Uphill Diffusion Induced Point Contact Reaction in Si Nanowires.

The events of repeating nucleation in point contact reactions between nanowires of Si and Ni or Co have been revisited here due to uphill diffusion as well as an extremely high supersaturation, over a factor of 1000, needed for the nucleation. Also what is the diameter of the point contact needs to be defined. The stepwise growth of nanoscale epitaxial silicide can occur because the repeating nucleation events are restricted in nanoscale wires.

Organic Lead Halide Nanocrystals Providing an Ultra-Wide Color Gamut with Almost-Unity Photoluminescence Quantum Yield.

The most attractive aspect of perovskite nanocrystals (NCs) for optoelectronic applications is their widely tunable emission wavelength, but it has been quite challenging to tune it without sacrificing the photoluminescence quantum yield (PLQY). In this work, we report a facile ligand-optimized ion-exchange (LOIE) method to convert room-temperature spray-synthesized, perovskite parent NCs that emit a saturated green color to NCs capable of emitting colors across the entire visible spectrum. These NCs exhibited exceptionally stable and high PLQYs, particularly for the pure blue (96%) and red (93%) primary colors that are indispensable for display applications. Surprisingly, the blue- and red-emissive NCs obtained using the LOIE method preserved the cubic shape and cubic phase structure that they inherited from their parent NCs, while exhibiting high crystallinity and high color-purity. Together with the parent green-emissive NCs, the obtained blue- and red-emissive NCs provided a very wide color gamut, corresponding to a Digital Cinema Initiatives-P3 of 140% or an International Telecommunication Union Recommendation BT.2020 of 102%. With the superior optical merits of these LOIE-manipulated NCs, a corresponding color conversion luminescence device provided a high external quantum efficiency (10.5%) and extremely high brightness (970 000 cd/m2). This study provides a valid route toward highly stable, extremely emissive, and panchromatic perovskite NCs with potential use in a variety of future optoelectronic applications.

Distinct Carrier Transport Properties Across Horizontally vs Vertically Oriented Heterostructures of 2D/3D Perovskites.

Two-dimensional-on-three-dimensional (2D/3D) halide perovskite heterostructures have been extensively utilized in optoelectronic devices. However, the labile nature of halide perovskites makes it difficult to form such heterostructures with well-defined compositions, orientations, and interfaces, which inhibits understanding of the carrier transfer properties across these heterostructures. Here, we report solution growth of both horizontally and vertically aligned 2D perovskite (PEA)2PbBr4 (PEA = phenylethylammonium) microplates onto 3D CsPbBr3 single crystal thin films, with well-defined heterojunctions. Time-resolved photoluminescence (TRPL) transients of the heterostructures exhibit the monomolecular and bimolecular dynamics expected from exciton annihilation, dissociation, and recombination, as well as evidence for carrier transfer in these heterostructures. Two kinetic models based on Type-I and Type-II band alignments at the interface of horizontal 2D/3D heterostructures are applied to reveal a shift in balance between carrier transfer and recombination: Type-I band alignment better describes the behaviors of heterostructures with thin 2D perovskite microplates but Type-II band alignment better describes those with thick 2D microplates (>150 nm). TRPL of vertically aligned 2D microplates is dominated by directly excited PL and is independent of the height above the 3D film. Electrical measurements reveal current rectification behaviors in both heterostructures with vertical heterostructures showing better electrical transport. As the first systematic study on comparing models of 2D/3D perovskite heterostructures with controlled orientations and compositions, this work provides insights on the charge transfer mechanisms in these perovskite heterostructures and guidelines for designing better optoelectronic devices.

Aluminum Plasmonics Enriched Ultraviolet GaN Photodetector with Ultrahigh Responsivity, Detectivity, and Broad Bandwidth.

Plasmonics have been well investigated on photodetectors, particularly in IR and visible regimes. However, for a wide range of ultraviolet (UV) applications, plasmonics remain unavailable mainly because of the constrained optical properties of applicable plasmonic materials in the UV regime. Therefore, an epitaxial single-crystalline aluminum (Al) film, an abundant metal with high plasma frequency and low intrinsic loss is fabricated, on a wide bandgap semiconductive gallium nitride (GaN) to form a UV photodetector. By deliberately designing a periodic nanohole array in this Al film, localized surface plasmon resonance and extraordinary transmission are enabled; hence, the maximum responsivity (670 A W-1) and highest detectivity (1.48 × 1015 cm Hz1/2 W-1) is obtained at the resonance wavelength of 355 nm. In addition, owing to coupling among nanoholes, the bandwidth expands substantially, encompassing the entire UV range. Finally, a Schottky contact is formed between the single-crystalline Al nanohole array and the GaN substrate, resulting in a fast temporal response with a rise time of 51 ms and a fall time of 197 ms. To the best knowledge, the presented detectivity is the highest compared with those of other reported GaN photodetectors.

