Cubic form of Pb(2-x)Sn(x)S2 stabilized through size reduction to the nanoscale

We demonstrate the synthesis of semiconductor Pb(2-x)Sn(x)S(2) nanocrystals with a cubic rock salt crystal structure in a composition range where this structure is unstable in the bulk. The cubic Pb(2-x)Sn(x)S(2) nanocrystals were prepared using a modified hot injection colloidal synthetic route. The x value is in the range 0.40 < x < 1. Even though these compositions lie in a region of the PbS-SnS phase diagram where no single phase exists, and despite the fact that PbSnS(2) is a distorted orthorhombic phase, the Pb(2-x)Sn(x)S(2) nanocrystals are single phase solid solutions with cubic NaCl-type structure. Experimental evidence for this derives from powder X-ray diffraction (PXRD), electron diffraction, and pair distribution function (PDF) analysis. Elemental compositions determined using scanning transmission electron microscopy/energy dispersive spectroscopy (STEM/EDS), inductively coupled plasma-atomic emission spectroscopy (ICP-AES), and electron energy loss spectroscopy (EELS) reveal a composition close to the nominal ones. The band gaps of the Pb(2-x)Sn(x)S(2) nanocrystals (0.52-0.57 eV) are blue-shifted by quantum confinement relative to that of the hypothetical cubic PbSnS(2) phase which density functional theory (DFT) calculations show to be much narrower (0.2 eV) than in the case of orthorhombic PbSnS(2) (1.1 eV). The Pb(2-x)Sn(x)S(2) nanocrystals exhibit a well-defined band gap in the near-IR region and are stable up to ~300 °C above which they phase separate into cubic PbS and orthorhombic α-SnS.     

Passivation of GaAs nanocrystals by chemical functionalization

The effective use of nanocrystalline semiconductors requires control of the chemical and electrical properties of their surfaces. We describe herein a chemical functionalization procedure to passivate surface states on GaAs nanocrystals. Cl-terminated GaAs nanocrystals have been produced by anisotropic etching of oxide-covered GaAs nanocrystals with 6 M HCl(aq). The Cl-terminated GaAs nanocrystals were then functionalized by reaction with hydrazine or sodium hydrosulfide. X-ray photoelectron spectroscopic measurements revealed that the surfaces of the Cl-, hydrazine-, and sulfide-treated nanocrystals were As-rich, due to significant amounts of As0. However, no As0 was observed in the photoelectron spectra after the hydrazine-terminated nanocrystals were annealed at 350 degrees C under vacuum. After the anneal, the N 1s peak of hydrazine-exposed GaAs nanocrystals shifted to 3.2 eV lower binding energy. This shift was accompanied by the appearance of a Ga 3d peak shifted 1.4 eV from the bulk value, consistent with the hypothesis that a gallium oxynitride capping layer had been formed on the nanocrystals during the annealing process. The band gap photoluminescence (PL) was weak from the Cl- and hydrazine- or sulfide-terminated nanocrystals, but the annealed nanocrystals displayed strongly enhanced band-edge PL, indicating that the surface states of GaAs nanocrystals were effectively passivated by this two-step, wet chemical treatment.     

掺铝氧化锌纳米晶的超声-水热协同控制合成及其光催化性能

利用超声和水热的协同控制作用高效合成出了分散好、晶体结构完整、粒径尺寸约为20 nm的掺铝氧化锌(ZAO)纳米晶, 通过透射电子显微镜(TEM)、X射线粉末衍射仪(XRD)、傅里叶变换红外(FTIR)光谱仪、紫外-可见(UV-Vis)分光光度计和热重-差热分析(TG-DTA)手段对产物形貌、结构、光学性质及前驱物的热性质进行了研究, 对其降解罗丹明B (RhB)的光催化效果和光催化降解机理进行了探讨. 由于超声和水热的协同作用, 有效控制了产物的粒径, 提高了产物的结晶度. 产物的紫外-可见光谱吸收峰出现在369 nm左右, 计算其带隙约为3.36 eV. 同超声法或水热法制备的产物相比, 超声-水热法制备的ZAO纳米产物具有更高的光催化活性, 从而使光催化降解时间缩短为原来的77.8%. ZAO纳米光催化剂能够回收再利用.     

