanoribbons are predominantly 2H phase with zig-zag edges and an edge quality that is comparable to, or better than, that of graphene and TMD nanoribbons prepared through conventional top-down processing. Owing to their restricted dimensionality, the nominally one-dimensional MoS2 nanocrystals exhibit photoluminescence 50 meV higher in energy than that from two-dimensional MoS2 crystals. Moreover, this emission is precisely tunable through synthetic control of crystal width. Directed crystal growth on designer substrates has the potential to enable the preparation of low-dimensional materials with prescribed morphologies and tunable or emergent optoelectronic properties.

Rapid Room-Temperature Synthesis of a Metastable Ordered Intermetallic Electrocatalyst.

Metal alloys with atomic scale ordering (ordered intermetallics) have emerged as a new class of high performance materials for mediating electrochemical reactions. However, ordered intermetallic nanostructures often require long synthesis times and/or high temperature annealing to form because a high-activation energy barrier for interdiffusion must be overcome for the constituent metals to equilibrate into ordered structures. Here we report the direct synthesis of metastable ordered intermetallic Pd31Bi12 at room-temperature in minutes via electrochemical deposition. Pd31Bi12 is highly active for the reduction of O2 to H2O, delivering specific activities over 35× higher than those of commercial Pt and Pd nanocatalysts, placing it as the most active Pd-based catalyst, to the best of our knowledge, reported under similar testing conditions. Stability tests demonstrate minimal loss of activity after 10,000 cycles, and a retention of intermetallic crystallinity. This study demonstrates a new method of preparing ordered intermetallics with extraordinary catalytic activity at room temperature, providing a new direction in catalyst discovery and synthesis.

Molecular chains of coordinated dimolybdenum isonicotinate paddlewheel clusters.

A growing focus on the use of coordination polymers for active device applications motivates the search for candidate materials with integrated and optimized charge transport modes. We show herein the synthesis of a linear coordination polymer comprised of Mo2(INA)4 (INA = isonicotinate) metal-organic clusters. Single-crystal X-ray structure determination shows that this cluster crystallizes into one-dimensional molecular chains, whose INA-linked Mo2 cores engage in alternate axial and equatorial binding motifs along the chain axis. Electron paramagnetic resonance spectra, absorption spectra, and density functional theory calculations show that the aforementioned linear coordination environment significantly modifies the electronic structure of the clusters. This work expands the synthetic foundation for assembly of coordination polymers with tailorable dimensionalities and charge transport properties.

Hierarchically Ordered Two-Dimensional Coordination Polymers Assembled from Redox-Active Dimolybdenum Clusters.

Coordination polymers (CPs) supporting tunable through-framework conduction and responsive properties are of significant interest for enabling a new generation of active devices. However, such architectures are rare. We report a redox-active CP composed of two-dimensional (2D) lattices of coordinatively bonded Mo2(INA)4 clusters (INA = isonicotinate). The 2D lattices are commensurately stacked and their ordering topology can be synthetically tuned. The material has a hierarchical pore structure (pore sizes distributed between 7 and 33 Å) and exhibits unique CO2 adsorption (nominally Type VI) for an isotherm collected at 195 K. Furthermore, cyclic voltammetry and electrokinetic analyses identify a quasi-reversible feature at E1/2 = -1.275 V versus ferrocene/ferrocenium that can be ascribed to the [Mo2(INA)4]0/-1 redox couple, with an associated standard heterogeneous electron transfer rate constant ks = 1.49 s-1. The tunable structure, porosity, and redox activity of our material may render it a promising platform for CPs with responsive properties.

Anisotropic and Multicomponent Nanostructures by Controlled Symmetry Breaking of Metal Halide Intermediates.

