Branched Nanowire Heterostructures Research Articles

Lattice‐Matched Epitaxial Growth of Organic Heterostructures for Integrated Optoelectronic Application

AbstractDevelopment of nanowire photonics requires integration of different nanowire components into highly ordered functional heterostructures. Herein, we report a sequential self‐assembly of binary molecular components into branched nanowire heterostructures (BNHs) via lattice‐matched epitaxial growth, in which the microribbon backbone of 2,5‐Bis(5‐tert‐butyl‐2‐benzoxazolyl)thiophene (BBOT) functions as blue‐emitting microlaser source to pump the nanowire branches of BODIPY. By constructing Au electrodes on both branch sides and measuring the photocurrent in them, we successfully realize the integration of an organic laser and a power meter in a single device. This work provides a new insight into the integration of 1D organic nanostructures into BNHs for realizing organic multifunctional photonic devices.

Lattice-Matched Epitaxial Growth of Organic Heterostructures for Integrated Optoelectronic Application.

Development of nanowire photonics requires integration of different nanowire components into highly ordered functional heterostructures. Herein, we report a sequential self-assembly of binary molecular components into branched nanowire heterostructures (BNHs) via lattice-matched epitaxial growth, in which the microribbon backbone of 2,5-Bis(5-tert-butyl-2-benzoxazolyl)thiophene (BBOT) functions as blue-emitting microlaser source to pump the nanowire branches of BODIPY. By constructing Au electrodes on both branch sides and measuring the photocurrent in them, we successfully realize the integration of an organic laser and a power meter in a single device. This work provides a new insight into the integration of 1D organic nanostructures into BNHs for realizing organic multifunctional photonic devices.

High Capacity Li-Ion Anodes with Tunable Rate Capability Comprised of Si-Ge Branched Nanowire Heterostructures

Li-alloying nanowires (NWs) are promising anode materials for next generation lithium-ion batteries due to their large maximum theoretical capacity when compared with conventional graphitic based materials (372 mAh/g). Ge NWs, in particular, have shown great promise, exhibiting stable capacities of 900 mAh/g over 1000s of cycles and excellent rate capability due to the high rate of diffusivity of Li in Ge and its inherent high conductivity.1, 2 The superior capacity retention of Ge is attributed to the complete restructuring of the NWs that occurs within the first 100 cycles to form a continuous porous network that is mechanically robust. The possibility of incorporating Si into this stable network of Ge is very appealing, combining the very high capacity of Si with the excellent rate characteristics and capacity retention of Ge. Here we report the formation of high-performance and high-capacity lithium-ion battery anodes from high-density Si-Ge heterostructure nanowire arrays grown directly from the current collector.3 The unique morphology of the active material consists of Si NW branches grown from a Ge NW backbone. By tuning the ratio of Si to Ge in the material it is possible to design electrodes for either high-capacity applications (high Si : Ge mass ratio) or high rate capability applications (high Ge : Si mass ratio). We show by ex-situ high-resolution transmission electron microscopy (HRTEM) and high-resolution scanning electron microscopy (HRSEM) studies that the NW array transforms into a mechanically robust, porous network of Si and Ge ligaments. Once this network is formed it is highly stable, maintaining capacities of 1700 mAh/g over 100 cycles. The electrode material described here also has the advantage of being formed in a low energy, rapid synthetic protocol. Using a very simple reaction protocol, NW growth occurs by thermolytic decomposition of an organometallic precursor onto a preheated substrate in an inert atmosphere. 1. Kennedy, T.; Mullane, E.; Geaney, H.; Osiak, M.; O’Dwyer, C.; Ryan, K. M. Nano Lett. 2014, 14, (2), 716-723.2. Mullane, E.; Kennedy, T.; Geaney, H.; Ryan, K. M. ACS Appl. Mater. Interfaces 2014, 6, (21), 18800-18807.3. Kennedy, T.; Bezuidenhout, M.; Palaniappan, K.; Killian Stokes; Brandon, M.; Ryan, K. M. ACS Nano 2015, 9, 7456–7465. Figure 1

Nanowire Heterostructures Comprising Germanium Stems and Silicon Branches as High-Capacity Li-Ion Anodes with Tunable Rate Capability.

