Exceptional Thermochemical Stability of Graphene on N-Polar GaN for Remote Epitaxy.

In this study, we investigate the thermochemical stability of graphene on the GaN substrate for metal-organic chemical vapor deposition (MOCVD)-based remote epitaxy. Despite excellent physical properties of GaN, making it a compelling choice for high-performance electronic and light-emitting device applications, the challenge of thermochemical decomposition of graphene on a GaN substrate at high temperatures has obstructed the achievement of remote homoepitaxy via MOCVD. Our research uncovers an unexpected stability of graphene on N-polar GaN, thereby enabling the MOCVD-based remote homoepitaxy of N-polar GaN. Our comparative analysis of N- and Ga-polar GaN substrates reveals markedly different outcomes: while a graphene/N-polar GaN substrate produces releasable microcrystals (µCs), a graphene/Ga-polar GaN substrate yields nonreleasable thin films. We attribute this discrepancy to the polarity-dependent thermochemical stability of graphene on the GaN substrate and its subsequent reaction with hydrogen. Evidence obtained from Raman spectroscopy, electron microscopic analyses, and overlayer delamination points to a pronounced thermochemical stability of graphene on N-polar GaN during MOCVD-based remote homoepitaxy. Molecular dynamics simulations, corroborated by experimental data, further substantiate that the thermochemical stability of graphene is reliant on the polarity of GaN, due to different reactions with hydrogen at high temperatures. Based on the N-polar remote homoepitaxy of µCs, the practical application of our findings was demonstrated in fabrication of flexible light-emitting diodes composed of p-n junction µCs with InGaN heterostructures.

Self-Limiting Sub-5 nm Nanodiamonds by Geochemistry-Inspired Synthesis.

Controlling diamond structures with nanometer precision is fundamentally challenging owing to their extreme and far-from-equilibrium synthetic conditions. State-of-the-art techniques, including detonation, chemical vapor deposition, mechanical grinding, and high-pressure-high-temperature synthesis, yield nanodiamond particles with a broad distribution of sizes. Despite many efforts, the direct synthesis of nanodiamonds with precisely controlled diameters remains elusive. Here the geochemistry-inspired synthesis of sub-5 nm nanodiamonds with sub-nanometer size deviation is described. High-pressure-high-temperature treatment of uniform iron carbide nanoparticles embedded in iron oxide matrices yields nanodiamonds with tunable diameters down to 2.13 and 0.22 nm standard deviation. A self-limiting, redox-driven, and diffusion-controlled solid-state reaction mechanism is proposed and supported by in situ X-ray diffraction, ex situ characterizations, and computational modeling. This work provides a unique mechanism for the precise control of nanostructured diamonds under extreme conditions and paves the road for the full realization of their potential in emerging technologies.

Enhanced Nanobubble Formation: Gold Nanoparticle Conjugation to Qß Virus-like Particles.

Plasmonic gold nanostructures are a prevalent tool in modern hypersensitive analytical techniques such as photoablation, bioimaging, and biosensing. Recent studies have shown that gold nanostructures generate transient nanobubbles through localized heating and have been found in various biomedical applications. However, the current method of plasmonic nanoparticle cavitation events has several disadvantages, specifically including small metal nanostructures (≤10 nm) which lack size control, tuneability, and tissue localization by use of ultrashort pulses (ns, ps) and high-energy lasers which can result in tissue and cellular damage. This research investigates a method to immobilize sub-10 nm AuNPs (3.5 and 5 nm) onto a chemically modified thiol-rich surface of Qß virus-like particles. These findings demonstrate that the multivalent display of sub-10 nm gold nanoparticles (AuNPs) caused a profound and disproportionate increase in photocavitation by upward of 5-7-fold and significantly lowered the laser fluency by 4-fold when compared to individual sub-10 nm AuNPs. Furthermore, computational modeling showed that the cooling time of QßAuNP scaffolds is significantly extended than that of individual AuNPs, proving greater control of laser fluency and nanobubble generation as seen in the experimental data. Ultimately, these findings showed how QßAuNP composites are more effective at nanobubble generation than current methods of plasmonic nanoparticle cavitation.

