Formation of arrays of gallium nitride nanorods within mesoporous silica SBA-15

We report the first formation of arrays of GaN nanorods inside the nanoscale channels of mesoporous silica SBA-15. GaCl3 dissolved in toluene was incorporated into the methyl group-functionalized SBA-15 powder. The pore surfaces functionalized with methyl groups should facilitate the impregnation with GaCl3. Formation of GaN nanorod arrays within SBA-15 was carried out by heating the powder to 700 degrees C for 3 h under nitrogen atmosphere, followed by ammonolysis at 900 degrees C for 5 h. epsilon-Ga2O3, an unusual phase for Ga2O3, formed after the first thermal process and was converted into wurtzite GaN during ammonolysis. The final products have been characterized by FT-IR spectra, powder XRD patterns, TEM images and SAED patterns, EDS analysis, and nitrogen adsorption-desorption isotherm measurements to confirm the presence of GaN nanostructures. The nanorods are 6-7.5 nm in diameter, and can be a few hundreds of a nanometer in length to exhibit nanowire structure. Free-standing GaN nanorod arrays were revealed upon removal of the silica framework with HF solution. Optical characterization of the isolated GaN nanorod arrays shows a strong and sharp near band-edge emission at 375 nm, and two phonon-assisted donor-acceptor peaks at 395 and 415 nm. A broad but weak emission in the region of 335-360 nm due to the quantum confinement effect of short nanorods was observed.     

Patterned growth of ZnO nanorod arrays on a large-area stainless steel grid

Large-area ZnO nanorod arrays have been synthesized successfully on a stainless steel grid at a mild growth temperature of around 400 degrees C. The as-grown ZnO nanorods have uniform diameters of about 30-50 nm with approximately 5 nm tips. Patterned growth can be realized by engineering the shape of the grid in the growth. Photoluminescence demonstrates a sharp strong UV peak and a broad green band. The growth method provides a promising way of producing nanorod arrays with good controllability in patterns and morphologies, which will be critical in potential application such as high-efficiency filtering and catalysts.     

Growth and Characterization of [001] ZnO Nanorod Array on ITO Substrate with Electric Field Assisted Nucleation

This paper reports direct growth of [001] ZnO nanorod arrays on ITO substrate from aqueous solution with electric field assisted nucleation, followed with thermal annealing. X-ray diffraction analyses revealed that nanorods have wurtzite crystal structure. The diameter of ZnO nanorods was 60–300 nm and the length was up to 2.5 μm depending on the growth condition. Photoluminescence spectra showed a broad emission band spreading from 500 to 870 nm, which suggests that ZnO nanorods have a high density of oxygen interstitials. Low and nonlinear electrical conductivity of ZnO nanorod array was observed, which was ascribed to non-ohmic contact between top electrode and ZnO nanorods and the low concentration of oxygen vacancies.     

Strategic synthesis of SBA-15 nanorods

A simple synthesis of homogeneously sized, ordered mesoporous silica nanorods (SBA-15), spanning about 10 porous channels in width and ranging from 300 to 600 nm in length is reported.     

Low-temperature growth of ZnO nanorods by chemical bath deposition

Aligned ZnO nanorod arrays were synthesized using a chemical bath deposition method at normal atmospheric pressure without any metal catalyst. A simple two-step process was developed for growing ZnO nanorods on a PET substrate at 90-95 degrees C. The ZnO seed precursor was prepared by a sol-gel reaction. ZnO nanorod arrays were fabricated on ZnO-seed-coated substrate. The ZnO seeds were indispensable for the aligned growth of ZnO nanorods. The ZnO nanorods had a length of 400-500 nm and a diameter of 25-50 nm. HR-TEM and XRD analysis confirmed that the ZnO nanorod is a single crystal with a wurtzite structure and its growth direction is [0001] (the c-axis). Photoluminescence measurements of ZnO nanorods revealed an intense ultraviolet peak at 378.3 nm (3.27 eV) at room temperature.     

