Synthesis of ZnO nanorods and their application in quantum dot sensitized solar cells

ZnO nanorod thin films of different thicknesses and CdS quantum dots have been prepared by chemical method. X-ray diffraction pattern reveals that the CdS quantum dot and ZnO nanorods are of hexagonal structure. Field emission scanning electron microscope images show that the diameter of hexagonal shaped ZnO nanorods ranges from 110 to 200 nm and the length of the nanorod vary from 1.3 to 4.7 μm. CdS quantum dots with average size of 4 nm have been deposited onto ZnO nanorod surface using successive ionic layer adsorption and reaction method and the assembly of CdS quantum dot with ZnO nanorod has been used as photo-electrode in quantum dot sensitized solar cells. The efficiency of the fabricated CdS quantum dot-sensitized ZnO nanorod-based solar cell is 1.10 % and is the best efficiency reported so far for this type of solar cells.     

Solvothermal synthesis and luminescence properties of CdS:Mn nanorods

CdS:Mn nanorods have been produced via a solvothermal approach in the nonaqueous solvent of ethylenediamine. An absolutely dominant single Mn²⁺ emission originating from the d-d (⁴T₁-⁶A₁) transition was obtained in CdS:Mn nanocrystals at room temperature. The effects of varying reaction temperature, molar ratio of S/Cd, and reaction time on the crystallinity and luminescence of CdS:Mn nanocrystals were systematically investigated. 1% Mn²⁺-doped CdS nanorods without any other additives were synthesized at 130°C for 10 h with an S/Cd molar ratio of 2:1. They show a rod-like shape, and their luminescence intensity around 593 nm is almost the strongest of all the nanorod samples investigated. CdS:Mn nanorods promise potential applications in nanoscale electronic and photonic devices.     

Synthesis of hybrid CdS-Au colloidal nanostructures

We explore the growth mechanism of gold nanocrystals onto preformed cadmium sulfide nanorods to form hybrid metal nanocrystal/semiconductor nanorod colloids. By manipulating the growth conditions, it is possible to obtain nanostructures exhibiting Au nanocrystal growth at only one nanorod tip, at both tips, or at multiple locations along the nanorod surface. Under anaerobic conditions, Au growth occurs only at one tip of the nanorods, producing asymmetric structures. In contrast, the presence of oxygen and trace amounts of water during the reaction promotes etching of the nanorod surface, providing additional sites for metal deposition. Three growth stages are observed when Au growth is performed under air: (1) Au nanocrystal formation at both nanorod tips, (2) growth onto defect sites on the nanorod surface, and finally (3) a ripening process in which one nanocrystal tip grows at the expense of the other particles present on the nanorod. Analysis of the hybrid nanostructures by high-resolution TEM shows that there is no preferred orientation between the Au nanocrystal and the CdS nanorod, indicating that growth is nonepitaxial. The optical signatures of the nanocrystals and the nanorods (i.e., the surface plasmon and first exciton transition peaks, respectively) are spectrally distinct, allowing the different stages of the growth process to be easily monitored. The initial CdS nanorods exhibit band gap and trap state emission, both of which are quenched during Au growth.     

Photoluminescence resulting from semiconductor-metal solid solution observed in one-dimensional semiconductor nanostructures

A narrow band photoluminescence (PL) emission peak resulting from CdS-Au solid solution was observed when growing one-dimensional nanostructures of CdS via the vapor-liquid-solid mechanism by using Au as the catalyst. This emission peak was located at 680 nm, a wavelength longer than the near band edge emission of CdS at 520 nm, and was shown not to be caused by the usual trap states of CdS which lead to a broad band emission. Here, the one-dimensional nanostructures of CdS were grown in a simple, low-temperature (360 degrees C) metal-organic chemical vapor deposition process with a single source precursor of CdS. Straight nanowires of diameter 50-70 nm and wormlike nanorods of diameter 100-200 nm were obtained. Both the upper and lower portions of the nanorods/nanowires possessed single crystallinity as judged from the corresponding high-resolution transmission electron microscopy images and selected area electron diffraction data. This work demonstrates the feasibility of adjusting PL emission peaks of optoelectronic semiconductors through alloying with metals.     