Formation of indium nitride nanorods within mesoporous silica SBA-15

We report the first formation of arrays of InN nanorods inside the nanoscale channels of mesoporous silica SBA-15. In(NO3)3 dissolved in methanol was incorporated into SBA-15 powder without prior pore surface functionalization. Formation of InN nanorod arrays was carried out by ammonolysis at 700 degrees C for 8 h. The final products have been characterized by FT-IR spectra, (29)Si MAS NMR spectra, Raman spectra, XRD patterns, TEM images, nitrogen adsorption-desorption isotherm measurements, and optical spectroscopy. The freestanding InN nanorods observed after silica framework removal with HF solution show diameters of 6-7.5 nm and lengths of 25-50 nm. Formation of a trace amount of In2O3 was also verified. The InN nanorods exhibit a broad band centered at around 550-600 nm, and a band gap energy of 1.5 eV was determined. No light absorption in the near-IR region was measured. The nanorods give a weak emission band centered at around 600 nm. These optical properties are believed to be related to the possible incorporation of oxygen during InN nanorod synthesis.     

Epitaxial growth of InN films by molecular-beam epitaxy using hydrazoic acid (HN3) as an efficient nitrogen source

Epitaxial InN films have been successfully grown on c-plane GaN template by gas-source molecular-beam epitaxy with hydrazoic acid (HN3) as an efficient nitrogen source. Results in residual-gas analyzer show that the HN3 is highly dissociated to produce nitrogen radicals and can be controlled in the amounts of active nitrogen species by tuning HN3 pressure. A flat and high-purity InN epifilm has been realized at the temperature near 550 degrees C, and a growth rate of 200 nm/hr is also achieved. Moreover, the epitaxial relationship of the InN(002) on the GaN(002) is reflected in the X-ray diffraction, and the full-width at half-maximum of the InN(002) peak as narrow as 0.05 degrees is related to a high-quality crystallinity. An infrared photoluminescence (PL) emission peak at 0.705 eV and the integrated intensity increasing linearly with excitation power suggest that the observed PL can be attributed to a free-to-bound recombination.     

Direct observation of defect levels in InN by soft X-ray absorption spectroscopy

We have used synchrotron-based near-edge X-ray absorption fine structure (NEXAFS) spectroscopy to study the electronic structure of nitrogen-related defects in InN(0001). Several defect levels within the band gap or the conduction band of InN were clearly resolved in NEXAFS spectra around the nitrogen K-edge. We attribute the level observed at 0.3 eV below the conduction band minimum (CBM) to interstitial nitrogen, the level at 1.7 eV above the CBM to antisite nitrogen, and a sharp resonance at 3.2 eV above the CBM to molecular nitrogen, in full agreement with theoretical simulations.     

Investigation of photoelectrical properties and relaxation dynamics in photoexcited CdSe nanocrystals in thin film form

Electrical and photoelectrical properties of cubic CdSe nanocrystals in thin film form (including the relaxation dynamics of photocarriers) are investigated. Photoelectrical properties of the obtained films are controlled by chemical (varying the reagent concentration in the reaction system) and physical means (controlling the crystal dimensions). In the case of thin films with optimal photoelectrical properties, the calculated band gap energy and ionization energies of impurity levels (on the basis of experimentally obtained temperature dependence of dark electrical resistance) at 0 K are 1.85, 0.74 and 0.43 eV, correspondingly. The calculated optical band gap energy (on the basis of spectral dependence of photoconductivity) at room temperature of 1.75 eV is in excellent agreement with the value of 1.77 eV which is obtained on the basis of electronic absorption spectrum in the framework of parabolic approximation for dispersion relation. Upon thermal treatment of chemically deposited thin films of cubic CdSe quantum dots, as a result of processes of coalescence and crystal growth, the electronic contact between nanocrystals increases and the confinement effects irreversibly disappear. Relaxation of non-equilibrium charge carriers is practically carried out according to the linear mechanism. The calculated relaxation time of photoexcited charge carriers is 0.4 ms.     