We propose and validate herein a solution-phase synthetic strategy relying on in situ photostimulation and reduction of metal-halide intermediates to yield complex anisotropic and multicomponent nanostructures. Exposure of AgBr nanoparticles to ultraviolet light and l-Arginine forms dimers composed of crystalline Ag and AgBr nanophases. The Ag nanoparticle nucleates at and grows from a single point on the surface of the AgBr phase and the interface connecting these phases is atomically sharp. The complex nanostructures are generated at greater than 80% yield and are highly monodisperse in morphology and in size. The high crystallinity of the nanophases arises from an apparent solid-solid crystallization process and is unusual considering the nearly 40% lattice mismatch between Ag and AgBr. Such structures may be used to interrogate photocatalytic mechanisms or to construct more complex materials.

Influence of iron doping on tetravalent nickel content in catalytic oxygen evolving films.

Iron doping of nickel oxide films results in enhanced activity for promoting the oxygen evolution reaction (OER). Whereas this enhanced activity has been ascribed to a unique iron site within the nickel oxide matrix, we show here that Fe doping influences the Ni valency. The percent of Fe3+ doping promotes the formation of formal Ni4+, which in turn directly correlates with an enhanced activity of the catalyst in promoting OER. The role of Fe3+ is consistent with its behavior as a superior Lewis acid.

Micelle-Encapsulated Quantum Dot-Porphyrin Assemblies as in Vivo Two-Photon Oxygen Sensors.

Micelles have been employed to encapsulate the supramolecular assembly of quantum dots with palladium(II) porphyrins for the quantification of O2 levels in aqueous media and in vivo. Förster resonance energy transfer from the quantum dot (QD) to the palladium porphyrin provides a means for signal transduction under both one- and two-photon excitation. The palladium porphyrins are sensitive to O2 concentrations in the range of 0-160 Torr. The micelle-encapsulated QD-porphyrin assemblies have been employed for in vivo multiphoton imaging and lifetime-based oxygen measurements in mice with chronic dorsal skinfold chambers or cranial windows. Our results establish the utility of the QD-micelle approach for in vivo biological sensing applications.

High-throughput patterning of photonic structures with tunable periodicity.

A patterning method termed "RIPPLE" (reactive interface patterning promoted by lithographic electrochemistry) is applied to the fabrication of arrays of dielectric and metallic optical elements. This method uses cyclic voltammetry to impart patterns onto the working electrode of a standard three-electrode electrochemical setup. Using this technique and a template stripping process, periodic arrays of Ag circular Bragg gratings are patterned in a high-throughput fashion over large substrate areas. By varying the scan rate of the cyclically applied voltage ramps, the periodicity of the gratings can be tuned in situ over micrometer and submicrometer length scales. Characterization of the periodic arrays of periodic gratings identified point-like and annular scattering modes at different planes above the structured surface. Facile, reliable, and rapid patterning techniques like RIPPLE may enable the high-throughput and low-cost fabrication of photonic elements and metasurfaces for energy conversion and sensing applications.

Facile, rapid, and large-area periodic patterning of semiconductor substrates with submicron inorganic structures.

The development of high-throughput and scalable techniques for patterning inorganic structures is useful for the improved function and efficiency of photonic and energy conversion devices. Here we demonstrate a facile and rapid electrochemical method for patterning periodic metallic and nonmetallic submicron structures over large areas. Si substrates have been patterned with arrays of periodically spaced lines, rings, squares, and terraces of main-group and transition-metal oxides. In addition to planar substrates, three-dimensional surfaces and their vertical sidewalls have been patterned. The features are 20(±1) nm high and 360(±15) nm wide, and their period is finely tunable in situ from 500 nm to 7 µm. These features exhibit <3% variation in period and are rapidly patterned in <2 min. We demonstrate the versatility of the technique by rapidly patterning an efficient water splitting catalyst, Co phosphate oxide (CoPi), and show that the integrated materials system performs water splitting with complete Faradaic efficiency. More generally, the ability to pattern submicron structures over large areas in a facile, reliable, and timely manner may be useful for the fabrication of devices for energy, meta-material, and sensing applications.

