CdSe and CdSe/CdS nanorod solids

We demonstrate the self-organization of CdSe nanorods into nematic, smectic, and crystalline solids. Layered colloidal crystals of CdSe nanorods grow by slow destabilization of a nanocrystal solution upon allowing the diffusion of a nonsolvent into the colloidal solution of nanocrystals. The colloidal crystals of nanorods show characteristic birefringence, which we assign to specific spherulite-like texture of each nanorod assembly. To demonstrate the general character of nanorod self-assembly technique, CdSe/CdS heterostructure nanorods were organized into highly luminescent superlattices.     

Toward highly efficient CdS/CdSe quantum dots-sensitized solar cells incorporating ordered photoanodes on transparent conductive substrates

A series of ordered photoanodic architectures (including ordered TiO(2) nanotube arrays (TNT), ZnO nanorods, ZnO/TiO(2) core/shell nanostructures) for CdS/CdSe sensitized solar cells (QDSCs), were fabricated directly on transparent conductive oxide glasses by a facile sol-gel assisted template process. The morphologies, optical and electrical properties of TNTs and CdS/CdSe co-sensitized TNTs have been demonstrated. The effect of CdSe deposition time on the cell performance was clarified, and the growth mechanism of the CdSe quantum dots on the surface of the TNTs has been proposed as well. Furthermore, the evolution of open-circuit photovoltage (V(oc)) towards CdSe deposition time has been investigated by electrochemical impedance spectroscopy (EIS). A promising light-to-electricity conversion efficiency of up to 4.61% has been achieved with 3 μm long TNT arrays, which is the best record for sandwich-type ordered TNT-based QDSCs.     

氢氧化镍纳米棒的水热制备及其表征

以Ni₂SO₄·6H₂O和NaOH为原料,在水热条件下制备了氢氧化镍纳米棒.运用透射电子显微镜(TEM)和X射线衍射仪(XRD)对样品进行了表征,考察了水热反应温度和pH值对产物的形貌和结构的影响.结果表明,氢氧化镍纳米棒形成的最佳条件是180～200℃,pH为9～10.     

Selective synthesis of Fe7Se8 polyhedra with exposed high-index facets and Fe7Se8 nanorods by a solvothermal process in a binary solution and their collective intrinsic properties

Fe(7)Se(8) polyhedra with high-index facets and Fe(7)Se(8) nanorods can be selectively synthesized by a solvothermal reaction in a mixed solvent of diethylenetriamine (DETA) and deionized water (DIW). It is found that the morphologies of Fe(7)Se(8) nanocrystals can be effectively controlled by adjusting the volume ratio of DETA and DIW. The unusual polyhedral crystals are bounded by two {001} and twelve {012} facets. The intrinsic properties of Fe(7)Se(8) nanocrystals have been investigated. Magnetic measurements indicate that the obtained polyhedra and nanorods show a weak ferromagnetic ordering at room temperature. In particular, a new photoluminescence emission at 403 nm from the Fe(7)Se(8) nanocrystals has been observed. The described solvothermal reaction in a mixed solvent may be extended to the synthesis of other transition-metal chalcogenide crystals with controlled shape, facets, and structure, which may bring new functionalities.     

Synthesis and characterization of colloidal ternary ZnCdSe semiconductor nanorods

For the synthesis of colloidal ternary ZnCdSe nanorods, CdSe nanorods were first prepared under a mixture of tetradecylphosphonic acid/trioctylphosphine oxide surfactants at 250 degrees C, and then ZnSe shell layer was grown onto CdSe nanorods at 180 degrees C, forming CdSeZnSe core/shell nanorods. Green-yellow emitting ternary ZnCdSe nanorods were obtained by a subsequent alloying process at 270 degrees C for 1-3 h through the diffusion of Zn ions into CdSe nanorods. The photoluminescence quantum yield (QY) of ZnCdSe nanorods was 5%-10%, which is higher than that from pristine CdSe nanorods (0.6%). The QY of these alloy nanorods depends on the alloying time and is discussed in terms of compositional disorders and defects produced by the alloying process. The Raman and time resolved photoluminescence spectroscopies were used to understand the detailed alloying process from CdSeZnSe core/shell to ZnCdSe alloy nanorods.     