Nature of catalytic activities of CoO nanocrystals in thermal decomposition of ammonium perchlorate

This work addresses the chemical nature of the catalytic activity of X-ray "pure" CoO nanocrystals. All samples were prepared by a solvothermal reaction route. X-ray diffraction indicates the formation of CoO in a cubic rock-salt structure, while infrared spectra and magnetic measurements demonstrate the coexistence of CoO and Co 3O 4. Therefore, X-ray "pure" CoO nanocrystals are a unique composite structure with a CoO core surrounded by an extremely thin Co 3O 4 surface layer, which is likely a consequence of the surface passivation of CoO nanocrystals from the air oxidation at room temperature. The CoO core shows a particle size of 22 or 280 nm, depending on the types of the precursors used. This composite nanostructure was initiated as a catalytic additive to promote the thermal decomposition of ammonium perchlorate (AP). Our preliminary investigations indicate that the maximum decomposition temperature of AP is significantly reduced in the presence of CoO/Co 3O 4 composite nanocrystals and that the maximum decomposition peak shifts toward lower temperatures as the loading amount of the composite nanocrystals increases. These findings are different from the literature reports when using many nanoscale oxide additives. Finally, the decomposition heat for the low-temperature decomposition stages of AP was calculated and correlated to the chemical nature of the CoO/Co 3O 4 composite nanostructures.     

Novel bulk synthesis of magnesium oxide nanobelts networks by microwave hydrothermal route

Novel magnesium oxide (MgO) nanobelt structures were successfully synthesized on a large scale, low cost and catalyst free by a microwave hydrothermal route using the magnesium metal and potassium hydroxide precursors at 200 °C for 10 min. The synthesized MgO nanobelts were systemically characterized by power X-ray diffraction (XRD), scanning electron microscopy, energy dispersion spectroscopy and transmission-high resolution electron microscopy. The XRD results indicate that the MgO nanobelts have the well-crystalline cubic phase. The detailed morphological studies revealed that the synthesized products were nanobelts and were grown in large quantity. The optical energy gap of MgO nanobelts was found to be 3.1 eV. The photoluminescence spectra of the MgO nanobelts show a strong and broad green emission band, a weak ultraviolet emission band, and a weak red emission band. This novel method will open new dimensions for synthesized 1-D metal oxide and can be easily extended to the synthesis and assembly of other inorganic nanocrystals.     

Epitaxial growth of high purity cubic InN films on MgO substrates using HfN buffer layers by pulsed laser deposition

Cubic InN films have been grown on MgO substrates with HfN buffer layers by pulsed laser deposition (PLD). It has been found that the use of HfN (100) buffer layers allows us to grow cubic InN (100) films with an in-plane epitaxial relationship of [001]_InN//[001]_HfN//[001]_MgO. X-ray diffraction and electron back-scattered diffraction measurements have revealed that the phase purity of the cubic InN films was as high as 99%, which can be attributed to the use of HfN buffer layers and the enhanced surface migration of the film precursors by the use of PLD.     

Chemical deposition of semiconducting cadmium selenide quantum dots in thin film form and investigation of their optical and electrical properties

Cadmium selenide quantum dots with cubic crystal structure are chemically deposited in thin film form using selenosulfate as a precursor for selenide ions and ammonia buffer with double role: as a ligand and as a pH value controller. The optical band gap energies of as-deposited and thermally treated cadmium selenide thin films, calculated within the framework of parabolic approximation for the dispersion relation, on the basis of equations which arise from the Fermi's golden rule for electronic transitions from valence to conduction band, are 2.08 and 1.77 eV, correspondingly. The blue shift of band gap energy of 0.34 eV for as-deposited thin films with respect to the bulk value is due to the quantum size effects (i.e., nanocrystals behave as quantum dots) and this finding is in agreement with the theoretical predictions. During the thermal treatment the nanocrystals are sintered, the increase of crystal size being in correlation with the decrease of band gap energy. The annealed thin films are practically non-quantized. From the resistance-temperature measurements, on the basis of the dependence of ln(R/Ω) vs 1/T in the region of intrinsic conduction, the thermal band gap energy (at 0 K) of 1.85 eV was calculated.     