Highly Emissive Zero-Dimensional Cesium Lead Iodide Perovskite Nanocrystals with Thermally Activated Delayed Photoluminescence.

We utilized a modified reverse-microemulsion method to develop highly emissive and photostable zero-dimensional (0D) Cs4Pb(Br1-xIx)6 perovskite nanocrystals (PNCs). We employed single-particle photoluminescence (PL) spectroscopy to explore blinking statistics and demonstrate single-photon emission from individual PNCs. Low-temperature blinking and photon correlation studies revealed a transition from single- to multiphoton emission with progressively longer "delayed" PL components, reaching ∼70 ns at room temperature and representing a distinctive behavior to previously known iodide PNCs. Such thermally activated PL emission is explained by the existence of defect-related "reservoir" states, feeding back into the PNC's emissive state and providing multiple photons within a single excitation cycle. This work establishes a new member in the 0D class of perovskite materials, studies its photophysical properties, and reveals its potential for future optoelectronic applications.

Stable and Bright Electroluminescent Devices utilizing Emissive 0D Perovskite Nanocrystals Incorporated in a 3D CsPbBr3 Matrix.

The 0D cesium lead halide perovskite Cs4 PbBr6 has drawn remarkable interest due to its highly efficient robust green emission compared to its 3D CsPbBr3 counterpart. However, seizing the advantages of the superior photoluminescence properties for practical light-emitting devices remains elusive. To date, Cs4 PbBr6 has been employed only as a higher-bandgap nonluminescent matrix to passivate or provide quantum/dielectric confinement to CsPbBr3 in light-emitting devices and to enhance its photo-/thermal/environmental stability. To resolve this disparity, a novel solvent engineering method to incorporate highly luminescent 0D Cs4 PbBr6 nanocrystals (perovskite nanocrystals (PNCs)) into a 3D CsPbBr3 film, forming the active emissive layer in single-layer perovskite light-emitting electrochemical cells (PeLECs) is designed. A dramatic increase of the maximum external quantum efficiency and luminance from 2.7% and 6050 cd m-2 for a 3D-only PeLEC to 8.3% and 11 200 cd m-2 for a 3D-0D PNC device with only 7% by weight of 0D PNCs is observed. The majority of this increase is driven by the efficient inherent emission of the 0D PNCs, while the concomitant morphology improvement also contributes to reduced leakage current, reduced hysteresis, and enhanced operational lifetime (half-life of 129 h), making this one of the best-performing LECs reported to date.

Facet-selective morphology-controlled remote epitaxy of ZnO microcrystals via wet chemical synthesis.

We report on morphology-controlled remote epitaxy via hydrothermal growth of ZnO micro- and nanostructure crystals on graphene-coated GaN substrate. The morphology control is achieved to grow diverse morphologies of ZnO from nanowire to microdisk by changing additives of wet chemical solution at a fixed nutrient concentration. Although the growth of ZnO is carried out on poly-domain graphene-coated GaN substrate, the direction of hexagonal sidewall facet of ZnO is homogeneous over the whole ZnO-grown area on graphene/GaN because of strong remote epitaxial relation between ZnO and GaN across graphene. Atomic-resolution transmission electron microscopy corroborates the remote epitaxial relation. The non-covalent interface is applied to mechanically lift off the overlayer of ZnO crystals via a thermal release tape. The mechanism of facet-selective morphology control of ZnO is discussed in terms of electrostatic interaction between nutrient solution and facet surface passivated with functional groups derived from the chemical additives.

Enhancement in external quantum efficiency of AlGaInP red µ-LED using chemical solution treatment process.