Here we report the rational design of a high-capacity Li-ion anode material comprising Ge nanowires with Si branches. The unique structure provides an electrode material with tunable properties, allowing the performance to be tailored for either high capacity or high rate capability by controlling the mass ratio of Si to Ge. The binder free Si-Ge branched nanowire heterostructures are grown directly from the current collector and exhibit high capacities of up to ∼1800 mAh/g. Rate capability testing revealed that increasing the Ge content within the material boosted the performance of the anode at fast cycling rates, whereas a higher Si content was optimal at slower rates of charge and discharge. Using ex-situ electron microscopy, Raman spectroscopy and energy dispersive X-ray spectroscopy mapping, the composition of the material is shown to be transient in nature, transforming from a heterostructure to a Si-Ge alloy as a consequence of repeated lithiation and delithiation.

Three‐Dimensional Branched Nanowire Heterostructures as Efficient Light‐Extraction Layer in Light‐Emitting Diodes

A facile method to fabricate three‐dimensional branched ZnO/MgO nanowire heterostructures and their application as the efficient light‐extraction layer in light‐emitting diodes are reported. The branched MgO nanowires are produced on the hydrothermally‐grown ZnO nanowires with a small tapering angle towards the tip (≈6°), by the oblique angle flux incidence of MgO. The structural evolution during the growth verifies the formation of the MgO nanoscale islands with strong (111) preferred orientation on very thin (5–7 nm) MgO (110) layer. The MgO nanobranches, then grown on the islands, are polycrystalline consisting of many grains oriented in specific directions of <200> and <220>, supported by the nucleation theory. The LEDs with the branched ZnO/MgO nanowire arrays show a remarkable enhancement in the light output power by 21% compared with that of LEDs with pristine ZnO nanowires. Theoretical calculations using a finite‐difference time‐domain method reveal that the nanostructure is very effective in breaking the wave‐guiding mode inside the ZnO nanowires, extracting more light especially in radial direction through the MgO nanobranches.

Epitaxial Self-assembly of Binary Molecular Components into Branched Nanowire Heterostructures for Photonic Applications

We report a sequential epitaxial growth to prepare organic branched nanowire heterostructures (BNwHs) consisting of a microribbon trunk of 1,4-dimethoxy-2,5-di[4'-(cyano)styryl]benzene (COPV) with multiple nanowire branches of 2,4,5-triphenylimidazole (TPI) in a one-pot solution synthesis. The synthesis involves a seeded-growth process, where COPV microribbons are grown first as a trunk followed by a seeded-growth of TPI nanowire branches at the pregrown trunk surfaces. Selected area electron diffraction characterizations reveal that multiple hydrogen-bonding interactions between TPI and COPV components play an essential role in the epitaxial growth as a result of the structural matching between COPV and TPI crystals. A multichannel optical router was successfully realized on the basis of the passive waveguides of COPV green photoluminescence (PL) along TPI nanowire branches in a single organic BNwH.

Rational growth of branched nanowire heterostructures with synthetically encoded properties and function

Branched nanostructures represent unique, 3D building blocks for the "bottom-up" paradigm of nanoscale science and technology. Here, we report a rational, multistep approach toward the general synthesis of 3D branched nanowire (NW) heterostructures. Single-crystalline semiconductor, including groups IV, III-V, and II-VI, and metal branches have been selectively grown on core or core/shell NW backbones, with the composition, morphology, and doping of core (core/shell) NWs and branch NWs well controlled during synthesis. Measurements made on the different composition branched NW structures demonstrate encoding of functional p-type/n-type diodes and light-emitting diodes (LEDs) as well as field effect transistors with device function localized at the branch/backbone NW junctions. In addition, multibranch/backbone NW structures were synthesized and used to demonstrate capability to create addressable nanoscale LED arrays, logic circuits, and biological sensors. Our work demonstrates a previously undescribed level of structural and functional complexity in NW materials, and more generally, highlights the potential of bottom-up synthesis to yield increasingly complex functional systems in the future.

