Controlled nucleation and growth of CdS nanoparticles in a polymer matrix

In-situ synchrotron X-ray diffraction (XRD) was used to monitor the thermal decomposition (thermolysis) of Cd thiolates precursors embedded in a polymer matrix and the nucleation of CdS nanoparticles. A thiolate precursor/polymer solid foil was heated to 300 degrees C in the X-ray diffraction setup of beamline W1.1 at Hasylab, and the diffraction curves were each recorded at 10 degrees C. At temperatures above 240 degrees C, the precursor decomposition is complete and CdS nanoparticles grow within the polymer matrix forming a nanocomposite with interesting optical properties. The nanoparticle structural properties (size and crystal structure) depend on the annealing temperature. Transmission electron microscopy (TEM) and photoluminescence (PL) analyses were used to characterize the nanoparticles. A possible mechanism driving the structural transformation of the precursor is inferred from the diffraction features arising at the different temperatures.     

Low-temperature thermolysis behavior of tetramethyl- and tetraethyldistibines

The thermolysis behavior of tetramethyl- and tetraethyldistibine (Sb(2)Me(4) and Sb(2)Et(4)) was investigated using a mass spectrometer coupled to a tubular flow reactor under near-chemical vapor deposition (CVD) conditions. Sb(2)Me(4) undergoes a gas-phase disproportionation with an estimated activation energy of 163 kJ/mol. This reaction leads to the formation of methylstibinidine, SbMe, that reacts on the surface to produce antimony film and SbMe(3). Unfortunately, this clean decomposition pathway is limited to a narrow temperature range of 300-350 degrees C. At temperatures exceeding 400 degrees C, SbMe(3) decomposes following a radical route with a consequent risk of carbon contamination. In contrast, Sb(2)Et(4) disproportionates at the hot wall of the reactor. According to mass-spectrometric data, this reaction is significant starting at a temperature of 100 degrees C, with an apparent activation energy of 104 kJ/mol. Within the temperature range of 100-250 degrees C, the precursor decomposition leads to the formation of antimony films and SbEt(3), whereas different molecular reaction pathways are significantly activated above 250 degrees C. The use of Sb(2)Et(4) lowers the risk of carbon contamination compared to Sb(2)Me(4) at high temperature. Therefore, Sb(2)Et(4) is a promising CVD precursor for the growth of antimony films in the absence of hydrogen atmosphere in a wide temperature range.     

The Effect of a Magnetic Field on a RAPET (Reaction under Autogenic Pressure at Elevated Temperature) of MoO(OMe)(4): Fabrication of MoO(2) Nanoparticles Coated with Carbon or Separated MoO(2) and Carbon Particles

In this article, we present results of the RAPET dissociation of MoO(OMe)4 at 700 degrees C in a closed Swagelok cell. The reaction produces molybdenum dioxide nanoparticles (20 nm) coated with carbon (20 nm). We have also carried out the same reaction under an applied magnetic field of 10 T. This reaction yielded different products. It produces a mixture of comparatively larger (50 nm) molybdenum dioxide nanoparticles and separated uncoated carbon particles (20-30 nm).     

Precursor-induced hydrothermal synthesis of flowerlike cupped-end microrod bundles of ZnO

Flowerlike cupped-end ZnO microrod bundles have been hydrothermally synthesized from precursor ZnCl2(N2H4)2 in sheet shape at 140 degrees C for 12 h; under the same conditions using the same precursor in rod shape, uniform ZnO nanorods were obtained. XRD pattern indicated the sample is ZnO with hexagonal cell contants a = 3.251 A and c = 5.206 A. FE-SEM and TEM show the formation process of the ZnO sample. HRTEM revealed that the flowerlike cupped-end ZnO microrod bundles grow along the [101] axis. The UV emission peak at approximately 396 nm and the blue band emission peak at approximately 469 nm were observed by PL spectra. A possible formation mechanism was proposed.     