To investigate the effects of their surface recovery and optical properties, extremely small sized (12 µm × 12 µm mesa area) red AlGaInP micro light emitting diodes ([Formula: see text] LED) were fabricated using a diluted hydrofluoric acid (HF) surface etch treatment. After the chemical treatment, the external quantum efficiencies (EQEs) of [Formula: see text]-LED at low and high injection current regions have been improved by 35.48% and 12.86%, respectively. The different phenomena of EQEs have a complex relationship between the suppression of non-radiative recombination originating from the etching damage of the surface and the improvement of light extraction of the sidewalls. The constant enhancement of EQE at a high injection current it is attributed to the expansion of the active region's sidewall surface area by the selective etching of AlInP layers. The improved EQE at a low injection current is related to the minimization of the surface recombination caused by plasma damage from the surface. High-resolution transmission electron microscopy (HR-TEM) revealed physical defects on the sidewall surface, such as plasma-induced lattice disorder and impurity contamination damage, were eliminated using chemical treatment. This study suggests that chemical surface treatment using diluted HF acid can be an effective method for enhancing the [Formula: see text]-LED performance.

Surface Energy-Driven Preferential Grain Growth of Metal Halide Perovskites: Effects of Nanoimprint Lithography Beyond Direct Patterning.

Hybrid organic-inorganic lead halide perovskites have attracted much attention in the field of optoelectronic devices because of their desirable properties such as high crystallinity, smooth morphology, and well-oriented grains. Recently, it was shown that thermal nanoimprint lithography (NIL) is an effective method not only to directly pattern but also to improve the morphology, crystallinity, and crystallographic orientations of annealed perovskite films. However, the underlining mechanisms behind the positive effects of NIL on perovskite material properties have not been understood. In this work, we study the kinetics of perovskite grain growth with surface energy calculations by first-principles density functional theory (DFT) and reveal that the surface energy-driven preferential grain growth during NIL, which involves multiplex processes of restricted grain growth in the surface-normal direction, abnormal grain growth, crystallographic reorientation, and grain boundary migration, is the enabler of the material quality enhancement. Moreover, we develop an optimized NIL process and prove its effectiveness by employing it in a perovskite light-emitting electrochemical cell (PeLEC) architecture, in which we observe a fourfold enhancement of maximum current efficiency and twofold enhancement of luminance compared to a PeLEC without NIL, reaching a maximum current efficiency of 0.07598 cd/A at 3.5 V and luminance of 1084 cd/m2 at 4 V.

Nickel-Platinum Nanoparticles as Peroxidase Mimics with a Record High Catalytic Efficiency.

While nanoscale mimics of peroxidase have been extensively developed over the past decade or so, their catalytic efficiency as a key parameter has not been substantially improved in recent years. Herein, we report a class of highly efficient peroxidase mimic-nickel-platinum nanoparticles (Ni-Pt NPs) that consist of nickel-rich cores and platinum-rich shells. The Ni-Pt NPs exhibit a record high catalytic efficiency with a catalytic constant (Kcat) as high as 4.5 × 107 s-1, which is ∼46- and 104-fold greater than the Kcat values of conventional Pt nanoparticles and natural peroxidases, respectively. Density functional theory calculations reveal that the unique surface structure of Ni-Pt NPs weakens the adsorption of key intermediates during catalysis, which boosts the catalytic efficiency. The Ni-Pt NPs were applied to an immunoassay of a carcinoembryonic antigen that achieved an ultralow detection limit of 1.1 pg/mL, hundreds of times lower than that of the conventional enzyme-based assay.

Morphology-Invariant Metallic Nanoparticles with Tunable Plasmonic Properties.

Current methods for tuning the plasmonic properties of metallic nanoparticles typically rely on alternating the morphology (i.e., size and/or shape) of nanoparticles. The variation of morphology of plasmonic nanoparticles oftentimes impairs their performance in certain applications. In this study, we report an effective approach based on the control of internal structure to engineer morphology-invariant nanoparticles with tunable plasmonic properties. Specifically, these nanoparticles were prepared through selective growth of Ag on the inner surfaces of preformed Ag-Au alloyed nanocages as the seeds to form Ag@(Ag-Au) shell@shell nanocages. Plasmonic properties of the Ag@(Ag-Au) nanocages can be conveniently and effectively tuned by varying the amount of Ag deposited on the inner surfaces, during which the overall morphology of the nanocages remains unchanged. To demonstrate the potential applications of the Ag@(Ag-Au) nanocages, they were applied to colorimetric sensing of human carcinoembryonic antigen (CEA) that achieved low detection limits. This work provides a meaningful concept to design and craft plasmonic nanoparticles.