CdS量子点敏化ZnO纳米棒阵列电极的制备和光电化学性能

采用连续式离子层吸附与反应法制备了CdS量子点敏化的ZnO纳米棒电极.应用扫描电子显微镜(SEM)、X射线衍射(XRD)和透射电子显微镜(TEM)对CdS量子点/ZnO纳米棒电极的形貌、晶型和颗粒尺寸进行了分析和表征;采用光电流-电位曲线和光电流谱研究了不同CdS循环沉积次数及不同沉积浓度对复合电极的光电性能影响.结果表明,前驱体浓度都为0.1mol·L-1且沉积15次敏化后的ZnO纳米棒阵列电极光电性能最好.与单纯的ZnO纳米棒阵列电极和单纯的CdS量子点电极相比,其光电转换效率显著提高,单色光光子-电流转换效率(IPCE)在380nm处达到76%.这是因为CdS量子点可以拓宽光的吸收到可见光区,并且在所形成的界面上光生载流子更容易分离.荧光光谱实验进一步说明了光电增强的原因是,两者间形成的界面中表面态大大减少,有利于减少光生电子和空穴的复合.     

CdS nanocrystallites sensitized ZnO nanorods with plasmon enhanced photoelectrochemical performance

A novel architecture of CdS/ZnO nanorods with plasmonic silver (Ag) nanoparticles deposited at the interface of ZnO nanorods and CdS nanocrystallites, was designed as a photoanode for solar hydrogen generation, with photocurrent density achieving 4.7 mA/cm² at 1.6 V (vs. RHE), which is 8 and 1.7 times as high as those of pure ZnO and CdS/ZnO nanorod films, respectively. Additionally, with optical absorption onset extended to ～660 nm, CdS/Ag/ZnO nanorod film exhibits significantly increased incident photo-to-current efficiency (IPCE) in the whole optical absorption region, reaching 23.1% and 9.8% at 400 nm and 500 nm, respectively. The PEC enhancement can be attributed to the one-dimensional ZnO nanorod structure maintained for superior charge transfer, and the extended visible-light absorption of CdS nanocrystallites. Moreover, the incorporated plasmonic Ag nanoparticles could further promote the interfacial charge carrier transfer process and enhance the optical absorption ability, due to its excellent plasmon resonance effect.     

CdS nanocrystallites sensitized ZnO nanorods with plasmon enhanced photoelectrochemical performance

A sandwiched structure of CdS/Ag/ZnO nanorod photoanode exhibits greatly enhanced photoelectrochemical activity for solar hydrogen generation, due to synergistic effect of CdS nanocrystallites and plasmonic Ag nanoparticles for the enhanced optical absorption and the promoted charge carrier separation.     

Multicolor luminescence patterning by photoactivation of semiconductor nanoparticle films

Indiscriminate adsorption of nanoparticles (NPs) significantly complicates the preparation of mesoscale NP patterns considered as enabling technology for many devices and processes. Instead of selected chemical functionalization of the substrate surface prior to the assembly of nanocolloids, the required optical properties - in our case, high quantum yield luminescence - are imparted to the layer-by-layer assembled films by spatially selected photoactivation. The films are made by sequential adsorption of a positively charged polyelectrolyte and a negatively charged CdSe/CdS aqueous dispersion with an initial quantum yield of 0.5-2%. The photoactivation process takes place in the presence of oxygen and may be accompanied by photoetching. A 50-500-fold increase in the luminescence intensity of CdSe/CdS citrate-stabilized particles (quantum yield 25-45%) after visible light illumination provides excellent pattern contrast. Micron scale luminescence patterns were produced from NPs of various CdSe core diameters with red, yellow, and green emission. It was also demonstrated that different emission colors such as orange and green can be combined in one image by taking advantage of spatially selective photoetching. The presented optical patterning technique significantly simplifies the preparation of luminescence patterns as compared to conventional methods. The high signal-to-noise ratio associated with it is essential for optical devices, information processing, and biophotonics. The most immediate use of this approach is expected in cryptography and cell monitoring.     

A Single‐Step Reaction for Silicon and Germanium Nanorods

A single‐step reaction has been developed for colloidal quantum‐size silicon (Si) and germanium (Ge) nanorods. The nanorods are formed by solution–liquid–solid (SLS) growth from tin (Sn) seed particles prepared by in situ reduction of a molecular tin(II) complex by trisilane, the reactant for Si nanorod growth. Using the same procedure, Ge nanorods can be grown by including a diphenyl germane reactant. The nanorod length could be adjusted from several nanometers to more than a micrometer without significant increase of diameter by manipulating reactant concentrations.     

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.     

CdS量子点的制备及细胞膜初步荧光标记

以巯基乙酸为稳定剂,通过控制反应温度、反应时间及pH值,在水相中合成了稳定的受激发出紫光、蓝光、绿光、黄光和红光的CdS量子点;通过紫外可见吸收光谱、荧光光谱和X射线衍射谱(XRD)对产物的光学性能和晶体结构进行了表征,结果表明所合成的CdS量子点分散性较好,量子产率为8%,为立方晶型,粒径约1 nm;利用荧光倒置显微镜观察了量子点在洋葱内表皮细胞膜上聚集及受激发射荧光行为,实现细胞膜初步标记.     