Architectural control syntheses of CdS and CdSe nanoflowers, branched nanowires, and nanotrees via a solvothermal approach in a mixed solution and their photocatalytic property

Wurtzite CdS and CdSe nanostructures with complex morphologies such as urchin-like CdS nanoflowers, branched nanowires, and fractal nanotrees can be produced via a facile solvothermal approach in a mixed solution made of diethylenetriamine (DETA) and deionized water (DIW). The morphologies of CdS and CdSe nanocrystals can be easily controlled via tuning the volume ratio of DETA and DIW. Urchin-like CdS nanoflowers made of CdS nanorods are in a form of highly ordered hierarchical structures, while the nanowires are branched nanowires, and the fractal CdS nanotrees are a buildup of branched nanopines. The results demonstrated that solvothermal reaction in a mixed amine/water can access a variety of complex morphologies of semiconductor materials. The photocatalytic activity of CdS particles with different morphologies has been tested by the degradation of acid fuchsine under both UV and visible light, showing that the as-prepared branched CdS nanowires exhibit high photocatalytic activity for degradation of acid fuchsine.     

From (Cd2Se2)(pa) (pa=propylamine) hybrid precursors to various CdSe nanostructures: structural evolution and optical properties

Nanostructural evolution of II-VI semiconductors emerges as a hot research field because it offers a novel route for the synthesis of functional semiconductor nanomaterials. Here, we report a "top-down" process of structural evolution from two dimensional Cd(2)Se(2)(pa) hybrid structures to zero- or one- dimensional CdSe nanostructures. We firstly synthesized the Cd(2)Se(2)(pa) hybrid by a facile solvothermal reaction and determined the hybrid crystal structure through the Rietveld refinement based on the PXRD data. The (Cd(2)Se(2))(pa) hybrid consists of [Cd(2)Se(2)] slabs sandwiched by coordinated n-propylamine layers. Then, we used this hybrid as a precursor to explore the "top-down" fabrication process of structural evolution from two dimensional layered structures to zero- or one- dimensional nanocrystals. It has been shown that various CdSe nanostructures including lamellar structures, nanoparticles, nanowires, and nanorods can be obtained through the pyrolysis of (Cd(2)Se(2))(pa) hybrid precursor under different conditions. It is worth mentioning that the oriented attachment of nanoparticles has been observed during the pyrolysis process. Additionally, the variation of optical properties with structural evolution has been investigated in detail.     

TiO_2纳米棒和CdSe纳米棒复合膜与聚3-甲基噻吩杂化太阳能电池研究

采用水热法制备了TiO2和CdSe两种纳米棒材料,将两种纳米材料制备成TiO2/CdSe复合纳米棒膜电极,并在复合膜上电化学聚合生成聚3-甲基噻吩poly(3-methylthiophene)(PMeT),研究了其光电化学性能.实验表明,当TiO2与CdSe的物质的量复合比为2:1,PMeT的聚合时间为40s,在电极电势为-0.2V下ITO/TiO2/CdSe/PMeT电极光电转换效率(IPCE)达到56%,对比ITO/TiO2/CdSe复合膜电极在长波方向的光电转换效率明显提高,光吸收截止波长发生了明显的红移.同时以ITO/TiO2/CdSe/PMeT组装了简易的杂化太阳电池,初步研究了光电池性能,光电池总效率为0.08%,Voc=0.4V,jsc=0.61mA/cm2,ff=0.33.     

Surface-functionalized CdSe nanorods for assembly in diblock copolymer templates

Poly(ethylene oxide)-covered CdSe nanorods were prepared and assembled in diblock copolymer templates by floating the block copolymer templates onto aqueous nanorod solutions. The assembly was enabled by consideration of the surface ligand coverage of the nanorods. Alkane-covered CdSe nanorods prepared by state-of-the-art techniques are not compatible with this assembly process. However, poly(ethylene oxide) (PEO)-functionalized CdSe nanorods were successfully used to assemble the nanorods into the channels and pores of diblock copolymer templates. Other water-dispersible CdSe nanorods, such as those covered with 11-mercaptoundecanoic acid (MUA), did not give the desired assemblies. These results are understood by considering the surface energies of the PEO-covered CdSe nanorods in this interfacial assembly process.     

