Instantaneous formation of metal and metal oxide nanoparticles on carbon nanotubes and graphene via solvent-free microwave heating

Microwave irradiation was shown to be an effective energy source for the rapid decomposition of organic metal salts (such as silver acetate) in a solid mixture with various carbon and noncarbon substrates under completely solvent-free conditions. The rapid and local Joule heating of microwave absorbing substrates (i.e., carbon-based) resulted in the instantaneous formation of metal and metal oxide nanoparticles on the substrate surfaces within seconds of microwave exposure. Other less absorbing substrates (such as hexagonal boron nitride) required longer exposure times for the salt decomposition to occur. Details of the effects of microwave reaction time, temperature, power, and other experimental parameters were investigated and discussed. The solvent-free microwave method was shown to be widely applicable to various organic metal salts with different substrates including single- and multiwalled carbon nanotubes, graphene, expanded graphite, hexagonal boron nitride and silica-alumina particles, forming substrate-supported metal (e.g., Ag, Au, Co, Ni, Pd, Pt) or metal oxide (e.g., Fe?O?, MnO, TiO?) nanoparticles in high yields within short duration of microwave irradiation. The method was also successfully applied to large structural substrates such as nanotube yarns, further suggesting its application potential and versatility. To demonstrate one potential application, we successfully used both carbon nanotube powder and yarn samples decorated with Ag nanoparticles prepared via the above method to improve data acquisition in surface enhanced Raman spectroscopy.     

Temperature-dependent growth of germanium oxide and silicon oxide based nanostructures, aligned silicon oxide nanowire assemblies, and silicon oxide microtubes

We demonstrate the temperature-dependent growth of germanium oxide and silicon oxide based composite nanostructures (multiple nanojunctions of Ge nanowires and SiO(x) nanowires, Ge-filled SiO(2) nanotubes, Ge/SiO(2) coaxial nanocables, and a variety of interesting micrometer-sized structures), aligned SiO(x) nanowire assemblies, and SiO(x) microtubes. The structures were characterized by SEM, TEM, energy-dispersive X-ray spectroscopy, and electron diffraction. The combination of laser ablation of a germanium target and thermal evaoporation of silicon monoxide powders resulted in the formation of Ge and SiO(x) species in a carrier gas; the nano/micro-sized structures grow by either a Ge-catalyzed vapor-liquid-solid or a Ge-nanowire-templated vapor-solid process.     

Predictions of novel nanostructures of silicon by metal encapsulation

Recent studies using ab initio total energy calculations have shown exciting possibilities of developing novel metal encapsulated caged clusters of silicon with fullerene-like, Frank–Kasper and other polyhedral structures. In contrast to carbon for which empty cage fullerene structures are stable with 20 or more atoms, 10–16 atom silicon cage structures are stabilized by a guest metal atom. These nanoclusters are predicted to exhibit luminescence in the visible range and could find applications in biological systems, optoelectronics, and as tagging material. The Raman and infrared spectra have been calculated and they could help in the experimental identification of the structures. Interaction of these clusters with metal as well as oxygen or hydrogen atoms show that the fullerene structure is stable. Also the interaction between clusters themselves is weak and the ionization potentials, large. These properties make them attractive for cluster assembled materials such as nanowires, nanotubes, and other 2 and 3D structures. Studies on hydrogen interaction have led to the predictions of empty center hydrogenated silicon fullerenes Si_nH_n with large HOMO–LUMO gaps. These could further be doped endohedrally or exohedrally to produce novel silicon fullerenes with a variety of properties opening new ways of using silicon for diverse applications.     

Heterogeneous graphene nanostructures: ZnO nanostructures grown on large-area graphene layers

In this work, the synthesis and characterization of three-dimensional hetergeneous graphene nanostructures (HGN) comprising continuous large-area graphene layers and ZnO nanostructures, fabricated via chemical vapor deposition, are reported. Characterization of large-area HGN demonstrates that it consists of 1-5 layers of graphene, and exhibits high optical transmittance and enhanced electrical conductivity. Electron microscopy investigation of the three-dimensional heterostructures shows that the morphology of ZnO nanostructures is highly dependent on the growth temperature. It is observed that ordered crystalline ZnO nanostructures are preferably grown along the <0001> direction. Ultraviolet spectroscopy and photoluminescence spectroscopy indicates that the CVD-grown HGN layers has excellent optical properties. A combination of electrical and optical properties of graphene and ZnO building blocks in ZnO-based HGN provides unique characteristics for opportunities in future optoelectronic devices.     