Fabrication and magnetic properties of Ni nanospheres encapsulated in a fullerene-like carbon

A very simple, efficient, and economical synthetic technique, which produces fascinating fullerene-like Ni-C (graphitic) core-shell nanostructures at a relatively low temperature, is reported. The thermal dissociation of Ni acetylacetonate is carried out in a closed vessel cell (Swagelok) that was heated at 700 degrees C for 3 h. The encapsulation of ferromagnetic Ni nanospheres into the onion structured graphitic layers is obtained in a one-stage, single precursor reaction, without a catalyst, that possesses interesting magnetic properties. The magnetoresistance (MR) property of Ni nanospheres encapsulated in a fullerene-like carbon was measured, which shows large negative MR, of the order of 10%. The proposed mechanism for the formation of the Ni-C core-shell system is based on the segregation and the surface flux formed in the Ni and carbon particles during the reaction under autogenic pressure at elevated temperature.     

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.     

A general polymer-based process to prepare mixed metal oxides: the case of Zn1-xMgxO nanoparticles

Nanometer-sized mixed metal oxide (MMO) particles (Zn1-xMgxO) with very precise stoichiometry are prepared employing a polymer-based method. The precursor is formed by loading a polyacrylate with metal ions followed by purification of the polymer metal ion complex via repeated precipitation/redissolution cycles. Calcination of the polymer precursor at 550 degrees C gives particles of the metastable solid solution of the ZnO/MgO system in the composition range (x<0.2 and x>or=0.82). The MMO crystal particles are typically 20-50 nm in diameter. Doping of the ZnO by Mg2+ causes a shrinkage of lattice parameter c. Effects of band gap engineering on the optical band gap are reported. The photoluminescence in the visible is also affected, and its maximum shifts from 2.12 eV (pure ZnO) to 2.32 eV at x=0.21. The crystalline MMO particles start to undergo segregation into hexagonal and cubic phases upon annealing at 800 degrees C.     

Synthesis of WO3 nanorods by reacting WO(OMe)4 under autogenic pressure at elevated temperature followed by annealing

This article reports on the fabrication of WO(3) nanorods using an efficient straightforward synthetic technique, without a catalyst, and using a single precursor. The thermal dissociation of WO(OMe)(4) at 700 degrees C in a closed Swagelok cell under an air/inert atmosphere yielded W(18)O(49) nanorods. Annealing of W(18)O(49) at 500 degrees C under an air atmosphere led to the formation of pure WO(3) nanorods. The obtained products are characterized by morphological (scanning electron microscopy and transmission electron microscopy), structural (X-ray diffraction analysis, high-resolution scanning electron microscopy, and Raman spectroscopy), and compositional [energy-dispersive X-ray and elemental (C, H, N, S) analysis] measurements. The mechanism of the formation of nonstoichiometric W(18)O(49) nanorods is supported by the measured analytical data and several control experiments.     

Quenching of Photoluminescence in ZnO QDs Decorating Multiwalled Carbon Nanotubes

We report the controlled growth of ZnO quantum dots (QDs) on the sidewalls of multiwalled carbon nanotubes (MWCNTs) by a one‐step process and study the effect on the photoluminescence (PL) properties of the ZnO QDs‐MWCNT composite. The PL intensity of the composite is quenched and the lifetime is reduced compared to the only ZnO QDs. The origin of the PL quenching is discussed in terms of energy transfer, which is examined by varying the density and size of ZnO QDs by changing the molar concentration of the precursor solution for ZnO and the amount of MWCNT.     