ZnO Nanowires on Single-Crystalline Aluminum Film Coupled with an Insulating WO3 Interlayer Manifesting Low Threshold SPP Laser Operation.

ZnO nanowire-based surface plasmon polariton (SPP) nanolasers with metal-insulator-semiconductor hierarchical nanostructures have emerged as potential candidates for integrated photonic applications. In the present study, we demonstrated an SPP nanolaser consisting of ZnO nanowires coupled with a single-crystalline aluminum (Al) film and a WO3 dielectric interlayer. High-quality ZnO nanowires were prepared using a vapor phase transport and condensation deposition process via catalyzed growth. Subsequently, prepared ZnO nanowires were transferred onto a single-crystalline Al film grown by molecular beam epitaxy (MBE). Meanwhile, a WO3 dielectric interlayer was deposited between the ZnO nanowires and Al film, via e-beam technique, to prevent the optical loss from dominating the metallic region. The metal-oxide-semiconductor (MOS) structured SPP laser, with an optimal WO3 insulating layer thickness of 3.6 nm, demonstrated an ultra-low threshold laser operation (lasing threshold of 0.79 MW cm-2). This threshold value was nearly eight times lower than that previously reported in similar ZnO/Al2O3/Al plasmonic lasers, which were ≈2.4 and ≈3 times suppressed compared to the SPP laser, with WO3 insulating layer thicknesses of 5 nm and 8 nm, respectively. Such suppression of the lasing threshold is attributed to the WO3 insulating layer, which mediated the strong confinement of the optical field in the subwavelength regime.

Green Treatment of Phosphate from Wastewater Using a Porous Bio-Templated Graphene Oxide/MgMn-Layered Double Hydroxide Composite.

Excessive phosphorus in water is the primary culprit for eutrophication, which causes approximately $2.2 billion annual economic loss in the United States. This study demonstrates a phosphate-selective sustainable method by adopting Garcinia subelliptica leaves as a natural bio-template, where MgMn-layered double hydroxide (MgMn-LDH) and graphene oxide (GO) can be grown in situ to obtain L-GO/MgMn-LDH. After calcination, the composite shows a hierarchical porous structure and selective recognition of phosphate, which achieves significantly high and recyclable selective phosphate adsorption capacity and desorption rate of 244.08 mg-P g-1 and 85.8%, respectively. The detail variation of LDHs during calcination has been observed via in situ transmission electron microscope (TEM). Moreover, the roles in facilitating phosphate adsorption and antimicrobial ability of chemical constituents in Garcinia subelliptica leaves, biflavonoids, and triterpenoids have been investigated. These results indicate the proposed bio-templated adsorbent is practical and eco-friendly for phosphorus sustainability in commercial wastewater treatment.

Heterogeneous Supersaturation in Mixed Perovskites.

Thin-film solar cells based on hybrid lead halide perovskites have achieved certified power conversion efficiencies exceeding 24%, approaching those of crystalline silicon. This motivates deeper studies of the mechanisms that determine their performance. Twin defect sites have been proposed as a source of traps in perovskites, yet their origin and influence on photovoltaic performance remain unclear. It is found that twin defects-observed herein via both transmission electron microscopy and X-ray diffraction-are correlated with the amount of antisolvent added to the perovskite and that twin defects in the highest-performing perovskite photovoltaics are suppressed. Heterogeneous supersaturation nucleation is discussed as a contributor to efficient perovskite-based optoelectronic devices.

Facet-Dependent Surface Trap States and Carrier Lifetimes of Silicon.

