Sol-flame synthesis of hybrid metal oxide nanowires

Hybrid metal oxide nanowires (NWs), with small characteristic diameter and large aspect ratio, can have unique and yet tunable chemical, optical and electrical properties by independently controlling the chemical compositions and morphologies of the individual components. Such hybrid NWs are promising building blocks in many applications, such as catalysis, sensors, batteries, solar cells and photoelectrochemical devices. However, these applications are hindered by the lack of scalable and economic methods for the synthesis of hybrid NWs. Here, we report a simple, scalable and new sol-flame method to synthesize various hybrid metal oxide NWs, including nanoparticle-shell decorated NWs (NP-shell@NW), NP-chain decorated NW (NP-chain@NW) and doped NWs. The sol-flame process first coats existing NWs with NPs or dopants precursors prepared by the sol–gel process, and then dissociates/oxidizes these precursors in flame. The sol-flame method uniquely combines the merits of the flame process (e.g., high temperature and fast heating rate) with low temperature sol–gel method (e.g., broad material choices and excellent chemical composition control). For both the NP-shell@NW and NP-chain@NW cases, the high temperature flame, compared to furnace, provides much faster heating rate and shorter duration for annealing, which evaporates and burns the precursor solvent rapidly, causing NPs to quickly nucleate around NWs without significant agglomeration. Hence, higher loading density of NPs with smaller sizes is decorated to the NWs, and the formed hybrid NP@NW exhibits significantly higher catalytic activity than that of the furnace-annealed sample. Similarly when using the sol-flame method to dope NWs, the high temperature flame enables rapid dopant diffusion and short annealing duration that maintains the morphology of the original materials and protects the delicate NW substrates from damage. We believe that the new sol-flame method can be applied to synthesize various 1-D hybrid metal oxide nanostructures, thereby impacting diverse application fields.     

Growth and properties of self‐catalyzed (In,Mn)As nanowires

Mn‐assisted molecular beam epitaxy is used for the growth of (In,Mn)As nanowires (NWs) on GaAs(111)B. The transmission electron microscopy measurements revealed that despite the relatively high growth temperature regime this technique can be used to obtain (In,Mn)As NWs with high crystalline quality without any crystal defects, such as dislocations, stacking faults or precipitates inside the investigated NWs or on their side‐walls, although the growth processes of NWs were accompanied by the formation of MnAs precipitates between the NWs at the interface of the wetting layer. The results obtained are of importance for the realization of new spintronic nanostructured materials. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Quantitative analysis of the phonon confinement effect in arbitrarily shaped Si nanocrystals decorated on Si nanowires and its correlation with the photoluminescence spectrum

Arrays of single‐crystalline Si nanowires (NWs) decorated with arbitrarily shaped Si nanocrystals (NCs) are grown by a metal‐assisted chemical etching process using silver (Ag) as the noble metal catalyst. The metal‐assisted chemical etching‐grown Si NWs exhibit strong photoluminescence (PL) emission in the visible and near infrared region at room temperature. Quantum confinement of carriers in the Si NCs is believed to be primarily responsible for the observed PL emission. Raman spectra of the Si NCs decorated on Si NWs exhibit a red shift and an asymmetric broadening of first‐order Raman peak as well as the other multi‐phonon modes when compared with that of the bulk Si. Quantitative analysis of confinement of phonons in the Si NCs is shown to account for the measured Raman peak shift and asymmetric broadening. To eliminate the laser heating effect on the phonon modes of the Si NWs/NCs, the Raman measurement was performed at extremely low laser power. Both the PL and Raman spectral analysis show a log‐normal distribution for the Si NCs, and our transmission electron microscopy results are fully consistent with the results of PL and Raman analyses. We calculate the size distribution of these Si NCs in terms of mean diameter (D₀) and skewness (σ) by correlating the PL spectra and Raman spectra of the as‐grown Si NCs decorated on Si NWs. Copyright © 2015 John Wiley & Sons, Ltd.     

