Tak Fu Hung

Upconverting Near‐Infrared Light through Energy Management in Core–Shell–Shell Nanoparticles

Lanthanide-doped upconversion materials, capable of converting low-density (< 1000 W cm ) near-infrared (NIR) excitation to ultraviolet (UV) and visible emissions, have generated a large amount of interests in the areas of information technology, biotechnology, energy, and photonics. Significantly, recent developments in the synthetic and multicolor tuning methods have allowed easy access to upconversion nanoparticles with well-defined phase and size, core–shell structure, optical emission, and surface properties. The technological advances provide promising applications in sensitive biodetection and advanced bioimaging without many of the constraints associated with conventional optical biolabels. Despite the attractions, further progress in using upconversion processes has been largely hindered because upconversion nanoparticles are typically sensitized by Yb ions that only respond to narrowband NIR excitation centered at 980 nm. The absorption of 980 nm light by the water component in biological samples usually limits deep tissue imaging and induces potential thermal damages to cells and tissues. Excitation of conventional upconversion nanoparticles at other wavelengths has been proposed to minimize the effect of water absorption. But the use of this technique is limited mainly by the largely sacrificed excitation efficiency. Efforts have also been devoted to tuning the NIR response of photon upconversion through integration of various sensitizers such as metal ions (e.g.; Nd, V or Cr) and organic dyes. The progress has resulted in visible emission by NIR excitation in the 700–900 nm range where the transparency of biological samples is maximal. However, upconversion emission across a broad range of spectra in these systems have not been demonstrated largely owing to the uncontrollable nonradiative processes. Herein, we describe a novel design, based on nanostructural engineering to separate unwanted electronic transitions for constructing a new class of materials displaying tunable upconversion emissions spanning from UV to the visible spectral region by single wavelength excitation at 808 nm. We also show that these nanoparticles can surpass the constraints associated with conventional upconversion nanoparticles for biological studies. The nanostructure design for management of energy transitions is depicted in Figure 1. A core–shell–shell nanoparticle platform is used to host light-harvesting, upconvert-

Control of Emission Color of High Quantum Yield CH3NH3PbBr3 Perovskite Quantum Dots by Precipitation Temperature

Emission color controlled, high quantum yield CH3NH3PbBr3 perovskite quantum dots are obtained by changing the temperature of a bad solvent during synthesis. The products for temperatures between 0 and 60 °C have good spectral purity with narrow emission line widths of 28–36 nm, high absolute emission quantum yields of 74% to 93%, and short radiative lifetimes of 13–27 ns.

A Biomimetic Hierarchical Scaffold: Natural Growth of Nanotitanates on Three-Dimensional Microporous Ti-Based Metals

Nanophase materials are promising alternative implant materials in tissue engineering. Here we report for the first time the large-scale direct growth of nanostructured bioactive titanates on three-dimensional (3D) microporous Ti-based metal (NiTi and Ti) scaffolds via a facile low temperature hydrothermal treatment. The nanostructured titanates show characteristics of 1D nanobelts/nanowires on a nanoskeleton layer. Besides resembling cancelous bone structure on the micro/macroscale, the 1D nanostructured titanate on the exposed surface is similar to the lowest level of hierarchical organization of collagen and hydroxyapatite. The resulting surface displays superhydrophilicity and favors deposition of hydroxyapatite and accelerates cell attachment and proliferation. The remarkable simplicity of this process makes it widely accessible as an enabling technique for applications from engineering materials treatment including energy-absorption materials and pollution-treatment materials to biotechnology.

Tunable Electronic Transport Properties of Metal-Cluster- Decorated III-V Nanowire Transistors

A metal-cluster-decoration approach is utilized to tailor electronic transport properties (e.g., threshold voltage) of III-V NWFETs through the modulation of free carriers in the NW channel via the deposition of different metal clusters with different work function. The versatility of this technique has been demonstrated through the fabrication of high-mobility enhancement-mode InAs NW parallel FETs as well as the construction of low-power InAs NW inverters.