Synthesis and characterization of PbS nanorods in W/O microemulsion system

PbS nanorods have been successfully synthesized in water-in-oil (W/O) microemulsion containing non-ionic surfactant OP, n-pentanol, cyclohexane, and aqueous solution. The effects of the molar ratio of water to surfactant (ω₀), the concentration of reactants and the ageing time on the morphologies of PbS nanoparticles were investigated. The microstructures, morphologies and properties of the synthesized products were characterized by means of X-ray diffraction, transmission electron microscopy, and ultraviolet-visible (UV-VIS) absorption spectroscopy, respectively. The results showed that the synthesized rod-like products are composed of cubic phase PbS. These nanorods have an average diameter of about 100 nm, and an average length of about 500 nm. In the UV-VIS absorption spectrum, the absorption edge of PbS nanorods exhibit a blue shift compared with that of bulk PbS, indicating the quantum confinement effect of PbS nano-particles     

聚3-氯噻吩修饰CdSe纳米棒复合膜电极光电化学性能研究

采用水热法制备了具有闪锌矿和纤维锌矿结构的CdSe纳米棒. 纳米棒直径约为100 nm, 长度约为300 nm. 当外加电极电势为-0.6 V 时, 经聚3-氯噻吩[Poly(3-chlorothiophene), P3CT]修饰的CdSe纳米棒具有最大光电流, 并且CdSe/P3CT复合膜电极最高光电转换效率(IPCE)为13.5%, 低于CdSe纳米棒膜电极17.7%的最高IPCE. CdSe/P3CT复合膜电极中存在p-n异质结, p-n异质结的存在使得CdSe/P3CT复合膜电极在长波区(>410 nm)的IPCE整体高于CdSe纳米棒薄膜电极的IPCE.     

尺寸可控氢氧化镧纳米棒的水热合成及表征

以硝酸镧为镧源、三乙胺为碱源和络合剂,通过简便的水热法成功合成了大量均一的氢氧化镧纳米棒。详细研究了三乙胺的用量、表面活性剂、反应温度和时间对产物形貌及尺寸的影响。基于实验结果,提出了氢氧化镧纳米棒的形成机理。同时制备了稀土掺杂的氢氧化镧纳米棒。利用X射线衍射（XRD）、透射电子显微镜（TEM）、选区电子衍射（SAED）和高分辨透射电子显微镜（HRTEM）对所得产物的物相、结构和形貌进行了表征分析。     

Isotropic-liquid crystalline phase diagram of a CdSe nanorod solution

We report the isotropic-liquid crystalline phase diagram of 3.0 nm x 60 nm CdSe nanorods dispersed in anhydrous cyclohexane. The coexistence concentrations of both phases are found to be lower and the biphasic region wider than the results predicted by the hard rod model, indicating that the attractive interaction between the nanorods may be important in the formation of the liquid crystalline phase in this system.     

Controlled Synthesis of Se/Te Alloy and Te Nanowires

"Se/Te alloy and Te nanowires (NWs) with different morphologies were synthesized through a novel, control-lable solution-phase method. Sodium dodecylbenzene sulfonate was employed as a surfactant to control the reaction rate in the synthesis. Through reaction process dynamics control, both "bending" and "V-shaped" Se/Te alloy NWs were controllably produced. The phase structures and morphologies of the Se/Te and Te products were investigated with XRD, TEM, and HRTEM. The formation mechanisms of the NWs were investigated on the basis of the experimental results. The significance of these results lies in the important implications concerning the potential use of these NWs materials for nanoscale electronic devices."     

Near‐Infrared‐Emitting CdxHg1−xSe Nanorods Fabricated by Ion Exchange in an Aqueous Medium

Whereas CdSe nanorods that are grown in organic solution have a hexagonal wurtzite structure, which is the limiting case for exchange, HgSe is more commonly encountered as a cubic zinc blende system. An exchange process was performed at room temperature and at atmospheric pressure in an aqueous environment after phase transfer of the original CdSe nanorods, which reinforced the tendency for the endpoint of HgSe to be cubic. Consequently, we observed that under ambient conditions, the exchange process terminated with an average composition of only Cd_0.9Hg_0.1Se. Following the changes during the process by optical spectroscopy and high angle annular dark field (HAADF) scanning transmission electron microscopy (STEM), we observed that the Hg²⁺ ions diffused into the rods to a point limited by the formation of stacking faults due to the different lattice structures of the two limiting cases of zinc blende and wurtzite. HAADF‐STEM and energy dispersive spectroscopy analyses also confirmed that the Hg substitution did not occur uniformly throughout the individual nanorods, as Hg‐poor and Hg‐rich regions coexist around the stacking faults. The formation of near‐infrared‐emitting alloyed Cd_xHg_1?xSe nanorods in an aqueous medium highlights the subtle dependence of the ion‐exchange process on the differences in the crystal structures of the two endpoint lattices.     