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.     

Functionalized europium nanorods for in vitro imaging

Emissive europium hydroxide nanorods (ENR) (20 nm x 500 nm) functionalized by a surface coating of chromophore-containing organically modified silicate (ORMOSIL) layer, have been synthesized and characterized by high-resolution transmission electron microscopy (TEM). Low-temperature photophysical characterization of the functionalized nanorods (FENR) demonstrated a strong red 5D0 luminescence both in solid and in suspended solutions. Potentials of this nanorod material for live cell imaging have also been explored. Both the bare and functionalized nanorods are able to enter living human cells with no discernible cytotoxicity. Chromophore-to-Eu3+ energy-transfer in the functionalized nanorods enables staining of the cytoplasm of living human cells. This is confirmed by costaining with fluorescent dextran. The red chromophore-sensitized luminescence from the internalized nanorods in live human lung carcinoma cells (A549) can be observed by confocal microscopy 2 h after loading and reaches maximal emission after 24 h.     

Fabrication and photoluminescent properties of heteroepitaxial ZnO/Zn0.8Mg0.2O coaxial nanorod heterostructures

ZnO/Zn0.8Mg0.2O coaxial nanorod heterostructures were prepared by employing catalyst-free metal-organic vapor-phase epitaxy, and their structural and photoluminescent (PL) properties were investigated using transmission electron microscopy (TEM) and temperature-dependent PL spectroscopy. TEM images show that ZnO/Zn0.8Mg0.2O layers were epitaxially grown on the entire surfaces of the ZnO nanorods and the ZnO nanorod diameters as a core material were as small as 9 +/- 2 nm. A dominant PL peak was observed at 3.316 eV, from room-temperature PL spectra of ZnO/Zn0.8Mg0.2O coaxial nanorod heterostructures with ZnO core diameters of 9 nm, indicating a PL blue shift of 30 meV, which resulted from a quantum confinement effect along the radial direction in ZnO nanorods. Furthermore, temperature-dependent PL properties of the coaxial nanorod heterostructures were investigated, showing much higher PL intensity for the coaxial nanorod heterostructures than that of bare ZnO nanorods at room temperature. The origin of the enhanced PL intensity and reduced thermal quenching for the coaxial nanorod heterostructures is also discussed.     

Chemical bath deposition of CdS quantum dots on vertically aligned ZnO nanorods for quantum dots-sensitized solar cells

Formation of CdS quantum dots (Q dots) on the vertically aligned ZnO nanorods electrode was carried out by chemical bath deposition. The diameter and thickness of ZnO nanorods are ～100–150 nm and ～1.6 μm, respectively, and CdS Q dots on ZnO nanorods have a diameter of smaller than 15 nm. In application of the Q dots-sensitized solar cells, composite film exhibited a power conversion efficiency of 0.54% under air mass 1.5 condition (80 mW/cm²), and incident-photon-to-current conversion efficiency showed 18.6%.     

化学溶液沉积法制备单分散氧化锌纳米棒阵列

在由溶胶凝胶法制备的纳米ZnO薄膜基底上, 采用化学溶液沉积法制备了单分散、高度取向的ZnO纳米棒阵列膜. 通过控制纳米ZnO薄膜的制备工艺, 可以调节氧化锌纳米棒的直径. 利用FESEM, TEM, HRTEM, SAED和XRD表征了氧化锌纳米棒阵列的形貌和晶体结构. ZnO纳米棒的室温PL谱具有很高的紫外带边发射峰, 在可见光波段无发射峰, 表明该方法制备的ZnO纳米棒晶体结构完整, 晶体中O空位的浓度很低.     

手性模板合成CdS纳米棒

由于纳米材料具有量子尺寸效应及大的比表面积等性质而使其在电子学[1]、光学[2]、催化[3]和陶瓷[4]等领域显示出诱人的应用前景. 近年来纳米材料的制备及纳米技术发展迅速, 特别是具有特殊光电活性的新型无机纳米材料的制备已引起人们的普遍关注. 现在合成纳米材料的方法主要包括反相胶束法[5]、 LB膜法[6]、嵌段共聚物法[7]和模板合成法[8]. 其中模板合成技术不仅可以通过设计新型的模板分子, 还可通过模板分子的不同自组装行为来调控纳米材料的尺寸和形貌. Stupp等[9]曾利用溶致液晶的六方中间相作为模板, 在其纳米孔隙中成功地合成了具有六方排列超晶格纳米结构的材料. 本文以双亲性丙氨酸衍生物为模板, 在不同的化学微环境下合成了结构不同的CdS纳米棒.     