XPS depth profile study of porous zirconia films deposited on stainless steel by spray pyrolysis: the problem of substrate corrosion

Zirconia (ZrO₂) films of tissue‐like structure and narrow pore size distribution have been deposited by spray pyrolysis using aqueous zirconyl chloride octahydrate (ZrOCl₂·8H₂O) precursor solutions. Stainless‐steel sheets, protected or unprotected by a ZnO barrier layer, have been used as the substrate material held at 473 K. The ZnO barrier layers have been deposited on the stainless steel held at 523 K by spray pyrolysis using a zinc acetate precursor. Their property of corrosion protection to stainless steel has been proved by electrochemical polarization measurements in 0.5 M NaCl solution. A complementary study of XPS (depth profiling, mapping) and x‐ray diffraction has shown that the unprotected steel substrates were corroded during ZrO₂ film post‐annealing in air at T ≥ 773 K, whereas steel substrates protected with a compact barrier layer of crystalline ZnO before ZrO₂ film deposition did not show surface corrosion even after annealing up to 997 K. Copyright © 2004 John Wiley & Sons, Ltd.     

Facile synthesis of photoluminescent ZnS and ZnSe nanopowders

The solid state thermal, one pot, efficient chemical reaction between Zn and S or Se elements in a closed reactor at 650 degrees C/60 min under their autogenic pressure in an inert atmosphere yielded luminescent ZnS and ZnSe semiconducting nanopowders (NPs). Scanning and Transmission electron microscopy measurements confirmed the size and shape of the as formed ZnS and ZnSe NPs. The wide size distributions of ZnS and ZnSe NPs are confirmed by UV-vis and TEM measurements. The crystalline wurtzite phase of ZnS and face centered cubic phase of ZnSe NPs is revealed from XRD and HR-TEM measurements. The obtained Raman scattering bands also supports the formation of pure ZnS and ZnSe phases. At room temperature, a strong visible green emission centered at approximately 525 nm is measured for ZnS, while ZnSe NPs showed a broad red emission band extending from 550 to 760 nm. The putative reaction mechanism is based on the low melting and boiling points of reactants (Zn, S and Se) under their autogenic pressure in an inert atmosphere.     

From triazines to heptazines: deciphering the local structure of amorphous nitrogen-rich carbon nitride materials

Nitrogen-rich carbon nitride (CN x , x >/= 1) network materials have been produced as disordered structures by a variety of precursor-based methods, many that involve solid-state thermolysis at or above 500 degrees C. One popular precursor building block is the triazine unit (C 3N 3), and most postulated amorphous CN x network structures are based on cross-linked triazine units. Since hydrogen is most often observed in the product, these materials are usually more appropriately described as CN x H y materials. Results from recent carbon nitride studies using larger conjugated heptazine (C 6N 7) precursors and from rigorous structural investigations of triazine to heptazine thermal conversion processes have prompted a reexamination of likely local structures present in amorphous carbon nitride networks formed by triazine thermolysis reactions. In the present study, the formation and local structure of a CN x H y material formed via the rapid and exothermic decomposition of a reactive triazine precursor, C 3N 3(NHCl) 3, was examined by byproduct gas mass spectrometry, NMR and IR spectroscopy, base hydrolysis, and crystallographic analysis. The combined results clearly indicate that the moderate-temperature ( approximately 400 degrees C) self-sustaining decomposition of trichloromelamine results in ring fragmentation and reorganization into a CN x H y product that contains predominantly larger heptazine-like structural building blocks. These results may have applicability to many other disordered carbon nitride materials that are formed via triazine thermolysis. It also provides clearer and more accurate structural guidance in the use of these carbon nitrides as photoactive materials or coordination supports for metal and nonmetal species.     

Structure-controlled solventless thermolytic synthesis of uniform silver nanodisks

Monodisperse silver nanodisks are synthesized on the gram scale from a well-characterized layered silver thiolate precursor via thermolysis at 180-225 degrees C under a N(2) atmosphere. XRD, TEM, HRTEM, and AFM analyses indicate that the nanodisks generated at 180 degrees C over 2 h have an average diameter of about 16.1 nm (sigma = +/-12%) and a thickness of 2.3 nm (sigma = +/-14%), and they lie on their (111) faces. The disk shape is considered to be predestined by the crystal structure of the precursor. Important aspects regarding the stability of the precursor, the thermolysis temperature, and the annealing time, as well as a possible conversion mechanism, are discussed.     