草酸钴纳米棒的一步固相化学合成及其表征

在非离子表面活性剂聚乙二醇(PEG)存在的条件下, 利用不同的钴盐分别与草酸进行低热固相化学反应, 一步合成了一系列金属配合物草酸钴纳米棒, 并采用XRD, TEM, SEM等分析手段对其结构和形貌进行了表征. 实验结果表明: 在合适的表面活性剂存在下, 利用钴盐与草酸的固相反应一步即可得到一维草酸钴纳米棒, 钴盐的不同及表面活性剂聚合度的不同均会影响纳米棒的形貌. 表面活性剂PEG在草酸钴纳米棒的形成过程中起到类似软模板的作用, 并诱导产物纳米晶沿某一方向定向生长从而生成纳米棒.     

Structure-directing coordination template effect of ethylenediamine in formations of ZnS and ZnSe nanocrystallites via solvothermal route

ZnS and ZnSe precursors (ZnS x 0.5en and ZnSe x 0.5en, en = ethylenediamine) were prepared via a solvothermal process using ethylenediamine as solvent. Phase-pure hexagonal wurtzite ZnS and ZnSe products were obtained by annealing the precursors in argon stream at temperatures above 350 degrees C. The role of ethylenediamine as a structure-directing coordination molecular template responsible for the morphologies of the annealed products was discussed. This work provided further insights into the solvent coordination molecular template (SCMT) mechanism previously proposed to explain the growth mechanism of CdE (E = S, Se, Te) nanorods in ethylenediamine (Inorg. Chem. 1999, 38, 1382). The as-prepared precursors as well as the annealed products were characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), infrared absorbance spectroscopy (IR), thermogravimetric analysis (TGA), X-ray fluorescence (XRF) analysis, and combustion analysis for C, N, H contents.     

Novel inorganic-organic-layered structures: crystallographic understanding of both phase and morphology formations of one-dimensional CdE (E = S,Se, Te) nanorods in ethylenediamine

A novel class of inorganic-organic-layered structures, CdE.0.5en (E = S, Se, Te; en = ethylenediamine), were obtained through reactions between elemental S, Se, or Te and Cd(2+) at appropriate solvothermal temperatures. These compounds contain atomic sheets of inorganic CdE frameworks spaced by ethylenediamine molecules, which serve as bridged ligands between two Cd atoms in neighboring inorganic layers and also prevent these inorganic slabs from collapsing and condensing into the bulk CdE phase. From the structural viewpoint, the essential mechanism for the formation of CdE nanorods in ethylenediamine-mediated solvothermal synthesis and the unique striated morphologies of the CdE products obtained through post-hydrothermal treatment of the CdE.0.5en layered precursors were revealed. The structure-selective crystallization of II-VI compound semiconductors in ethylenediamine under conditions of direct solvothermal synthesis or during the postconversion of the layered precursors was also explained on the basis of the similarity in atomic connectivity between the inorganic slabs in the precursors and those in wurtzite or zinc-blende phases. In addition, the CdE.0.5en precursors, which possess strong quantum-confinement effects resulting from their special inorganic-organic structures with alternating CdE and ethylenediamine layers, provide further possibilities of tailoring their electronic, magnetic, and optical properties through the structural modification of either the inorganic or the organic components.     

Core-shell nanorods of SnS-C and SnSe-C: synthesis and characterization

The straightforward, efficient, solventless, RAPET (reactions under autogenic pressure at elevated temperature) approach was explored for the fabrication of core-shell nanomaterials. Carbon-encapsulated SnS and SnSe nanorods were synthesized by a one-step thermal decomposition of tetramethyltin in the presence of either S or Se powder in a closed reactor at 700 degrees C for 40 min, under their autogenic pressure in an inert atmosphere. The powder X-ray diffraction measurements provided structural evidence for the formation of pure orthorhombic phases of SnS or SnSe particles. The Raman spectroscopy measurements ensured that the nature of the coated carbon was semigraphitic. The scanning electron micrographs verified the 1D morphology of the formed SnS and SnSe chalcogenides, and their stoichiometry was confirmed by EDAX measurements. The HR-TEM micrographs distinguished between core and shell morphologies. The nitrogen gas adsorption on the surface of core-shell nanostructures was determined by BET surface area analysis. The plausible mechanism for the creation of chalcogenide cores (SnS or SnSe) with a carbon shell was elucidated.