Preparation and Photoluminescence of ZnO Comb-Like Structure and Nanorod Arrays

A large quantity of Zinc oxide (ZnO) comb-like structure and high-density well-aligned ZnO nanorod arrays were prepared on silicon substrate via thermal evaporation process without any catalyst. The morphology, growth mechanism, and optical properties of the both structures were investigated using XRD, SEM, TEM and PL. The resulting comb-teeth, with a diameter about 20 nm, growing along the 0001 direction have a well-defined epitaxial relationship with the comb ribbon. The ZnO nanorod arrays have a diameter about 200 nm and length up to several micrometers growing approximately vertical to the Si substrate. A ZnO film was obtained before the nanorods growth. A growth model is proposed for interpreting the growth mechanism of comb-like zigzag-notch nanostructure. Room temperature photoluminescence measurements under excitation wavelength of 325 nm showed that the ZnO comb-like nanostructure has a weak UV emission at around 384 nm and a strong green emission around 491 nm, which correspond to a near band-edge transition and the singly ionized oxygen vacancy, respectively. In contrast, a strong and sharp UV peak and a weak green peak was obtained from the ZnO nanorod arrays.     

Precise placement of gold nanorods by capillary assembly

Capillary assembly was explored for the precise placement of 25 nm × 70 nm colloidal gold nanorods on prestructured poly(dimethylsiloxane) template surfaces. The concentration of nanorods and cationic surfactant cetyltrimethylammonium bromide (CTAB), the template wettability, and most critically the convective transport of the dispersed nanorods were tuned to study their effect on the resulting assembly yield. It is shown that gold nanorods can be placed into arrayed 120-nm diameter holes, achieving assembly yields as high as 95% when the local concentration of nanorods at the receding contact line is sufficiently high. Regular arrays of gold nanorods have several benefits over randomly deposited nanorod arrangements. Each assembled nanorod resides at a precisely defined location and can easily be found for subsequent characterization or direct utilization in a device. The former is illustrated by collecting scattering spectra from single nanorods and nanorod dimers, followed by subsequent SEM characterization without the need for intricate registration schemes.     

高度有序氧化钨纳米棒的制备和表征

采用直流磁控溅射法结合阳极氧化法在铝基纳米点阵上制备氧化钨(WO3)纳米棒. 运用原子力学显微镜(AFM), 电子扫描显微镜(SEM), X射线衍射仪(XRD), 电化学工作站(EW)和紫外-可见分光光度计(UV)观察表征了WO3纳米棒的表面形貌、结构、光学性能和电致变色性能. 结果表明: 在溅射过程中, 溅射粒子优先沉积于铝基纳米点阵的凸点上, 然后成核并形成棒状; WO3纳米棒的直径约为200 nm, 与铝基纳米点阵的直径一致, 拥有一定的电致变色性能.     

ZnO纳米棒阵列在TiO2介孔薄膜上的生长及其表征

通过低温水热法成功地将ZnO纳米棒阵列定向生长在了介孔锐钛矿TiO2纳米晶薄膜上,并主要利用X射线衍射、场发射扫描电子显微镜和光致发光光谱等对其进行了表征。所制备的纳米棒具有六边形的端面,纳米棒的尺寸及端面边长分布范围窄,并且沿c轴方向(002)表现出了明显的择优化生长。此外,相比于玻璃基底或TiO2纳米颗粒薄膜,生长在介孔TiO2薄膜上的ZnO纳米棒阵列表现出了较好的取向生长,表明基底的表面结构和组成对ZnO纳米棒阵列的生长有显著的影响。根据基底有序的多孔结构,讨论了纳米棒阵列可能的生长机理。所得到的ZnO纳米棒阵列在室温下分别表现出了以370 nm为中心的强近紫外光和以530 nm为中心的弱绿光两条荧光谱带。     

Self-assembly of a metallosupramolecular coordination polyelectrolyte in the pores of SBA-15 and MCM-41 silica

It is shown that intrinsically stiff chain aggregates of a metallosupramolecular coordination polyelectrolyte (MEPE) can form in the cylindrical nanopores of MCM-41 and SBA-15 silica by self-assembly of its constituents (metal ions and organic ligand). The UV/vis spectra of the resulting MEPE-silica composites exhibit the characteristic metal-to-ligand charge transfer band of the MEPE complex in solution. For the MEPE-silica composite in SBA-15 an iron content of 1.2 wt % was found, corresponding to ca. 10 MEPE chains disposed side by side in the 8 nm wide pores of the SBA-15 matrix. In the case of MCM-41 (pore width < 3 nm), where only one MEPE chain per pore can be accommodated, an iron content of 0.3 wt % was obtained, corresponding to half-filling of the pores. It was also found that MEPE chains spontaneously enter the pores of SBA-15, when a solution of MEPE is exposed to the silica matrix.     