Laterally assembled nanowires for ultrathin broadband solar absorbers.

We studied optical resonances in laterally oriented Si nanowire arrays by conducting finite-difference time-domain simulations. Localized Fabry-Perot and whispering-gallery modes are supported within the cross section of each nanowire in the array and result in broadband light absorption. Comparison of a nanowire array with a single nanowire shows that the current density (J(SC)) is preserved for a range of nanowire morphologies. The J(SC) of a nanowire array depends on the spacing of its constituent nanowires, which indicates that both diffraction and optical antenna effects contribute to light absorption. Furthermore, a vertically stacked nanowire array exhibits significantly enhanced light absorption because of the emergence of coupled cavity-waveguide modes and the mitigation of a screening effect. With the assumption of unity internal quantum efficiency, the J(SC) of an 800-nm-thick cross-stacked nanowire array is 14.0 mA/cm², which yields a ~60% enhancement compared with an equivalent bulk film absorber. These numerical results underpin a rational design strategy for ultrathin solar absorbers based on assembled nanowire cavities.

Design of nanowire optical cavities as efficient photon absorbers.

Recent investigations of semiconductor nanowires have provided strong evidence for enhanced light absorption, which has been attributed to nanowire structures functioning as optical cavities. Precise synthetic control of nanowire parameters including chemical composition and morphology has also led to dramatic modulation of absorption properties. Here we report finite-difference time-domain (FDTD) simulations for silicon (Si) nanowire cavities to elucidate the key factors that determine enhanced light absorption. The FDTD simulations revealed that a crystalline Si nanowire with an embedded 20-nm-thick amorphous Si shell yields 40% enhancement of absorption as compared to a homogeneous crystalline Si nanowire, under air-mass 1.5 global solar spectrum for wavelengths between 280 and 1000 nm. Such a large enhancement in absorption results from localization of several resonant modes within the amorphous Si shell. A nanowire with a rectangular cross section exhibited enhanced absorption at specific wavelengths with respect to a hexagonal nanowire. The pronounced absorption peaks were assigned to resonant modes with a high symmetry that red-shifted with increasing size of the rectangular nanowire. We extended our studies to investigate the optical properties of single- and multilayer arrays of these horizontally oriented nanowire building blocks. The absorption efficiency of a nanowire stack increases with the number of nanowire layers and was found to be greater than that of a bulk structure or even a single nanowire of equivalent thickness. Lastly, we found that a single-layer nanowire array preserves the structured absorption spectrum of a single nanowire and ascribed this result to a diffraction effect of the periodic nanowire array. The results from these provide insight into the design of nanowire optical cavities with tunable and enhanced light absorption and thus, could help enable the development of ultrathin solar cells and other nanoscale optoelectronic devices.

Facet-selective growth on nanowires yields multi-component nanostructures and photonic devices.

Enhanced synthetic control of the morphology, crystal structure, and composition of nanostructures can drive advances in nanoscale devices. Axial and radial semiconductor nanowires are examples of nanostructures with one and two structural degrees of freedom, respectively, and their synthetically tuned and modulated properties have led to advances in nanotransistor, nanophotonic, and thermoelectric devices. Similarly, developing methods that allow for synthetic control of greater than two degrees of freedom could enable new opportunities for functional nanostructures. Here we demonstrate the first regioselective nanowire shell synthesis in studies of Ge and Si growth on faceted Si nanowire surfaces. The selectively deposited Ge is crystalline, and its facet position can be synthetically controlled in situ. We use this synthesis to prepare electrically addressable nanocavities into which solution soluble species such as Au nanoparticles can be incorporated. The method furnishes multicomponent nanostructures with unique photonic properties and presents a more sophisticated nanodevice platform for future applications in catalysis and photodetection.

Tuning light absorption in core/shell silicon nanowire photovoltaic devices through morphological design.