Atomic Layer Deposition of Layered Boron Nitride for Large-Area 2D Electronics.

Hexagonal boron nitride (h-BN) has been considered a promising dielectric for two-dimensional (2D) material-based electronics due to its atomically smooth and charge-free interface with an in-plane lattice constant similar to that of graphene. Here, we report atomic layer deposition of boron nitride (ALD-BN) using BCl3 and NH3 precursors directly on thermal SiO2 substrates at a relatively low temperature of 600 °C. The films were characterized by X-ray photoelectron spectroscopy, atomic force microscopy, and transmission electron microscopy wherein the uniform, atomically smooth, and nanocrystalline layered-BN thin film growth is observed. The growth rate is ∼0.042 nm/cycle at 600 °C, a temperature significantly lower than that of h-BN grown by chemical vapor deposition. The dielectric properties of the ALD-BN measured from Metal Oxide Semiconductor Capacitors are comparable with that of SiO2. Moreover, the ALD-BN exhibits a 2-fold increase in carrier mobility of graphene field effect transistors (G-FETs/ALD-BN/SiO2) due to the lower surface charge density and inert surface of ALD-BN in comparison to that of G-FETs fabricated on bare SiO2. Therefore, this work suggests that the transfer-free deposition of ALD-BN on SiO2 may be a promising candidate as a substrate for high performance graphene devices.

Strain-Engineered Anisotropic Optical and Electrical Properties in 2D Chiral-Chain Tellurium.

Atomically thin materials, leveraging their low-dimensional geometries and superior mechanical properties, are amenable to exquisite strain manipulation with a broad tunability inaccessible to bulk or thin-film materials. Such capability offers unexplored possibilities for probing intriguing physics and materials science in the 2D limit as well as enabling unprecedented device applications. Here, the strain-engineered anisotropic optical and electrical properties in solution-grown, sub-millimeter-size 2D Te are systematically investigated through designing and introducing a controlled buckled geometry in its intriguing chiral-chain lattice. The observed Raman spectra reveal anisotropic lattice vibrations under the corresponding straining conditions. The feasibility of using buckled 2D Te for ultrastretchable strain sensors with a high gauge factor (≈380) is further explored. 2D Te is an emerging material boasting attractive characteristics for electronics, sensors, quantum devices, and optoelectronics. The results suggest the potential of 2D Te as a promising candidate for designing and implementing flexible and stretchable devices with strain-engineered functionalities.

Remote heteroepitaxy of GaN microrod heterostructures for deformable light-emitting diodes and wafer recycle.

There have been rapidly increasing demands for flexible lighting apparatus, and micrometer-scale light-emitting diodes (LEDs) are regarded as one of the promising lighting sources for deformable device applications. Herein, we demonstrate a method of creating a deformable LED, based on remote heteroepitaxy of GaN microrod (MR) p-n junction arrays on c-Al2O3 wafer across graphene. The use of graphene allows the transfer of MR LED arrays onto a copper plate, and spatially separate MR arrays offer ideal device geometry suitable for deformable LED in various shapes without serious device performance degradation. Moreover, remote heteroepitaxy also allows the wafer to be reused, allowing reproducible production of MR LEDs using a single substrate without noticeable device degradation. The remote heteroepitaxial relation is determined by high-resolution scanning transmission electron microscopy, and the density functional theory simulations clarify how the remote heteroepitaxy is made possible through graphene.

Strong Second Harmonic Generation in a Tungsten Bronze Oxide by Enhancing Local Structural Distortion.