Cauliflower-like CdS microspheres composed of nanocrystals and their physicochemical properties

Cauliflower-like cadmium sulfide (CdS) microspheres composed of nanocrystals have been successfully synthesized by a hydrothermal method using poly(ethylene glycol) (PEG) as the template coordination agent and characterized by a variety of methods. Our experiments confirmed that the size of the CdS microspheres could be easily modified by controlling the chain length of PEG. Powder X-ray diffraction and Raman spectroscopy measurements revealed the cubic structure of the CdS microspheres; morphological studies performed by HR-SEM and HR-TEM methods showed the cauliflower-like structure of the synthesized CdS microspheres. Each microsphere was identified to be created by the self-assembly of CdS nanocrystals and is attributed to the oriented aggregation of the CdS nanocrystals around a polymer-Cd(2+) complex spherical framework structure. X-ray photoelectron spectroscopy (XPS) and energy-dispersive X-ray (EDX) analysis confirmed the stoichiometries of the CdS microspheres. Diffuse reflectance spectrum (DRS) measurements showed that increasing the PEG chain length increased the band gap value of the CdS microspheres slightly, from 1.99 to 2.06 eV. The cauliflower-like CdS microspheres could be applied to photocatalytic degradation studies.     

Surface passivated silicon nanocrystals with stable luminescence synthesized by femtosecond laser ablation in solution

We report the synthesis of silicon nanocrystals via a one-step route, namely, femtosecond laser ablation in 1-hexene under ambient conditions. The size of these silicon nanocrystals is 2.37 ± 0.56 nm as determined by transmission electron microscopy. Fourier transform infrared spectra and X-ray photoelectron spectra indicate that the surface of the silicon nanocrystals is passivated by organic molecules and is also partially oxidized by O(2) and H(2)O dissolved in the solution. These silicon nanocrystals emit stable and bright blue photoluminescence. We suggest that the photoluminescence originates from the radiative recombination of electron-hole pairs through the oxide-related centers on the surface of the silicon nanocrystals. The decay rate of the oxide-related surface recombination can be comparable to that of the direct band gap transition. In the excitation and emission spectra, a vibrational structure with nearly constant spacings (0.18 eV) is observed. We propose that the strong electron-phonon coupling between excitons and the longitudinal optical (LO) phonons of the Si-C vibration is responsible for this vibrational structure. The fluctuations in the peak resolution, about ±0.01 eV, are ascribed to the size distribution and presence of Si-O vibrations. These silicon nanocrystals offer stable luminescence and are synthesized through a "green" and simple route. They may find important applications in many fields, such as bioimaging and environmental science.     

Optical properties of ZnO nanocrystals doped with Cd, Mg, Mn, and Fe ions

ZnO nanocrystals doped with Cd, Mg, Mn, and Fe ions were obtained by thermolysis of a family of metal cupferrates. The nanocrystals were characterized by X-ray diffraction, energy-dispersive X-ray analysis, transmission electron microscopy, UV-visible, luminescence, and excitation spectroscopy. The band gap of the nanocrystals can be tuned in the range of 2.9-3.8 eV by the use of the dopants. In most cases, the nanocrystals are sufficiently defect-free to exhibit band edge luminescence.     