New technique for heterogeneous vapor-phase synthesis of nanostructured metal layers from low-dimensional volatile metal complexes

A new technique for depositing thin nanostructured layers on semiconductor and insulating substrates that is based on heterogeneous gas-phase synthesis from low-dimensional volatile metal complexes is suggested and tried out. Thin nanostructured copper layers are deposited on silicon and quartz substrates from low-dimensional formate complexes using a combined synthesis-mass transport process. It is found that copper in layers thus deposited is largely in a metal state (Cu⁰) and has the form of closely packed nanograins with a characteristic structure.     

Theory of oxidation/reduction-induced valence transformations of metal ion dopants in oxide crystals mediated by oxide-vacancy diffusion: II. Kinetic analysis

We consider theoretically valence transformations of doping metal ions in oxide crystals induced by oxidation and reduction obtained by changes in the ambient oxygen partial pressure. Three types of oxygen vacancies are assumed to mediate transformations: neutral, singly ionized, and doubly ionized. In the companion part I paper we provide thermodynamic analyses yielding concentration relations among the oxygen vacancy, metal ions, holes and electrons, as functions of the ambient oxygen pressure. In the present companion part II paper we provide time dependent concentration profiles of the various species and reaction rate profiles. The diffusion exhibits a complex behavior; under some conditions, it may be described by a constant diffusivity, and is symmetric with respect to oxidation and reduction. However, under a wide range of conditions, the ionic state changes are highly asymmetric with respect to oxidation and reduction. For example, in the case of a neutral vacancy, a very narrow reaction front may establish during reduction. In the inverse (oxidation) process, however, the different species' profiles are quite smooth.     

Fabrication of metal/quantum dot/semiconductor structure on silicon substrate

A fabrication technique and optimal growth conditions are reported to develop a Sb-based quantum dot (QD) structure as a nanostructured III–V semiconductor on a silicon substrate. By using solid-source molecular beam epitaxy, high-density (>10¹⁰ cm⁻²) InGaSb QD structures can be obtained under a low growth temperature, which is compatible for use with Si-CMOS processes. We also proposed the construction of a metal/quantum dot/semiconductor (MDS) structure by using the InGaSb QD on a Si substrate. An infrared light emission with a photon energy of 0.95 eV is successfully observed from the fabricated MDS structure under the current injection conditions. It is expected that a MDS structure using a Sb-based QD will be used as a small-sized infrared light source for silicon photonic technology.     

Preparation of silver nanoparticles on zinc oxide nanowires by photocatalytic reduction for use in surface‐enhanced Raman scattering measurements

To increase the sensitivity in surface‐enhanced Raman scattering (SERS) measurements, the high surface area of zinc oxide nanowires (ZnO NWs) was used. ZnO NWs on silicon substrates were prepared and used as substrates for further growth of silver nanoparticles (AgNPs). Ultraviolet (UV) irradiation was used to reduce silver ions to AgNPs on the ZnO wires. With proper growth conditions for both ZnO NWs and AgNPs, the substrates exhibit SERS enhancement factors greater than 10⁶. To understand the influences of the morphologies of the ZnO NWs on the growth of AgNPs, the growing time and temperature were varied. The concentration of silver nitrate and irradiation time of UV radiation were also varied. The resulting AgNPs were probed with para‐nitrothiophenol to quantify the SERS enhancements obtained from the varying conditions. The results indicate that ZnO NWs could be grown at temperatures higher than 490 °C and higher growth temperatures result in smaller diameter of the formed ZnO NWs. Also, the morphologies of ZnO NWs did not significantly alter the SERS signals. The concentration of silver nitrate affects the SERS signals significantly and the optimal concentration was found to be in the range of 10–20 mM. With irradiation times longer than 90 s, the resulting AgNPs showed similar SERS intensities. With optimized conditions, the AgNPs/ZnO substrates are highly suitable for SERS measurements with a typical enhancement factor of higher than 10⁶. Copyright © 2010 John Wiley & Sons, Ltd.     