Biofunctional ZnO nanorod arrays grown on flexible substrates

A square pattern of thioctic acid self-assembled ZnO nanorod arrays was grown on a large 4-in. thermoplastic polyurethane (TPU) flexible substrate via an in situ soluthermal process at low temperature (348 K). With the addition of dimercaptosuccinic acid (DMSA), the surface chemistry forms a disordered ZnO phase, and the morphology of the ZnO-DMSA nanorods changes with various DMSA addition times. As evidenced by the Zn2p3/2, C1s, O1s, S2p, and N-1s scans of X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD), DMSA and proteins were conjugated on the single crystalline ZnO nanorods. The photoluminescence (PL) spectra indicated that the optical properties of ZnO nanorod arrays were changed while the DMSA was inserted, and proteins were conjugated. Furthermore, a control test found that the ZnO nanorods show a significant improvement in sensitive characterization over the ZnO film. As another proteins (e.g., human serum albumin, HSA) were bound onto the ZnO-bovine serum albumin (BSA) nanorod arrays, an enhanced ultraviolet emission intensity was detected. On the basis of these results, one might be expected to conjugate specific biomolecules on the biofunctional ZnO nanorod arrays to detect the complementary biomolecules by PL detecting.     

Synthesis of mesoporous carbons using ordered and disordered mesoporous silica templates and polyacrylonitrile as carbon precursor

Mesoporous carbons were synthesized from polyacrylonitrile (PAN) using ordered and disordered mesoporous silica templates and were characterized using transmission electron microscopy (TEM), powder X-ray diffraction, nitrogen adsorption, and thermogravimetry. The pores of the silica templates were infiltrated with carbon precursor (PAN) via polymerization of acrylonitrile from initiation sites chemically bonded to the silica surface. This polymerization method is expected to allow for a uniform filling of the template with PAN and to minimize the introduction of nontemplated PAN, thus mitigating the formation of nontemplated carbon. PAN was stabilized by heating to 573 K under air and carbonized under N2 at 1073 K. The resulting carbons exhibited high total pore volumes (1.5-1.8 cm3 g(-1)), with a primary contribution of the mesopore volume and with relatively low microporosity. The carbons synthesized using mesoporous templates with a 2-dimensional hexagonal structure (SBA-15 silica) and a face-centered cubic structure (FDU-1 silica) exhibited narrow pore size distributions (PSDs), whereas the carbon synthesized using disordered silica gel template had broader PSD. TEM showed that the SBA-15-templated carbon was composed of arrays of long, straight, or curved nanorods aligned in 2-D hexagonal arrays. The carbon replica of FDU-1 silica appeared to be composed of ordered arrays of spheres. XRD provided evidence of some degree of ordering of graphene sheets in the carbon frameworks. Elemental analysis showed that the carbons contain an appreciable amount of nitrogen. The use of our novel infiltration method and PAN as a carbon precursor allowed us to obtain ordered mesoporous carbons (OMCs) with (i) very high mesopore volume, (ii) low microporosity, (iii) low secondary mesoporosity, (iv) large pore diameter (8-12 nm), and (v) semi-graphitic framework, which represent a desirable combination of features that has not been realized before for OMCs.     

Ordered SBA-15 nanorod arrays inside a porous alumina membrane

The growth of ordered nanorods of mesoporous SBA-15 inside a porous alumina membrane has been achieved for the first time by a simple sol-gel method. The obtained SBA-15 nanorods themselves have ordered hexagonal mesochannels with a size of about 6 nm and have been arranged to form hexagonal arrays by the limitation of pores of the alumina membrane. The synthesized alumina membrane with mesoporous SBA-15 inside combines the advantages of porous alumina membranes and mesoporous SBA-15 and provides fine and vertical mesochannels, which may serve as a new and efficient mold and lead to extensive applications in nanodevice fabrication, biomacromolecule separations, etc.     