The facet-dependent electrical conductivity properties of silicon wafers result from significant band structure differences and variations in bond length, bond geometry, and frontier orbital electron distribution between the metal-like and semiconducting planes of silicon. To further understand the emergence of conductivity facet effects, electrochemical impedance measurements were conducted on intrinsic Si {100}, {110}, and {111} wafers. The attempt-to-escape frequency, obtained from temperature-dependent capacitance versus applied frequency curves, and other parameters derived from typical semiconductor property measurements were used to construct a diagram of the trap energy level (Et) and the amount of trap states Nt(Et). The trap states are located 0.61-0.72 eV above the silicon conduction band. Compared to {100} and {110} wafers, Si {111} wafer shows far less densities of trap states over the range of -0.2 to 2 V. Since these trap states inhibit direct electron excitation to the conduction band, the {111} wafer having much fewer trap states presents the best electrical conductivity property. Impedance data also provide facet-specific carrier lifetimes. The {111} surface gives consistently the lowest carrier lifetime, which reflects its high electrical conductivity. Lastly, ultraviolet photoelectron spectra and diffuse reflectance spectra were taken to obtain Schottky barriers between Ag and contacting Si wafers. The most conductive {111} surface presenting the largest Schottky barrier means the degrees of surface band bending used to explain facet-dependent electrical behaviors cannot be reliably attained this way.

Tunable Moiré Superlattice of Artificially Twisted Monolayers.

Twisting between two stacked monolayers modulates periodic potentials and forms the Moiré electronic superlattices, which offers an additional degree of freedom to alter material property. Considerable unique observations, including unconventional superconductivity, coupled spin-valley states, and quantized interlayer excitons are correlated to the electronic superlattices but further study requires reliable routes to study the Moiré in real space. Scanning tunneling microscopy (STM) is ideal to precisely probe the Moiré superlattice and correlate coupled parameters among local electronic structures, strains, defects, and band alignment at atomic scale. Here, a clean route is developed to construct twisted lattices using synthesized monolayers for fundamental studies. Diverse Moiré superlattices are predicted and successfully observed with STM at room temperature. Electrical tuning of the Moiré superlattice is achieved with stacked TMD on graphite.

Low threshold room-temperature UV surface plasmon polariton lasers with ZnO nanowires on single-crystal aluminum films with Al2O3 interlayers.

ZnO is one of the most promising optical gain media and allows lasing in ZnO nanowires at room temperature. Plasmonic lasers are potentially useful in applications in biosensing, photonic circuits, and high-capacity signal processing. In this work, we combine ZnO nanowires and single-crystalline aluminum films to fabricate Fabry-Perot type surface plasmon polariton (SPP) lasers to overcome the diffraction limit of conventional optics. High quality ZnO nanowires were synthesized by a vapor phase transport process via catalyzed growth. The ZnO nanowires were placed on a single-crystalline Al film grown by molecular beam epitaxy with an interlayer Al2O3 deposited by atomic layer deposition. The plasmonic laser is of metal-oxide-semiconductor (MOS) structure, compatible with silicon device processing. An optimal thickness of atomic layer deposited Al2O3 layer can lead to a low lasing threshold, 6.27 MW cm-2, which is 3 times and 12 times lower than that of previous reports for ZnO/Al and Zno/Al2O3/Al plasmonic lasers, respectively, owing to low materials loss. Both the thickness and quality of insulating layers were found to critically influence the lasing threshold of the SPP nanolasers in the subwavelength regime. The simulation results also manifest the importance of the quality of the dielectric interlayer.

Germanium Wafers Possessing Facet-Dependent Electrical Conductivity Properties.

Electrical conductivity properties of Ge {100}, {110}, {111}, and {211} facets have been measured by breaking Ge (100) and (111) wafers to expose {110} and {211} surfaces and contacting the different facets with tungsten probes. Ge {111} and {211} faces are far more conductive than the already conductive Ge {100} and {110} faces, matching with recent density functional theory (DFT) predictions. Asymmetric I-V curves resembling those of p-n junctions have been collected for the {110}/{111} and {110}/{211} facet combinations. The current-rectifying effects stem from different degrees of surface band bending for the highly and less conductive faces and the direction of current flow. This work demonstrates that germanium wafers also possess facet-dependent electrical conductivity responses that can be utilized in the fabrication of novel fin field-effect transistors (finFET).

Copper-on-nitride enhances the stable electrosynthesis of multi-carbon products from CO2.