The synthesis, structure, optical and photocatalytic properties of silica-coated cadmium sulfide nanocomposites of different shapes

The CdS nanostructure undergoes photochemical dissolution, and hence, the photocatalytic activity deteriorates with light irradiation time. A thin layer of silica coating over CdS surface may prevent the photocorrosion and coalescence of quantum size CdS particles. Hence, we synthesized SiO(2)@CdS nanocomposites of different shapes and characterized them by XRD, HRTEM, EDX, SAED, BET surface area measurement and absorption and emission study. The dispersion of spherical CdS (Cd-2.62 at% and S-2.33 at%) nanoparticles of cubic crystal structure into thick amorphous SiO(2) (43.79 at%) matrix is demonstrated here. The fabrication of core (CdS)-shell (SiO(2)) structure (SiO(2)@CdS) consisting of CdS nanorod (Cd-19.79 at% and S-22.90 at%) core (length ~126 nm and width ~6 nm) having characteristic lattice fringes of hexagonal crystals and thin SiO(2) (12.81 at%) shell (thickness=1-1.4 nm) is successfully achieved for the first time. The surface area (21.2m(2)/g) of CdS nanorod (aspect ratio=21) is found to increase (42.3m(2)/g) after SiO(2) coating. The photoluminescence of CdS nanosphere (485 nm) and nanorod (501 nm) is highly quenched after SiO(2) layer formation. The superior photocatalytic activity of SiO(2)@CdS composites for the benzaldehyde oxidation under UV irradiation has been displayed.     

Surface-tunable photoluminescence from block copolymer-stabilized cadmium sulfide quantum dots

The static and time-resolved photoluminescence properties of polystyrene-b-poly(acrylic acid) (PS-b-PAA)-stabilized cadmium sulfide quantum dots (CdS QDs) have been characterized for the first time, demonstrating tunable emission spectra and quantum yields via different chemical treatments of the PAA layer. Samples with the PAA layer in its cadmium carboxylate form showed more-intense band-edge emission and relatively high quantum yields compared with samples in which the PAA layer was in its acid form. This activation effect is explained in terms of passivation of trap sites on the QD surface by specific interactions between the QD and the cadmium-neutralized PAA layer. Lifetimes of band-edge and trap state emission for the various samples ranged from 40 to 61 ns and 244 to 360 ns, respectively. Impressive long-term stability was also shown for a sample of cadmium-neutralized PS-b-PAA-stabilized QDs dispersed in toluene, which maintained 90% of its photoluminescence over 57 days aging under ambient conditions. It is also shown that Cd2+ activation of photoluminescence does not occur when Mg2+ ions are added to similar QD solutions, indicating potential of these block copolymer-stabilized QDs as Cd2+-selective sensors. Irrespective of chemical treatment of the PAA layer, the external PS brush layer effectively stabilized all samples in various organic solvents, resulting in clear CdS colloids with no observed precipitation over several months. Dynamic light scattering and gel permeation chromatography revealed differences in the aggregation numbers and hydrodynamic radii of colloidal QDs for different treatments of the PAA layer, attributed to the lower solubility of the poly(cadmium acrylate) blocks compared to the PAA blocks in the acid form. Finally, it was demonstrated that the PS-b-PAA-stabilized QDs could be well dispersed in PS homopolymer, producing optically transparent photoluminescent films which retained the emission features of the colloidal QDs. Stable and surface-tunable optical properties via the PAA layer and polymer solubility and processability via the PS layer make these PS-b-PAA-stabilized CdS QDs exciting "building blocks" for the bottom-up assembly of functional hierarchical materials for photonics, sensors, and bio-labeling applications.     

荧光磁性双功能树状分子微球的制备与表征

采用化学共沉淀法, 以FeCl₃·6H₂O和FeSO₄·7H₂O为原料制备了磁性Fe₃O₄纳米颗粒, 采用树状大分子对其进行修饰, 然后通过树状大分子具有的大量空腔及末端丰富的氨基, 经吸附、 键合, 与大量巯基乙酸修饰的CdSe/CdS量子点连接, 得到三代具有荧光磁性双功能的树状分子微球, 并对其进行结构表征与性能测试. 结果表明: 三代复合后的微球的平均粒径分别为15, 34和49 nm; 一代荧光磁性微球的发光性能最佳, 其量子产率达24.1%; 零代荧光磁性微球磁性能最优, 其饱和磁化强度为15.96 A·m²/kg. 这种具有荧光和磁性的双功能纳米复合微粒有望在免疫检测、 靶向治疗、 荧光追踪和磁性分离等方面得到广泛应用.