银纳米线表面等离激元波导的能量损耗

金属纳米结构的表面等离激元可以突破光学衍射极限,为光子器件的微型化和集成光学芯片的实现奠定基础.基于表面等离激元的各种基本光学元件已经研制出来.然而,由于金属结构的固有欧姆损耗以及向衬底的辐射损耗等,表面等离激元的传输能量损耗较大,极大地制约了其在纳米光子器件和回路中的应用.研究能量损耗的影响因素以及如何有效降低能量损耗对未来光子器件的实际应用具有重要意义.本文从纳米线表面等离激元的基本模式出发,介绍了它在不同条件下的场分布和传输特性,在此基础上着重讨论纳米线表面等离激元传输损耗的影响因素和测量方法以及目前常用的降低传输损耗的思路.最后给出总结以及如何进一步降低能量损耗方法的展望.表面等离激元能量损耗的相关研究对于纳米光子器件的设计和集成光子回路的构建有着重要作用.     

Fabrication of nanostructured silicon surface using selective chemical etching

A two-stage process based on selective chemical etching induced by metal nanoclusters is used to fabricate nanostructured surfaces of silicon plates with a relatively low reflectance. At silicon surfaces covered with silver nanoclusters, the SERS effect is observed for rhodamine concentrations of about 10^–12 M. At certain technological parameters, the depth of the nanostructured layer weakly depends on the conditions for the two-stage etching, in particular, etching time. Under otherwise equal conditions for etching, the rate of the formation of textured layer in the p-type silicon is two times greater than the formation rate in the n-type silicon.     

Theory of oxidation/reduction-induced valence transformations of metal ion dopants in oxide crystals mediated by oxide-vacancy diffusion: I. Thermodynamic analysis

We consider theoretically valence transformations of doping metal ions in oxide crystals induced by oxidation and reduction obtained by changes in the ambient oxygen partial pressure. Three types of oxygen vacancies are assumed to mediate transformations: neutral, singly ionized, and doubly ionized. We provide thermodynamic equilibrium analyses, yielding concentration relations among the oxygen vacancy, metal ions, holes and electrons as functions of the ambient oxygen pressure. The results suggest that experimental study of different species concentrations at thermodynamic equilibrium as functions of pressure and temperature should allow assessment of various reversible reaction constants controlling the process. In the Part II companion paper, the kinetic (diffusion) characteristics are considered in detail.     

Surface‐enhanced Raman scattering from gold‐coated germanium oxide nanowires

We utilized bulk‐synthesized nanowires (NWs) of germanium dioxide as nanoscale structures that can be coated with noble metals to allow the excitation of surface plasmons over a broad frequency range. The NWs were synthesized on substrates of silicon using gold‐catalyst‐assisted vapor–liquid–solid (VLS) growth mechanism in a simple quartz tube furnace setup. The resulting NWs have diameters of ∼100–200 nm, with lengths averaging ∼10–40 µm and randomly distributed on the substrate. The NWs are subsequently coated with thin films of gold, which provide a surface‐plasmon‐active surface. Surface‐enhanced Raman scattering (SERS) studies with near‐infrared (NIR) excitation at 785 nm show significant enhancement (average enhancement > 10⁶) with good uniformity to detect submonolayer concentrations of 4‐methylbenzenethiol (4‐MBT), trans‐1,2‐bis(4‐pyridyl)ethylene (BPE), and 1,2‐benzendithiol (1,2‐BDT) probe molecules. We also observed an intense, broad continuum in the Raman spectrum of NWs after metal coating, which tended to diminish with the analyte monolayer formation. Copyright © 2008 John Wiley & Sons, Ltd.     