Plasmon coupling in nanorod assemblies: optical absorption, discrete dipole approximation simulation, and exciton-coupling model

The shape anisotropy of nanorods gives rise to two distinct orientational modes by which nanorods can be assembled, i.e., end-to-end and side-by-side, analogous to the well-known H and J aggregation in organic chromophores. Optical absorption spectra of gold nanorods have earlier been observed to show a red-shift of the longitudinal plasmon band for the end-to-end linkage of nanorods, resulting from the plasmon coupling between neighboring nanoparticles, similar to the assembly of gold nanospheres. We observe, however, that side-by-side linkage of nanorods in solution shows a blue-shift of the longitudinal plasmon band and a red-shift of the transverse plasmon band. Optical spectra calculated using the discrete dipole approximation method were used to simulate plasmon coupling in assembled nanorod dimers. The longitudinal plasmon band is found to shift to lower energies for end-to-end assembly, but a shift to higher energies is found for the side-by-side orientation, in agreement with the optical absorption experiments. The strength of plasmon coupling was seen to increase with decreasing internanorod distance and an increase in the number of interacting nanorods. For both side-by-side and end-to-end assemblies, the strength of the longitudinal plasmon coupling increases with increasing nanorod aspect ratio as a result of the increasing dipole moment of the longitudinal plasmon. For both the side-by-side and end-to-end orientation, the simulation of a dimer of nanorods having dissimilar aspect ratios showed a longitudinal plasmon resonance with both a blue-shifted and a red-shifted component, as a result of symmetry breaking. A similar result is observed for a pair of similar aspect ratio nanorods assembled in a nonparallel orientation. The internanorod plasmon coupling scheme concluded from the experimental results and simulations is found to be qualitatively consistent with the molecular exciton coupling theory, which has been used to describe the optical spectra of H and J aggregates of organic molecules. The coupled nanorod plasmons are also suggested to be electromagnetic analogues of molecular orbitals. Investigation of the plasmon coupling in assembled nanorods is important for the characterization of optical excitations and plasmon propagation in these nanostructures. The surface plasmon resonance shift resulting from nanorod assembly also offers a promising alternative for analyte-sensing assays.     

Controllable synthesis of ZnO nanorod and prism arrays in a large area

ZnO nanorod and nanoprism arrays have been directly synthesized on a large-area zinc substrate via a convenient solution method. The products were characterized with XRD, SEM, HRTEM, and photoluminescence (PL) spectroscopy. The influence of the solvent and the concentration of NaOH on the size and shapes of the as-prepared ZnO samples have been studied. It was found that ZnO nanorod or nanowire arrays were fabricated in alcohol, whereas ZnO nanoprisms with pyramid tips were produced in an alcohol-water mixture. The diameters of the nanorods or nanoprisms became thicker when a higher concentration of NaOH was used. Room-temperature PL spectra of the ZnO products showed a UV emission and a broad green band. The mechanism of the nanorods and nanoprisms in two systems is briefly discussed.     

Enhancement at the junction of silver nanorods

The enhancement of surface enhanced Raman scattering (SERS) at the junction of linearly joined silver nanorods (31 nm in diameter) deposited in the pores of anodic aluminum oxide templates was studied systematically by excitation with a 632.8 nm laser line. The single and joined silver nanorod arrays showed a similar extinction spectrum when their length was the same. Maximum enhancement was observed from the junction system of two nanorods of the same size with a total length of 62 nm. This length also corresponded to the optimum length of single nanorods for SERS by excitation with a 632.8 nm laser line. The enhancement at the junction was approximately 40 times higher than that of the 31 nm single nanorod, while it was 4 times higher than that of the 62 nm single nanorod. The enhancement factor at the junction after oxide removal was approximately 3.9 x 10 (9).     