Copper-based materials are promising electrocatalysts for CO2 reduction. Prior studies show that the mixture of copper (I) and copper (0) at the catalyst surface enhances multi-carbon products from CO2 reduction; however, the stable presence of copper (I) remains the subject of debate. Here we report a copper on copper (I) composite that stabilizes copper (I) during CO2 reduction through the use of copper nitride as an underlying copper (I) species. We synthesize a copper-on-nitride catalyst that exhibits a Faradaic efficiency of 64 ± 2% for C2+ products. We achieve a 40-fold enhancement in the ratio of C2+ to the competing CH4 compared to the case of pure copper. We further show that the copper-on-nitride catalyst performs stable CO2 reduction over 30 h. Mechanistic studies suggest that the use of copper nitride contributes to reducing the CO dimerization energy barrier-a rate-limiting step in CO2 reduction to multi-carbon products.

Room-temperature ferromagnetic Cr-doped Ge/GeOx core-shell nanowires.

The Cr-doped tunable thickness core-shell Ge/GeOx nanowires (NWs) were synthesized and characterized using x-ray diffraction, field-emission scanning electron microscopy, transmission electron microscopy, energy-dispersive x-ray spectroscopy, x-ray photoelectron spectroscopy and magnetization studies. The shell thickness increases with the increase in synthesis temperature. The presence of metallic Cr and Cr3+ in core-shell structure was confirmed from XPS study. The magnetic property is highly sensitive to the core-shell thickness and intriguing room temperature ferromagnetism is realized only in core-shell NWs. The magnetization decreases with an increase in shell thickness and practically ceases to exist when there is no core. These NWs show remarkably high Curie temperature (TC > 300 K) with the dominating values of its magnetic remanence (MR) and coercivity (HC) compared to germanium dilute magnetic semiconductor nanomaterials. We believe that our finding on these Cr-doped Ge/GeOX core-shell NWs has the potential to be used as a hard magnet for future spintronic devices, owing to their higher characteristic values of ferromagnetic ordering.

In Situ Investigation of Defect-Free Copper Nanowire Growth.

The fabrication and placement of high purity nanometals, such as one-dimensional copper (Cu) nanowires, for interconnection in integrated devices have been among the most important technological developments in recent years. Structural stability and oxidation prevention have been the key issues, and the defect control in Cu nanowire growth has been found to be important. Here, we report the synthesis of defect-free single-crystalline Cu nanowires by controlling the surface-assisted heterogeneous nucleation of Cu atomic layering on the graphite-like loop of an amorphous carbon (a-C) lacey film surface. Without a metal-catalyst or induced defects, the high quality Cu nanowires formed with high aspect ratio and high growth rate of 578 nm/s. The dynamic study of the growth of heterogeneous nanowires was conducted in situ with a high-resolution transmission electron microscope. The study illuminates the new mechanism by heterogeneous nucleation control and laying the groundwork for better understanding of heterosurface-assisted nucleation of defect-free Cu nanowire on a-C lacey film.

Silicon Wafers with Facet-Dependent Electrical Conductivity Properties.

By breaking intrinsic Si (100) and (111) wafers to expose sharp {111} and {112} facets, electrical conductivity measurements on single and different silicon crystal faces were performed through contacts with two tungsten probes. While Si {100} and {110} faces are barely conductive at low applied voltages, as expected, the Si {112} surface is highly conductive and Si {111} surface also shows good conductivity. Asymmetrical I-V curves have been recorded for the {111}/{112}, {111}/{110}, and {112}/{110} facet combinations because of different degrees of conduction band bending at these crystal surfaces presenting different barrier heights to current flow. In particular, the {111}/{110} and {112}/{110} facet combinations give I-V curves resembling those of p-n junctions, suggesting a novel field effect transistor design is possible capitalizing on the pronounced facet-dependent electrical conductivity properties of silicon.

Single Atomically Sharp Lateral Monolayer p-n Heterojunction Solar Cells with Extraordinarily High Power Conversion Efficiency.

The recent development of 2D monolayer lateral semiconductor has created new paradigm to develop p-n heterojunctions. Albeit, the growth methods of these heterostructures typically result in alloy structures at the interface, limiting the development for high-efficiency photovoltaic (PV) devices. Here, the PV properties of sequentially grown alloy-free 2D monolayer WSe2 -MoS2 lateral p-n heterojunction are explores. The PV devices show an extraordinary power conversion efficiency of 2.56% under AM 1.5G illumination. The large surface active area enables the full exposure of the depletion region, leading to excellent omnidirectional light harvesting characteristic with only 5% reduction of efficiency at incident angles up to 75°. Modeling studies demonstrate the PV devices comply with typical principles, increasing the feasibility for further development. Furthermore, the appropriate electrode-spacing design can lead to environment-independent PV properties. These robust PV properties deriving from the atomically sharp lateral p-n interface can help develop the next-generation photovoltaics.