Ambient pressure syntheses of size-controlled corundum-type In2O3 nanocubes

Hydrolysis of In(O-iPr)3 by 10 molar excess of water at 90 degrees C in a surfactant/solvent mixture of oleylamine/oleic acid/trioctylamine provides very small nanoparticles (<5 nm in diameter) of In(O)(OH). Subsequent in situ thermolysis of the formed In(O)(OH) nanoparticles at 350 degrees C and ambient pressure produces monodisperse h-In2O3 nanocubes, which can form an extended two-dimensional array on a flat surface. The size of the In2O3 nanocubes (8, 10, and 12 nm) could be easily controlled by the simple change in the amounts of employed surfactants. The h-In2O3 nanocube samples show blue PL emissions at room temperature due to, presumably, systematic oxygen vacancy.     

Flowerlike ZnO nanostructures via hexamethylenetetramine-assisted thermolysis of zinc-ethylenediamine complex

Flowerlike ZnO nanostructures (FZNs) have been deposited on Si substrate from aqueous solution by the hexamethylenetetramine (HMT)-assisted thermolysis of zinc-ethylenediamine (en) complex at low temperature (95 degrees C) and in a short time (60 min). Obtained FZNs exhibit well-defined flowerlike morphology, hexagonal wurtzite structure, and strong UV photoluminescence. The flower petals constructed by many well-aligned nanorods possess the typical tapering feature with tip sizes of 30-50 nm. Effects of en, zinc-en molar ratio, HMT, and reaction time were investigated. Results show that en is determinative to the formation of FZNs, and the partial capping of NH(3).(CH(2))(2).NH(3) molecules on the side surface of the ZnO crystal is responsible for the tapering feature of petals. HMT can step into the nucleation process of ZnO and inhibit the formation of nanorods on the substrate by preventing heterogeneous precipitation. Moreover, the formation of twin crystal ZnO nuclei at low precursor concentrations and their further evolution into spindle crystals with clear middle interfaces are also vitally important for the development of FZNs.     

Organic–inorganic nanocomposites of (2‐hydroxypropyl)cellulose as a precursor of nanocrystalline zinc oxide layers

The sol–gel method of synthesis of the hybrid nanocomposite films of ZnO/(2‐hydroxypropyl) cellulose (HPC) on silica glass is presented. The sol phases were prepared for different weight ratios of zinc acetate dihydrate to HPC in the presence of triethylamine (TEA). Raman spectrum of the mixture of ZnAc and HPC indicates coordinating interaction between zinc ion and HPC. The generation of ZnO nanoparticles in the HPC matrix proceeds in situ through the annealing of the gel phase at a temperature of 160°C. Identification of ZnO nanoparticles in the HPC matrix is done by using photoluminescence (PL), UV–Vis, and Raman spectroscopy. The films of ZnO/HPC nanocomposite are transparent in the visible light and show a higher energy value of absorption edge compared with ZnO in the bulk. Nanocrystalline films of ZnO were obtained by the calcination of ZnO/HPC nanocomposite at 500°C. ZnO films possess a good transparency for the visible light and high absorbance for UV light. Nanocrystallite sizes of ZnO particles were estimated from the X‐ ray lines broadening. The properties of ZnO layers were studied by the evaluation of PL, X‐ray investigation and atom force microscope (AFM) scanning, and the optical absorption edge. Copyright © 2008 John Wiley & Sons, Ltd.     