Subwavelength diameter semiconductor nanowires can support optical resonances with anomalously large absorption cross sections, and thus tailoring these resonances to specific frequencies could enable a number of nanophotonic applications. Here, we report the design and synthesis of core/shell p-type/intrinsic/n-type (p/i/n) Si nanowires (NWs) with different sizes and cross-sectional morphologies as well as measurement and simulation of photocurrent spectra from single-NW devices fabricated from these NW building blocks. Approximately hexagonal cross-section p/i/n coaxial NWs of various diameters (170-380 nm) were controllably synthesized by changing the Au catalyst diameter, which determines core diameter, as well as shell deposition time, which determines shell thickness. Measured polarization-resolved photocurrent spectra exhibit well-defined diameter-dependent peaks. The corresponding external quantum efficiency (EQE) spectra calculated from these data show good quantitative agreement with finite-difference time-domain (FDTD) simulations and allow assignment of the observed peaks to Fabry-Perot, whispering-gallery, and complex high-order resonant absorption modes. This comparison revealed a systematic red-shift of equivalent modes as a function of increasing NW diameter and a progressive increase in the number of resonances. In addition, tuning shell synthetic conditions to enable enhanced growth on select facets yielded NWs with approximately rectangular cross sections; analysis of transmission electron microscopy and scanning electron microscopy images demonstrate that growth of the n-type shell at 860 °C in the presence of phosphine leads to enhanced relative Si growth rates on the four {113} facets. Notably, polarization-resolved photocurrent spectra demonstrate that at longer wavelengths the rectangular cross-section NWs have narrow and significantly larger amplitude peaks with respect to similar size hexagonal NWs. A rectangular NW with a diameter of 260 nm yields a dominant mode centered at 570 nm with near-unity EQE in the transverse-electric polarized spectrum. Quantitative comparisons with FDTD simulations demonstrate that these new peaks arise from cavity modes with high symmetry that conform to the cross-sectional morphology of the rectangular NW, resulting in low optical loss of the mode. The ability to modulate absorption with changes in nanoscale morphology by controlled synthesis represents a promising route for developing new photovoltaic and optoelectronic devices.

Coaxial multishell nanowires with high-quality electronic interfaces and tunable optical cavities for ultrathin photovoltaics.

Silicon nanowires (NWs) could enable low-cost and efficient photovoltaics, though their performance has been limited by nonideal electrical characteristics and an inability to tune absorption properties. We overcome these limitations through controlled synthesis of a series of polymorphic core/multishell NWs with highly crystalline, hexagonally-faceted shells, and well-defined coaxial (p/n) and p/intrinsic/n (p/i/n) diode junctions. Designed 200-300 nm diameter p/i/n NW diodes exhibit ultralow leakage currents of approximately 1 fA, and open-circuit voltages and fill-factors up to 0.5 V and 73%, respectively, under one-sun illumination. Single-NW wavelength-dependent photocurrent measurements reveal size-tunable optical resonances, external quantum efficiencies greater than unity, and current densities double those for silicon films of comparable thickness. In addition, finite-difference-time-domain simulations for the measured NW structures agree quantitatively with the photocurrent measurements, and demonstrate that the optical resonances are due to Fabry-Perot and whispering-gallery cavity modes supported in the high-quality faceted nanostructures. Synthetically optimized NW devices achieve current densities of 17 mA/cm(2) and power-conversion efficiencies of 6%. Horizontal integration of multiple NWs demonstrates linear scaling of the absolute photocurrent with number of NWs, as well as retention of the high open-circuit voltages and short-circuit current densities measured for single NW devices. Notably, assembly of 2 NW elements into vertical stacks yields short-circuit current densities of 25 mA/cm(2) with a backside reflector, and simulations further show that such stacking represents an attractive approach for further enhancing performance with projected efficiencies of > 15% for 1.2 µm thick 5 NW stacks.