基于聚吡咯/氧化石墨烯电极的MEMS微电容的性能研究

MEMS微电容具有高比容量、高储能密度和抗高过载等特点,在微电源系统、引信系统以及物联网等技术领域具有广泛的应用前景。设计制作了一种三维结构的聚吡咯/氧化石墨烯电极的MEMS微电容。该微电容由三维结构集流体、功能薄膜、凝胶电解质和BCB封装构成,其三维结构集流体是基于RIE刻蚀等微加工工艺加工实现的,而功能薄膜是通过电化学沉积工艺在集流体表面沉积聚吡咯/氧化石墨烯制备而成的,具有阻抗低、容量高、循环性能好的优点。电极的结构表征表明,聚吡咯中充分掺杂了氧化石墨烯,功能材料微观结构规整。器件电化学测试结果表明,放电电流为3mA时,MEMS微电容具有30μF的电容值,比容量达到7mF/cm2,在4000次充放电循环后,器件比容量仍保持在90%,电容量无明显衰减,具有稳定的电容性能和良好的循环性能。     

Aqueous-phase synthesis of Ag-TiO2-reduced graphene oxide and Pt-TiO2-reduced graphene oxide hybrid nanostructures and their catalytic properties

We demonstrate an aqueous solution method for the synthesis of a Ag-TiO₂-reduced graphene oxide (rGO) hybrid nanostructure (NS) in which the Ag and TiO₂ particles are well dispersed on the rGO sheet. The Ag-TiO₂-rGO NS was then used as a template to synthesize Pt-TiO₂-rGO NS. The resulting hybrid NSs were characterized by transmission electron microscopy (TEM), high-resolution TEM (HRTEM), energy-dispersive X-ray (EDX) spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR) spectroscopy, UV-vis spectroscopy, Raman spectroscopy, inductively coupled plasma mass spectrometry (ICP-MS), and catalytic studies. It was found that TiO₂-rGO, Ag-TiO₂-rGO and Pt-TiO₂-rGO NSs all show catalytic activity for the reduction of p-nitrophenol to p-aminophenol by NaBH₄, and that Pt-TiO₂-rGO NS exhibits the highest catalytic activity as well as excellent stability and easy recyclability.      

Emerging transparent electrodes based on thin films of carbon nanotubes, graphene, and metallic nanostructures

Transparent electrodes are a necessary component in many modern devices such as touch screens, LCDs, OLEDs, and solar cells, all of which are growing in demand. Traditionally, this role has been well served by doped metal oxides, the most common of which is indium tin oxide, or ITO. Recently, advances in nano-materials research have opened the door for other transparent conductive materials, each with unique properties. These include CNTs, graphene, metal nanowires, and printable metal grids. This review will explore the materials properties of transparent conductors, covering traditional metal oxides and conductive polymers initially, but with a focus on current developments in nano-material coatings. Electronic, optical, and mechanical properties of each material will be discussed, as well as suitability for various applications.     

Patterning of porous silicon nanostructures and eliminating microcracks on silicon nitride mask using metal assisted chemical etching

A method for selective formation of reproducible, high fidelity and controllable nano and micrometer size porous Si areas over n-type Si wafers is provided. A 400 nm thick Silicon Nitride layer was used as the mask layer while Platinum and Palladium nanoparticles were deposited over the unprotected areas to obtain porous areas through metal assisted chemical etching process. Nanoparticles were deposited by electroless plating solutions containing H₂PtCl₆ and PdCl₂. Good controls over pore size and depth were obtained with well defined and sharp edges of the patterned areas. The results were compared to porous structures obtained via electrochemical etching process, indicating the superiority of metal assisted etching in terms of its simplicity as well as the ability of Silicon Nitride layer acting as the mask layer.     

Low temperature formation of silicon oxide

Silicon oxide films have been formed at temperatures as low as 25°C, using a reaction of Si with a vapor mixture containing either NO, HF and H₂O or NO, HF, H₂O and O₂. Experimental data relating silicon oxide film growth with processing parameters such as vapor composition, temperature and time are presented. Conditions for the growth of silicon oxide films of specific thicknesses are outlined.     

Fluorescence studies of Rhodamine 6G functionalized silicon oxide nanostructures

Selective anchoring of optically active molecules on nanostructured surfaces is a promising step towards the creation of nanoscale devices with new functionalities. Recently we have demonstrated the electrostatic attachment of charged fluorescent molecules on silicon oxide nanostructures prepared by atomic force microscopy (AFM) nanolithography via local anodic oxidation (LAO) of dodecyl-terminated silicon. In this paper we report on our findings from a more detailed optical investigation of the bound dye Rhodamine 6G. High sensitivity optical wide field microscopy as well as confocal laser microscopy have been used to characterize the Rhodamine fluorescence emission. A highly interesting question concerns the interaction between an emitter close to a silicon surface because mechanisms such as energy transfer and fluorescence quenching will occur which are still not fully understood. Since the oxide thickness can be varied during preparation continuously from 1 to ～ 5 nm, it is possible to investigate the fluorescence of the bound dye in close proximity to the underlying silicon. Using confocal laser microscopy we were also able to obtain optical spectra from the bound molecules. Together with the results from an analysis of their photochemical bleaching behaviour, we conjecture that some of the Rhodamine 6G molecules on the structure are interacting with the oxide, causing a spectral shift and differences in their photochemical properties.     