Omnidirectional Harvesting of Weak Light Using a Graphene Quantum Dot-Modified Organic/Silicon Hybrid Device.

Despite great improvements in traditional inorganic photodetectors and photovoltaics, more progress is needed in the detection/collection of light at low-level conditions. Traditional photodetectors tend to suffer from high noise when operated at room temperature; therefore, these devices require additional cooling systems to detect weak or dim light. Conventional solar cells also face the challenge of poor light-harvesting capabilities in hazy or cloudy weather. The real world features such varying levels of light, which makes it important to develop strategies that allow optical devices to function when conditions are less than optimal. In this work, we report an organic/inorganic hybrid device that consists of graphene quantum dot-modified poly(3,4-ethylenedioxythiophene) polystyrenesulfonate spin-coated on Si for the detection/harvest of weak light. The hybrid configuration provides the device with high responsivity and detectability, omnidirectional light trapping, and fast operation speed. To demonstrate the potential of this hybrid device in real world applications, we measured near-infrared light scattered through human tissue to demonstrate noninvasive oximetric photodetection as well as characterized the device's photovoltaic properties in outdoor (i.e., weather-dependent) and indoor weak light conditions. This organic/inorganic device configuration demonstrates a promising strategy for developing future high-performance low-light compatible photodetectors and photovoltaics.

High-efficiency omnidirectional photoresponses based on monolayer lateral p-n heterojunctions.

Electrical and optical properties of lateral monolayer WSe2-MoS2 p-n heterojunctions were characterized to demonstrate a high responsivity of 0.26 A W-1 with an excellent omnidirectional photodetection capability. The heterojunction functioning as a diode exhibits a prominent gate-tuning behavior with an ideality factor of 1.25. In addition, ultrafast photoresponse, low-light detectability, and high-temperature operation have been achieved. These unique characteristics pave a way for the future development of sub-nano semiconductor devices.

Thermal dewetting with a chemically heterogeneous nano-template for self-assembled L1(0) FePt nanoparticle arrays.

A design for the fabrication of metallic nanoparticles is presented by thermal dewetting with a chemically heterogeneous nano-template. For the template, we fabricate a nanostructured polystyrene-b-polydimethylsiloxane (PS-b-PDMS) film on a Si|SiO2 substrate, followed by a thermal annealing and reactive ion etching (RIE) process. This gives a template composed of an ordered hexagonal array of SiOC hemispheres emerging in the polystyrene matrix. After the deposition of a FePt film on this template, we utilize the rapid thermal annealing (RTA) process, which provides in-plane stress, to achieve thermal dewetting and structural ordering of FePt simultaneously. Since the template is composed of different composition surfaces with periodically varied morphologies, it offers more tuning knobs to manipulate the nanostructures. We show that both the decrease in the area of the PS matrix and the increase in the strain energy relaxation transfer the dewetted pattern from the randomly distributed nanoparticles into a hexagonal periodic array of L10 FePt nanoparticles. Transmission electron microscopy with the in situ heating stage reveals the evolution of the dewetting process, and confirms that the positions of nanoparticles are aligned with those of the SiOC hemispheres. The nanoparticles formed by this template-dewetting show an average diameter and center-to-center distance of 19.30 ± 2.09 nm and 39.85 ± 4.80 nm, respectively. The hexagonal array of FePt nanoparticles reveals a large coercivity of 1.5 T, much larger than the nanoparticles fabricated by top-down approaches. This approach offers an efficient pathway toward self-assembled nanostructures in a wide range of material systems.

Optimization of the nanotwin-induced zigzag surface of copper by electromigration.

By adding nanotwins to Cu, the surface electromigration (EM) slows down. The atomic mobility of the surface step-edges is retarded by the triple points where a twin meets a free surface to form a zigzag-type surface. We observed that EM can alter the zigzag surface structure to optimize the reduction of EM, according to Le Chatelier's principle. Statistically, the optimal alternation is to change an arbitrary (111)/(hkl) zigzag pair to a pair having a very low index (hkl) plane, especially the (200) plane. Using in situ ultrahigh vacuum and high-resolution transmission electron microscopy, we examined the effects of different zigzag surfaces on the rate of EM. The calculated rate of surface EM can be decreased by a factor of ten.