Hierarchical assembly of Ti(IV)/Sn(II) co-doped SnO2 nanosheets along sacrificial titanate nanowires: synthesis, characterization and electrochemical properties

Hierarchical assembly of Ti(IV)/Sn(II)-doped SnO₂ nanosheets along titanate nanowires serving as both sacrificial templates and a Ti(IV) source is demonstrated, using SnCl2 as a tin precursor and Sn(II) dopants and NaF as the morphology controlling agent. Excess fluoride inhibits the hydrolysis of SnCl2, promoting heterogeneous nucleation of Sn(II)-doped SnO₂ on the titanate nanowires due to the insufficient oxidization of Sn(II) to Sn(IV). Simultaneously, titanate nanowires are dissolved forming Ti(4+) species under the etching effect of in situ generated HF resulting in spontaneous Ti(4+) ion doping of SnO₂ nanosheets formed under hydrothermal conditions. Compositional analysis indicates that Ti(4+) ions are incorporated by substitution of Sn sites at a high level (16-18 at.%), with uniform distribution and no phase separation. Mössbauer spectroscopy quantified the relative content of Sn(II) and Sn(IV) in both Sn(II)-doped and Ti(IV)/Sn(II) co-doped SnO₂ samples. Electrochemical properties were investigated as an anode material in lithium ion batteries, demonstrating that Ti-doped SnO₂ nanosheets show improved cycle performance, which is attributed to the alleviation of inherent volume expansion of the SnO₂-based anode materials by substituting part of Sn sites with Ti dopants.

Stoichiometric Effect on Electrical, Optical, and Structural Properties of Composition-Tunable InxGa1–xAs Nanowires

Ternary InGaAs nanowires have recently attracted extensive attention due to their superior electron mobility as well as the ability to tune the band gap for technological applications ranging from high-performance electronics to high-efficiency photovoltaics. However, due to the difficulties in synthesis, there are still considerable challenges to assess the correlation among electrical, optical, and structural properties of this material system across the entire range of compositions. Here, utilizing a simple two-step growth method, we demonstrate the successful synthesis of composition and band gap tunable In(x)Ga(1-x)As alloy nanowires (average diameter = 25-30 nm) by manipulating the source powder mixture ratio and growth parameters. The lattice constants of each NW composition have been well correlated with the chemical stoichiometry and confirmed by high-resolution transmission electron microscopy and X-ray diffraction. Importantly, the as-grown NWs exhibit well-controlled surface morphology and low defect concentration without any phase segregation in all stoichiometric compositions. Moreover, it is found that the electrical nanowire device performances such as the turn-off and I(ON)/I(OFF) ratios are improved when the In concentration decreases at a cost of mobility degradation. More generally, this work suggests that a careful stoichiometric design is required for achieving optimal nanowire device performances.

Approaching the Hole Mobility Limit of GaSb Nanowires

In recent years, high-mobility GaSb nanowires have received tremendous attention for high-performance p-type transistors; however, due to the difficulty in achieving thin and uniform nanowires (NWs), there is limited report until now addressing their diameter-dependent properties and their hole mobility limit in this important one-dimensional material system, where all these are essential information for the deployment of GaSb NWs in various applications. Here, by employing the newly developed surfactant-assisted chemical vapor deposition, high-quality and uniform GaSb NWs with controllable diameters, spanning from 16 to 70 nm, are successfully prepared, enabling the direct assessment of their growth orientation and hole mobility as a function of diameter while elucidating the role of sulfur surfactant and the interplay between surface and interface energies of NWs on their electrical properties. The sulfur passivation is found to efficiently stabilize the high-energy NW sidewalls of (111) and (311) in order to yield the thin NWs (i.e., <40 nm in diameters) with the dominant growth orientations of ⟨211⟩ and ⟨110⟩, whereas the thick NWs (i.e., >40 nm in diameters) would grow along the most energy-favorable close-packed planes with the orientation of ⟨111⟩, supported by the approximate atomic models. Importantly, through the reliable control of sulfur passivation, growth orientation and surface roughness, GaSb NWs with the peak hole mobility of ∼400 cm(2)V s(-1) for the diameter of 48 nm, approaching the theoretical limit under the hole concentration of ∼2.2 × 10(18) cm(-3), can be achieved for the first time. All these indicate their promising potency for utilizations in different technological domains.