Formation of titanium nitride nanoparticles within mesoporous silica SBA-15

We report the first synthesis of titanium nitride (TiN) nanoparticles inside the nanoscale channels of mesoporous silica SBA-15. The TiN precursor, Ti(NMe(2))(4) in toluene, was incorporated into the methyl group-modified channels of the SBA-15 powder. The functionalization of pore surfaces with methyl groups generates hydrophobic surfaces that facilitate impregnation with Ti(NMe(2))(4) and minimizes reactions between the TiN precursor and the hydroxyl groups on the surface of SBA-15. Formation of TiN nanoparticles inside the mesoporous channels of SBA-15 was carried out by subsequent ammonolysis at high temperatures (700-750 degrees C). The final products have been characterized by TEM and EELS images, powder XRD patterns, FTIR spectra, UV-vis absorption spectra, and nitrogen adsorption isotherm measurements to confirm the presence and distribution of TiN nanoparticles in the SBA-15 samples.     

A family of ordered mesoporous carbons derived from mesophase pitch using ordered mesoporous silicas as templates

A variety of ordered mesoporous carbons (OMCs) were synthesized using ordered mesoporous silicas (OMSs) as hard templates and the mesophase pitch (MP) as a carbon precursor. The synthesis included the mixing of OMS with MP, the infiltration of OMS with MP at 450–550?°C and the carbonization of MP in OMS/MP composite followed by the dissolution of the OMS template. OMCs with structures of two-dimensional hexagonal arrays of nanorods and three-dimensional arrays of nanospheres were obtained through the replication of silica templates, including large-pore SBA-15, KIT-6, large-pore FDU-12 and SBA-16. In particular, 2-D hexagonal array of carbon nanorods (CMK-3 carbon) with (100) interplanar spacing of ～13 nm as well as an array of carbon nanospheres arranged in the face-centered cubic structure with the unit-cell parameter of 33 nm were successfully prepared. The specific surface areas of the resulting carbons were up to 400 m²/g, and the total pore volumes were up to 0.43 cm³/g, with the highest values achieved when the MP infiltration temperature was 500?°C. The OMCs exhibited narrow mesopore size distributions. As inferred from XRD, the frameworks of OMCs featured semi-graphitic structures even though moderate carbonization temperature (850?°C) was employed.     

One-pot hydrothermal synthesis of heterostructured ZnO/ZnS nanorod arrays with high ethanol-sensing properties

ZnO/ZnS heterostructured nanorod arrays with uniform diameter and length were synthesized from zinc substrates in a one-pot procedure by using a simple hydrothermal method. Structural characterization by HRTEM indicated that the heterostructured nanorods were composed of parallel segments of wurtzite-type ZnO and zinc-blende ZnS, with a distinct interface along the axial direction, which revealed the epitaxial relationship, ZnO (1010) and ZnS (111). The as-prepared ZnO/ZnS nanorods showed only two green emissions at around 523?nm and 576?nm. We also found that the nanorods exhibited high sensitivity to ethanol at relatively low temperatures, owing to their smaller size and structure.     

Mechanism for the formation of tin oxide nanoparticles and nanowires inside the mesopores of SBA-15

The formation of polycrystalline tin oxide nanoparticles (NP) and nanowires was investigated using nanocasting approach included solid-liquid strategy for insertion of SnCl₂ precursor and SBA-15 silica as a hard template. HR-TEM and XRD revealed that during the thermal treatment in air 5 nm tin oxide NP with well defined Cassiterite structure were formed inside the SBA-15 matrix mesopores at 250 °C. After air calcination at 700 °C the NP assembled inside the SBA-15 mesopores as polycrystalline nanorods with different orientation of atomic layers in jointed nanocrystals. It was found that the structure silanols of silica matrix play a vital role in creating the tin oxide NP at low temperature. The pure tin chloride heated in air at 250 °C did not react with oxygen to yield tin oxide. Tin oxide NP were also formed during the thermal treatment of the tin chloride loaded SBA-15 in helium atmosphere at 250 °C. Hence, it is well evident that silanols present in the silica matrix not only increase the wetting of tin chloride over the surface of SBA-15 favoring its penetration to the matrix pores, but also react with hydrated tin chloride according to the proposed scheme to give tin oxide inside the mesopores. It was confirmed by XRD, N₂-adsorption, TGA-DSC and FTIR spectra. This phenomenon was further corroborated by detecting the inhibition of SnO₂ NP formation at 250 °C after inserting the tin precursor to SBA-15 with reduced silanols concentration partially grafted with tin chloride.