The Optical Properties of ZnO Nanoparticles Capped with Polyvinyl Butyral

ZnO nanoparticles capped with polyvinyl butyral (PVB) have been synthesized by the sol-gel process. Photoluminescence (PL) spectra show a remarkable decrease in visible emission intensity after ZnO nanoparticles are capped with PVB, which indicates that dangling bonds and defect states at the surface of ZnO nanoparticles are markedly passivated. As a result, the process of surface-trapped hole tunneling back into the particles to form V**_O recombination center is blocked. The PL spectra of thin films show a strong ultraviolet (UV) emission with very weak visible emission. The typical intensity ratio of the UV emission at 3.45 eV to the visible emission at about 2.41 eV is 43.3, which shows an obvious improvement in luminescence properties by the surface passivation with PVB. Low-temperature PL spectra of ZnO powder at 93.8 K are dominated by free exciton, bound exciton and the LO-phonon replica of the bound exciton.     

Effect of Al-doping on the structure and optical properties of electrospun zinc oxide nanofiber films

Electrospun ZnO precursor nanofibers of average diameters 122±64 nm, 117±44 nm and 110±39 nm were fabricated by controlling the Al concentration of a polymeric solution. The resulting nanofibers were characterized by the XRD, SEM, EDS, TEM, XPS and PL. The electrospun Al-doped ZnO nanofiber films were polycrystalline and composed of densely packed grains, with crystallite size ranging from 28.7 nm, 25.7 nm, 25.4 nm to 20.4 nm corresponding to the atomic concentration of aluminum from 0, 1.6, 2.5 to 5.8 at.%. The incorporation of aluminum resulted in a decrease trend in the grain size and lattice parameter of the ZnO nanofiber films. The room temperature PL spectra of all samples show three different emissions, including UV (ultraviolet) emission with an obvious blue shift, Vis (visible) emission and NIR (near infrared) emission, the intensity of which decreases monotonically as the doping concentration is increased except for the highest doping level. The impurity content correlates with changes in the PL spectra, and the appropriate Al doping can improve the optical properties of ZnO nanofibers. The small size effect and Al-doping or the impurity incorporation should be responsible for the blue shift observation in Al-doped ZnO nanofiber films.     

碱式硫酸锌转化法制备ZnO多孔片及其光致发光性能

采用化学浴沉积法制备了碱式硫酸锌(ZSH)纳米片, 并经1000 ℃煅烧处理得到了ZnO多孔片. 详细研究了ZSH在Zn²⁺-六亚甲基四胺前驱体溶液体系中的形成机理、ZSH 的热解过程、ZnO的结晶性、微结构以及光致发光性能. 结果表明, 所得ZnO多孔片呈规则六角形状, 其尺寸为10-50 μm, 厚度为200-500 nm, 由于高温固相反应中传质等因素的限制, 构成薄片的ZnO晶粒呈多边形或不规则形貌, 晶粒间的孔为亚微米孔, 尺寸在100-500 nm范围. ZnO多孔薄片结晶性良好, 在388 nm处表现出较强紫外发光, 无可见光区的缺陷发光. 机理分析表明, SO₄^2- 与Zn²⁺的高亲和力是Zn²⁺-六亚甲基四胺体系中ZSH生成的根本原因, 而ZSH的热分解过程对ZnO多孔片的形貌和微结构影响显著. 本研究提出了一种制备高结晶质量ZnO多孔材料的新方法, 所得ZnO多孔片可望在催化、染料敏化太阳能电池、紫外光电器件等领域得到应用.     

Enhanced ultraviolet emission from ZnS-coated ZnO nanowires fabricated by self-assembling method

A simple chemical route for ZnS-coated ZnO nanowires with preferential (002) orientation is reported. Sodium sulfide and zinc nitrate were employed to supply S and Zn atoms at 60 degrees C to form ZnS-coated ZnO nanowires structures. Electron diffraction measurement shows that the ZnO/ZnS core-shell nanostructure is single crystalline. Interesting features are found in the photoluminescence (PL) spectra of ZnS-coated ZnO nanostructures. After coating, the UV emission of nanorods is dramatically enhanced at the expense of the green emission. The core/shell structure with higher band gap shell material and reduced surface states should be responsible for this PL enhancement.