In situ growth, structure characterization, and enhanced photocatalysis of high-quality, single-crystalline ZnTe/ZnO branched nanoheterostructures

Single-crystalline, high-quality branched ZnTe-core/ZnO-branch nanoheterostructures were synthesized by an in situ strategy in an environmental scanning electron microscope. Composition and structure characterization confirmed that ZnO nanowires were perfectly epitaxially grown on ZnTe nanowires as branches. Noticeably, growth temperature plays a crucial role in determining the density and diameter of the ZnO nanobranches on ZnTe nanowires: a higher growth temperature leads to ZnO nanowires with higher density and smaller diameter. It was demonstrated that ZnO nanobranches exhibited a selective nucleation behavior on distinct side facets of ZnTe nanowires. Highly ordered ZnO nanobranches were found epitaxially grown on {211} facet of ZnTe nanowires, while there was no ZnO nanowire growth on {110} facet of ZnTe nanowires. Using first-principles calculation, we found that surface energy of distinct side facets has a strong impact on ZnO nucleation, and confirm that {211} facet of ZnTe nanowires is energetically more favorable for ZnO nanowire growth than {110} facet, which is in good agreement with our experimental findings. Remarkably, such unique ZnTe/ZnO 3D branched nanowire heterostructures exhibited improved photocatalytic abilities, superior to ZnO nanowires and ZnTe nanowires, due to the much enhanced effective surface area of their unique architecture and effective electron-hole separation at the ZnTe/ZnO interfaces.

Solution Synthesis of Large-Scale, High-Sensitivity ZnO/Si Hierarchical Nanoheterostructure Photodetectors

This Communication reports a low-cost solution fabrication of wafer-scale ZnO/Si branched nanowire heterostructures and their high photodetection sensitivity, with an ON/OFF ratio larger than 250 and a peak photoresponsivity of 12.8 mA/W at 900 nm. This reported unique 3D branched nanowire structure offers a generic approach for the integration of new functional materials for photodetection and photovoltaic applications.

Evolution of InAs branches in InAs∕GaAs nanowire heterostructures

Branched nanowire heterostructures of InAs∕GaAs were observed during Au-assisted growth of InAs on GaAs nanowires. The evolution of these branches has been determined through detailed electron microscopy characterization with the following sequence: (1) in the initial stage of InAs growth, the Au droplet is observed to slide down the side of the GaAs nanowire, (2) the downward movement of Au nanoparticle later terminates when the nanoparticle encounters InAs growing radially on the GaAs nanowire sidewalls, and (3) with further supply of In and As vapor reactants, the Au nanoparticles assist the formation of InAs branches with a well-defined orientation relationship with GaAs∕InAs core/shell stems. We anticipate that these observations advance the understanding of the kink formation in axial nanowire heterostructures.

The Morphology of Axial and Branched Nanowire Heterostructures

We present an extensive investigation of the epitaxial growth of Au-assisted axial heterostructure nanowires composed of group IV and III-V materials and derive a model to explain the overall morphology of such wires. By analogy with 2D epitaxial growth, this model relates the wire morphology (i.e., whether it is kinked or straight) to the relationship of the interface energies between the two materials and the particle. This model suggests that, for any pair of materials, it should be easier to form a straight wire with one interface direction than the other, and we demonstrate this for the material combinations presented here. However, such factors as kinetics and the use of surfactants may permit the growth of straight double heterostructure nanowires. Finally, we demonstrate that branched nanowire heterostructures, also known as nanotrees, can be successfully explained by the same model.

Synthesis and Structural Characterization of Single-Crystalline Branched Nanowire Heterostructures

We report the synthesis of three-dimensional single-crystalline branched nanowire heterostructures, where the backbones and branches are assembled with ZnS and CdS, respectively. Growth of branch and backbones with control over the compositions was enabled via sequential seeding of gold nanocluster catalysts. Elemental mapping data confirmed that branched nanowire heterostructures were synthesized with the intended chemical modulation, CdS branches on ZnS backbones. Transmission electron microscopy studies showed that the growth of heterostructure branches occurs epitaxially from the backbone while maintaining single-crystalline structure. This unique class of heterostructures holds great potential in assembling electronics and photonics in three dimensions.