Resonance Raman study of He+ ion implanted nanostructured ZnS

ZnS nanocrytsals of size ∼2.5 nm were prepared by chemical precipitation technique. Pressed pellets of nanostructured ZnS were implanted with He⁺ ions at doses of 5 × 10¹⁴, 1 × 10¹⁵ and 5 × 10¹⁵ ions/cm². Raman spectra of both unimplanted and He⁺ ion implanted samples were recorded with ultraviolet (UV) excitation. LO, 2LO, 2TO, (LO + TA) and (2TO − TA) modes of ZnS were observed in the resonance Raman spectra of the unimplanted nanostructured ZnS samples. In addition, a surface mode was observed at 294 cm⁻¹. With the implantation of He⁺ ions, the 2TO mode disappeared and 2LO mode became prominent and this observation was attributed to the decrease in band gap of ZnS nanocrytsals due to ion implantation. The exciton–LO phonon coupling strength was determined from the intensity ratio of 2LO to LO modes and it was observed that the exciton–LO phonon coupling strength increases with increase in implantation dose. In the present work, we report for the first time the observation of 2TO mode in the resonance Raman spectrum of nanostructured ZnS and also the modification of exciton–LO phonon coupling strength of semiconductor nanoparticles by ion implantation. Copyright © 2008 John Wiley & Sons, Ltd.     

Identification and control of multiple leaky plasmon modes in silver nanowires

Leaky plasmon modes (LPMs) in metal nanowires (NWs), which combine the physical characteristic of both “plasmonics” and “leaky radiation”, present distinguished performances in terms of guiding and radiating light. In contrast to traditional light‐guiding in metal NWs with one single LPM, multiple LPMs are crucial for advanced uses such as augmenting data transmission channels, enhancing sensing performance, manipulating polarization and converting mode. Here, we demonstrate experimentally the control over multiple LPMs in pentagonal silver NWs. By combining far‐field real‐space imaging and leakage radiation microscopy, the three typical LPMs with fields mainly concentrating in corners surrounded by air are specifically identified. By manipulating excitation wavelengths and NW diameters, the number of the excited LPMs can be controlled. These findings reveal the physics of LPMs in silver NWs, thereby paving the way towards applying the high‐order leaky modes in silver NWs for photonic integrated circuits, nanoscale confinement, plasmonic sensing, QD‐nanowire coupling, etc.

     

Light Harvesting and Enhanced Performance of Si Quantum Dot/Si Nanowire Heterojunction Solar Cells

Si nanowires (Si NWs) structures with good antireflection and enhanced optical‐absorption properties are used to fabricate Si quantum dots/Si NWs heterojunction solar cells. The Si NWs prepared by the metal‐assisted chemical‐etching technique exhibit a very low reflection in a wide spectral range (300–1200 nm). Correspondingly, the optical absorption reaches as high as 88.9% by weighting AM1.5G solar spectrum. Both the short current density and open current voltage are improved compared to the reference flat cell. However, the photovoltaic properties are degraded by varying the Si NWs with long etching time, possibly due to the increased etching‐induced surface states. The optimal Si NWs lead to the best cell with the power conversion efficiency of 11.3%.     

Core–Shell Structured Nanocomposites for Photocatalytic Selective Organic Transformations

Core–shell structured nanocomposites, a type of talented functional materials with unique microstructure and properties, have shown great promise as photocatalysts for various applications, including photocatalytic degradation of pollutants, water splitting for hydrogen production, and selective organic transformations. The synthesis and utilization of efficient core–shell nanoarchitectured photocatalysts for selective organic synthesis are at the center of our research efforts and the focus of this minireview. Specifically, semiconductor‐based core–shell nanocomposites, including metal–semiconductor, semiconductor–semiconductor, semiconductor–shell (graphene and SiO₂) as photocatalysts/cocatalysts for selective oxidation of alcohols, reduction of nitro organics and carbon dioxide for synthesis of fine chemicals, and redox‐combined selective synthesis of pipecolinic acid are summarized. It is hoped that this minireview can make a contribution to catalyzing the development of smart core–shell nanostructures in the field of photocatalytic selective organic transformations for solar energy conversion.     

Ion‐Beam Sculpting of Nanowires

Nanomaterials often undergo unusual mechanical deformations compared to their bulk counterparts when irradiated with ion‐beams. This study visualizes and investigates some of the unusual interactions that can occur in nanomaterials during irradiation with medium‐energy ion‐beams using a helium‐ion microscope (HIM). Ion‐beam sculpting of semiconductor nanowires (NWs) with sub‐10 nm features is demonstrated. Moreover, irradiation‐induced growth of NWs at room‐temperature is discovered. The new concept and possible mechanism of irradiation‐induced VLS (vapor–liquid–solid) growth of NWs is introduced. These results are the basis for further fundamental and technological developments toward manipulation and visualization of ion–matter interactions at the nanoscale.     