Estimation of oxide related electron trap energy of porous silicon nanostructures

Estimation of electron trap energy (E_t), with respect to bulk Si valence band, of oxidized porous silicon (PS) nanostructures is reported. Photoluminescence (PL) spectra of oxidized PS prepared with different formation parameters have been investigated and the room temperature PL characteristics have been successfully explained on the basis of oxide related trap assisted transitions. PL peak energy for the oxidized samples with low porosity exhibited a blue shift with increasing formation current density (J). For the high porosity samples double peaks appeared in the PL spectra. One of these peaks remained constant at ∼730 nm while the other was blue shifted with increase in J. Evolution of PS nanostructure was correlated to the formation parameters using a simple growth mechanism. PS nanostructure was modelled as an array of regular hexagonal pores and the average value of E_t was estimated to be 1.67 eV.     

Light-trapping design of graphene transparent electrodes for efficient thin-film silicon solar cells

In this paper, the performance of solar cells with graphene transparent electrodes is compared with cells using conventional indium tin oxide (ITO) electrodes, and it is demonstrated the optical absorption of solar cells with bare graphene structure is worse than that of bare ITO structure because of the higher refractive index of graphene. To enhance the light trapping of graphene-based thin-film solar cells, a simple two-layer SiO₂/SiC structure is proposed as antireflection coatings deposited on top of graphene transparent electrodes, and the thickness of each layer is optimized by differential evolution in order to enhance the optical absorption of a-Si:H thin-film solar cells to the greatest degree. The optimization results demonstrate the optimal SiO₂/SiC/graphene structure can obtain 37.30% enhancement with respect to bare ITO structure, which has obviously exceeded the light-trapping enhancement of 34.15% for the optimal SiO₂/SiC/ITO structure. Therefore, with the aid of the light-trapping structure, the graphene films are a very promising indium-free transparent electrode substitute for the conventional ITO electrode for use in cost-efficient thin-film silicon solar cells.     

The synthesis of graphene oxide nanostructures for supercapacitors: a simple route

In this work, we report a simple strategy for synthesis of graphene oxide nanostructures with various morphologies including single-, few-layer, and three-dimensional networks. Morphology control is achieved by adding different amounts of Ni²⁺ into a one-step hydrothermal process. The involved growth mechanisms for the morphology control are discussed. A random arrangement of graphene oxide nanosheets is suggested to induce the networks’ formation. Ni²⁺ facilitates the formation of graphene oxide’s preferential face-to-face overlapping structure, and high Ni²⁺ concentrations render adjacent graphene oxide sheets to combine each other tightly to form closely packed, layered structures. Compared with single-, few-layer graphene oxide, the electrode prepared by three-dimensional networks has a mass specific capacitance of 352 F g^?1 at v = 5 mV s^?1, which is much higher than that of recently reported three-dimensional graphene oxide nanostructures (240 F g^?1).     

Effect of seeding on formation of silicon carbide nanostructures from mesoporous silica-carbon nanocomposites

Mesoporous silica-carbon nanocomposites (C-SiO(2)) were synthesized for the fabrication of highly crystalline silicon carbide (SiC) nanoparticles and nanofibers via carbothermal reduction. SiC nuclei were introduced into the mesopores as seeds by infiltration of preceramic precursor polycarbosilane (PCS) prior to the heat treatment of carbothermal reduction. When PCS with a mass percentage of 11-13% was infiltrated into the mesoporous C-SiO(2), SiC nanofibers and nanoparticles were produced at 1450?°C, even in the sample with low carbon content. The major morphology formed from the mesoporous C-SiO(2) nanocomposites without PCS infiltration was nanoparticles, while nanofibers dominated in the products of PCS-infiltrated compositions. The results indicate that the conversion of PCS into SiC nuclei in mesopores prior to carbothermal reduction has facilitated the formation of SiC nanofibers. Therefore infiltration of seeds into mesopores of C-SiO(2) precursors appears to be an effective means of accelerating the reaction and controlling SiC nanostructures.     

Supercapacitors based on pillared graphene nanostructures

We describe the fabrication of highly conductive and large-area three dimensional pillared graphene nanostructure (PGN) films from assembly of vertically aligned CNT pillars on flexible copper foils for applications in electric double layer capacitors (EDLC). The PGN films synthesized via a one-step chemical vapor deposition process on flexible copper foils exhibit high conductivity with sheet resistance as low as 1.6 ohms per square and possessing high mechanical flexibility. Raman spectroscopy indicates the presence of multi walled carbon nanotubes (MWCNT) and their morphology can be controlled by the growth conditions. It was discovered that nitric acid treatment can significantly increase the specific capacitance of the devices. EDLC devices based on PGN electrodes (surface area of 565 m2/g) demonstrate enhanced performance with specific capacitance value as high as 330 F/g extracted from the current density-voltage (CV) measurements and energy density value of 45.8 Wh/kg. The hybrid graphene-CNT nanostructures are attractive for applications including supercapacitors, fuel cells and batteries.