To discover the nonlinear optical (NLO) materials with strong second harmonic generation (SHG), the design of NLO-active molecular units with large polarization is considered as a common strategy. Herein, we propose that the local structural distortion induced with vacancies, apart from the NLO-active units, can be employed to improve the NLO effect in solids as well. Accordingly, a new tungsten bronze (TB) oxide, Pb2(Pb0.15Li0.7□0.15)Nb5O15 (□ representing vacancies), is successfully designed and prepared, which exhibits a strong SHG response of 39 times that of KH2PO4. The detailed analysis reveals that the local structural distortions enhanced by the vacancies in PLN strengthen the local dipole moments of neighboring NbO6 octahedra, and thus significantly prompt the SHG effect. Moreover, a series of new TB compounds with large NLO effects are discovered by this molecular design strategy, which are perspectives for new NLO materials synthesis.

Template Regeneration in Galvanic Replacement: A Route to Highly Diverse Hollow Nanostructures.

The ability to produce a diverse spectrum of hollow nanostructures is central to the advances in many current and emerging areas of technology. Herein, we report a general method to craft hollow nanostructures with highly tunable physical and chemical parameters. The key strategy is to regenerate the nanoscale sacrificial templates in a galvanic replacement reaction through site-selective overgrowth. As examples, we demonstrate the syntheses of nanocages and nanotubes made of silver, gold, palladium, and/or platinum with well-controlled wall thicknesses and elemental distributions. Using the nanocages of silver and gold as models, we demonstrate they possess intriguing plasmonic properties and offer superior performance in biosensing applications. This study provides a powerful platform to customize hollow nanostructures with desired properties and therefore is expected to enable a variety of fundamental studies and technologically important applications.

Parallel Nanoimprint Forming of One-Dimensional Chiral Semiconductor for Strain-Engineered Optical Properties.

The low-dimensional, highly anisotropic geometries, and superior mechanical properties of one-dimensional (1D) nanomaterials allow the exquisite strain engineering with a broad tunability inaccessible to bulk or thin-film materials. Such capability enables unprecedented possibilities for probing intriguing physics and materials science in the 1D limit. Among the techniques for introducing controlled strains in 1D materials, nanoimprinting with embossed substrates attracts increased attention due to its capability to parallelly form nanomaterials into wrinkled structures with controlled periodicities, amplitudes, orientations at large scale with nanoscale resolutions. Here, we systematically investigated the strain-engineered anisotropic optical properties in Te nanowires through introducing a controlled strain field using a resist-free thermally assisted nanoimprinting process. The magnitude of induced strains can be tuned by adjusting the imprinting pressure, the nanowire diameter, and the patterns on the substrates. The observed Raman spectra from the chiral-chain lattice of 1D Te reveal the strong lattice vibration response under the strain. Our results suggest the potential of 1D Te as a promising candidate for flexible electronics, deformable optoelectronics, and wearable sensors. The experimental platform can also enable the exquisite mechanical control in other nanomaterials using substrate-induced, on-demand, and controlled strains.

Fabrication of hexagonal boron nitride based 2D nanopore sensor for the assessment of electro-chemical responsiveness of human serum transferrin protein.

In this work, we present a step-by-step workflow for the fabrication of 2D hexagonal boron nitride (h-BN) nanopores which are then used to sense holo-human serum transferrin (hSTf) protein at pH ∼8 under applied voltages ranging from +100 mV to +800 mV. 2D nanopores are often used for DNA, however, there is a great void in the literature for single-molecule protein sensing and this, to the best of our knowledge, is the first time where h-BN-a material with large band-gap, low dielectric constant, reduced parasitic capacitance and minimal charge transfer induced noise-is used for protein profiling. The corresponding ΔG (change in pore conductance due to analyte translocation) profiles showed a bimodal Gaussian distribution where the lower and higher ΔG distributions were attributed to (pseudo-) folded and unfolded conformations respectively. With increasing voltage, the voltage induced unfolding increased (evident by decrease in ΔG) and plateaued after ∼400 mV of applied voltage. From the ΔG versus voltage profile corresponding to the pseudo-folded state, we calculated the molecular radius of hSTf, and was found to be ∼3.1 nm which is in close concordance with the literature reported value of ∼3.25 nm.