Passivation at semiconductor/electrolyte interface: Role of adsorbate solvation and reactivity in surface atomic and electronic structure modification of III-V semiconductor

These studies are focused on understanding the role played by a solvent in chemical and electronic processes occurred in the course of semiconductor surface passivation at semiconductor/electrolyte interface. It is shown that the chemical reactivity of the ionic adsorbate at a semiconductor/electrolyte interface can be changed considerably through interaction with solvent molecules. The reactivity of anions depends essentially on the solvating solvent: hydrated ions could be either slightly electrophilic or slightly nucleophilic, whereas the ions solvated by alcohol molecules are always strongly nucleophilic. Mechanism of interaction of such solvated ions with the semiconductor surface atoms depends on the solvent, as is demonstrated by the example of processes occurred at GaAs(1 0 0)/sulfide solution interfaces. It is found that on adsorption of HS⁻ ions from different solvents the AsS bonds with solvent-dependent ionic character are formed on a GaAs(1 0 0) surface. The surface obtained in such a way possesses different ionization energy and exhibit different electronic properties dependent on the solvent.     

Reduction of hexavalent chromium with colloidal and supported palladium nanocatalysts

Zinc oxide (ZnO) nanowires (NWs) are exposed to energetic proton (H⁺), nitrogen (N⁺), phosphorus (P⁺), and argon (Ar⁺) ions to understand the radiation hardness and structural changes induced by these irradiations. High-resolution transmission electron microscopy is utilized to see the irradiation effects in NWs. Multiple doses and energies of radiation at different temperatures are used for different set of samples. The study reveals that wurtzite (crystalline)-structured ZnO NWs experience amorphization, degradation, and morphological changes after the irradiation. At room temperature, deterioration of the crystalline structure is observed under high fluence of H⁺, N⁺, and P⁺ ions. While for ZnO NWs, bombarded by Ar⁺ and P⁺ ions, nano-holes are produced. The ZnO NWs surfaces also show corrugated morphology full of nano-humps when irradiated by Ar⁺ ions at 400 °C. The corrugated surface could serve as tight-holding interface when interconnecting it with other NWs/nanotubes. These nano-humps may have the function of increasing the surface for surface-oriented sensing applications in the future.     

Magneto-transport properties of thin flakes of Weyl semiconductor tellurium

As an elemental semiconductor, tellurium has recently attracted intense interest due to its non-trivial band topology, and the resulted intriguing topological transport phenomena. In this study we report systematic electronic transport studies on tellurium flakes grown via a simple vapor deposition process. The sample is self-hole-doped, and exhibits typical weak localization behavior at low temperatures. Substantial negative longitudinal magnetoresistance under parallel magnetic field is observed over a wide temperature region, which is considered to share the same origin with that in tellurium bulk crystals, i.e., the Weyl points near the top of valence band. However, with lowering temperature the longitudinal magnetoconductivity experiences a transition from parabolic to linear field dependency, differing distinctly from the bulk counterparts. Further analysis reveals that such a modulation of Weyl behaviors in this low-dimensional tellurium structure can be attributed to the enhanced inter-valley scattering at low temperatures. Our results further extend Weyl physics into a low-dimensional semiconductor system, which may find its potential application in designing topological semiconductor devices.     

GaN nanowires for piezoelectric generators

We demonstrate the high potential of GaN nanowires (NWs) to convert mechanical energy into electric energy. Using an atomic force microscope equipped with a Resiscope module, an average output voltage of –74 mV and a maximum of –443 mV ± 2% per NW were measured. This latter value is the highest reported so far for GaN NWs. By considering these output signals, we have estimated an average and a maximum power density generated by one layer of GaN NWs of the order of 5.9 mW/cm² and 130 mW/cm², respectively. These results offer promising prospects for the use of GaN NWs for high‐efficiency ultracompact piezogenerators. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)