High-performance GaAs nanowire solar cells for flexible and transparent photovoltaics

Among many available photovoltaic technologies at present, gallium arsenide (GaAs) is one of the recognized leaders for performance and reliability; however, it is still a great challenge to achieve cost-effective GaAs solar cells for smart systems such as transparent and flexible photovoltaics. In this study, highly crystalline long GaAs nanowires (NWs) with minimal crystal defects are synthesized economically by chemical vapor deposition and configured into novel Schottky photovoltaic structures by simply using asymmetric Au-Al contacts. Without any doping profiles such as p-n junction and complicated coaxial junction structures, the single NW Schottky device shows a record high apparent energy conversion efficiency of 16% under air mass 1.5 global illumination by normalizing to the projection area of the NW. The corresponding photovoltaic output can be further enhanced by connecting individual cells in series and in parallel as well as by fabricating NW array solar cells via contact printing showing an overall efficiency of 1.6%. Importantly, these Schottky cells can be easily integrated on the glass and plastic substrates for transparent and flexible photovoltaics, which explicitly demonstrate the outstanding versatility and promising perspective of these GaAs NW Schottky photovoltaics for next-generation smart solar energy harvesting devices.

Crystal Orientation Controlled Photovoltaic Properties of Multilayer GaAs Nanowire Arrays

In recent years, despite significant progress in the synthesis, characterization, and integration of various nanowire (NW) material systems, crystal orientation controlled NW growth as well as real-time assessment of their growth-structure-property relationships still presents one of the major challenges in deploying NWs for practical large-scale applications. In this study, we propose, design, and develop a multilayer NW printing scheme for the determination of crystal orientation controlled photovoltaic properties of parallel GaAs NW arrays. By tuning the catalyst thickness and nucleation and growth temperatures in the two-step chemical vapor deposition, crystalline GaAs NWs with uniform, pure ⟨110⟩ and ⟨111⟩ orientations and other mixture ratios can be successfully prepared. Employing lift-off resists, three-layer NW parallel arrays can be easily attained for X-ray diffraction in order to evaluate their growth orientation along with the fabrication of NW parallel array based Schottky photovoltaic devices for the subsequent performance assessment. Notably, the open-circuit voltage of purely ⟨111⟩-oriented NW arrayed cells is far higher than that of ⟨110⟩-oriented NW arrayed counterparts, which can be interpreted by the different surface Fermi level pinning that exists on various NW crystal surface planes due to the different As dangling bond densities. All this indicates the profound effect of NW crystal orientation on physical and chemical properties of GaAs NWs, suggesting the careful NW design considerations for achieving optimal photovoltaic performances. The approach presented here could also serve as a versatile and powerful platform for in situ characterization of other NW materials.

Complementary Metal Oxide Semiconductor-Compatible, High-Mobility, ⟨111⟩-Oriented GaSb Nanowires Enabled by Vapor–Solid–Solid Chemical Vapor Deposition

Using CMOS-compatible Pd catalysts, we demonstrated the formation of high-mobility ⟨111⟩-oriented GaSb nanowires (NWs) via vapor-solid-solid (VSS) growth by surfactant-assisted chemical vapor deposition through a complementary experimental and theoretical approach. In contrast to NWs formed by the conventional vapor-liquid-solid (VLS) mechanism, cylindrical-shaped Pd5Ga4 catalytic seeds were present in our Pd-catalyzed VSS-NWs. As solid catalysts, stoichiometric Pd5Ga4 was found to have the lowest crystal surface energy and thus giving rise to a minimal surface diffusion as well as an optimal in-plane interface orientation at the seed/NW interface for efficient epitaxial NW nucleation. These VSS characteristics led to the growth of slender NWs with diameters down to 26.9 ± 3.5 nm. Over 95% high crystalline quality NWs were grown in ⟨111⟩ orientation for a wide diameter range of between 10 and 70 nm. Back-gated field-effect transistors (FETs) fabricated using the Pd-catalyzed GaSb NWs exhibit a superior peak hole mobility of ∼330 cm2 V-1 s-1, close to the mobility limit for a NW channel diameter of ∼30 nm with a free carrier concentration of ∼1018 cm-3. This suggests that the NWs have excellent homogeneity in phase purity, growth orientation, surface morphology and electrical characteristics. Contact printing process was also used to fabricate large-scale assembly of Pd-catalyzed GaSb NW parallel arrays, confirming the potential constructions and applications of these high-performance electronic devices.