Delayed Photoluminescence and Modified Blinking Statistics in Alumina-Encapsulated Zero-Dimensional Inorganic Perovskite Nanocrystals.

We demonstrate enhancement of the photoluminescence (PL) properties of individual zero-dimensional (0D) Cs4PbBr6 perovskite nanocrystals (PNCs) upon encapsulation by alumina using an appropriately modified atomic layer deposition method. In addition to the increased PL intensity and improved long-term stability of encapsulated PNCs, our single-particle studies reveal substantial changes in the PL blinking statistics and the persistent appearance of the long-lived, "delayed" PL components. The blinking patterns exhibit a modification from the fast switching between fluorescent ON and OFF states found in bare PNCs to a behavior with longer ON states and more isolated OFF states in alumina-encapsulated PNCs. Controlled exposure of 0D nanocrystals to moisture suggests that the observed PL lifetime changes may be related to water-induced "reservoir" states that allow for longer-lived charge storage with subsequent back-feeding into the emissive states. Viable encapsulation of PNCs with metal oxides that can preserve and even enhance their PL properties can be utilized in the fabrication of extended structures on their basis for optoelectronic and photonic applications.

MoS2 for Enhanced Electrical Performance of Ultrathin Copper Films.

Copper nanowires are widely used as on-chip interconnects due to their superior conductivity. However, with aggressive Cu interconnect scaling, surface scattering of electrons drastically increases the electrical resistivity. In this work, we have studied the electrical performance of Cu thin films deposited on different materials. By comparing the thickness dependence of Cu films' resistivity on MoS2 and SiO2, we have demonstrated that MoS2 can be used to enhance the electrical performance of ultrathin Cu films due to improved specular surface scattering by up to 40%. By fitting the experimental data with the theoretical Fuchs-Sondheimer (FS) model, we have determined the specularity parameter at the Cu/MoS2 interface to be p ≈ 0.4 at room temperature. Furthermore, first principle calculations based on density functional theory (DFT) indicate that the localized density of states (LDOS) at the Cu/amorphous SiO2 interface is larger than the LDOS at the Cu/MoS2 interface, which is believed to be responsible for the higher resistivity in the Cu thin films that are deposited on SiO2 substrates. Our results suggest that MoS2 may serve as a performance enhancer for future generations of Cu interconnects.

Regulated Interfacial Thermal Conductance between Cu and Diamond by a TiC Interlayer for Thermal Management Applications.

The metal/diamond interface consisting of two highly dissimilar materials is widely present in high-power microelectronic devices using a diamond film as a heat spreader or using a metal matrix/diamond filler composite as a heat sink for thermal management applications. To improve the interfacial thermal conductance (G), a common method is to add an appropriate interlayer in between the two materials; however, the effect of the interlayer on G is still not clear. In this work, we prepare a Cu/TiC/diamond structure by magnetron sputtering to detect how the crystallinity, grain size, and thickness of the TiC interlayer influence G between Cu and diamond. We characterize in detail the interface by transmission electron microscopy and X-ray photoelectron spectroscopy and measure experimentally G by the time-domain thermoreflectance technique. The results indicate that the higher crystallinity and thinner interlayer are both beneficial to the improvement of G between Cu and diamond, but the G is insensitive to the grain size of TiC. An increase of G between Cu and diamond as much as 48% can be reached by a highly crystallized 10 nm thick TiC interlayer. The microscopic characteristics of the TiC interlayer have played a decisive role for G between Cu and diamond. While an inserted interlayer in principle has a potential to enhance G between two dissimilar materials, the low crystallinity and large thickness of the interlayer will weaken the enhancement or even reverse this positive effect. The G of a sandwiched structure can be regulated in a wide range by the microscopic characteristics of the interlayer, which provides guidelines for preparation of metal/nonmetal interfaces with high interfacial thermal conductance for thermal management applications.