前驱体水解对纳米铂形状控制合成的影响

以聚丙烯酸钠(NaPA: M_w ≈ 2100)为保护剂，对比研究了H_2还原K_2PtCl_4 和K_2PtCl_6水溶液制备纳米铂晶粒的形状选择性，揭示了前驱体的水解对纳米铂 晶粒的形状控制合成具有显著影响。文献中通常采用的合成立方形状纳米铂的 K_2PtCl_4前驱体在水溶液中不稳定，避光静置一周会析出黑色沉淀。这种不稳定 性导致了以K_2PtCl_4为Pt前驱体的合成结果难以重复。相比而言，避光静墨的 K_2PtCl_6水溶液很稳定，以它为前驱体合成的纳米铂通常为削角八面体。 K_2PtCl_6水溶液暴露于室内光线中会出现[PtCl_6]~(-2)的光致水解。当[PtCl_6] ~(2-)的紫外特征吸收峰(260nm)由于光致水解完全消失后，以聚丙烯酸钠为保护剂 ，通过H_2还原可以有选择性地(约80%)合成由{100}晶面包裹的立方体形状的纳米 铂。     

Density functional study of the interfacial electron transfer pathway for monolayer-adsorbed InN on the TiO(2) anatase (101) surface

Density functional theory (DFT) in connection with ultrasoft pseudopotential (USP) and generalized gradient spin-polarized approximations (GGSA) is applied to calculate the adsorption energies and structures of monolayer-adsorbed InN on the TiO(2) anatase (101) surface and the corresponding electronic properties, that is, partial density of states (PDOS) for surface and bulk layers of the TiO(2) anatase (101) surface and monolayer-adsorbed InN, to shed light on the possible structural modes for initial photoexcitation within the UV/vis adsorption region followed by fast electron injection through the InN/TiO(2) interface for an InN/TiO(2)-based solar cell design. Our calculated adsorption energies found that the two most probable stable structural modes of monolayer-adsorbed InN on the TiO(2) anatase (101) surface are (1) an end-on structure with an adsorption energy of 2.52 eV through N binding to surface 2-fold coordinated O (O(cn2)), that is, InN-O(cn2), and (2) a side-on structure with an adsorption energy of 3.05 eV through both N binding to surface 5-fold coordinated Ti (Ti(cn5)) and In bridging two surface O(cn2), that is, (O(cn2))(2)-InN-Ti(cn5). Our calculated band gaps for both InN-O(cn2) and (O(cn2))2-InN-Ti(cn5) (including a 1.0-eV correction using a scissor operator) of monolayer-adsorbed InN on the TiO(2) anatase (101) surface are red-shifted to 1.7 eV (730 nm) and 2.3 eV (540 nm), respectively, which are within the UV/vis adsorption region similar to Gratzel's black dye solar cell. Our analyses of calculated PDOS for both surface and bulk layers of the TiO(2) anatase (101) surface and monolayer-adsorbed InN on the TiO(2) anatase (101) surface suggest that the (O(cn2))(2)-InN-Ti(n5) configuration of monolayer-adsorbed InN on the TiO(2) anatase (101) surface would provide a more feasible structural mode for the electron injection through the InN/TiO(2) interface. This is due to the presence of both occupied and unoccupied electronic states for monolayer-adsorbed InN within the band gap TiO(2) anatase (101) surface, which will allow the photoexcitation within the UV/vis adsorption region to take place effectively, and subsequently the photoexcited electronic states will overlap with the unoccupied electronic states around the lowest conduction band of the TiO(2) anatase (101) surface, which will ensure the electron injection through the InN/TiO(2) interface. Finally, another thing worth our attention is our preliminary study of double-layer-adsorbed InN on the TiO(2) anatase (101) surface, that is, (O(cn2))(2)-(InN)(2)-Ti(cn5), with a calculated band gap red-shifted to 2.6 eV (477 nm) and a different overlap of electronic states between double-layer-adsorbed InN and the TiO(2) anatase (101) surface qualitatively indicated that there is an effect of the thickness of adsorbed InN on the TiO(2) anatase (101) surface on both photoexcitation and electron injection processes involved in the photoinduced interfacial electron transfer through InN/TiO(2). A more thorough and comprehensive study of different layers of InN adsorbed in all possible different orientations on the TiO(2) anatase (101) surface is presently in progress.     

A density-functional theory of hydrogen adsorption on indium nitride nanotubes

First-principles calculations based on density functional theory (DFT) are used to study the chemisorption properties of one, two, and four hydrogen atoms on the zigzag and armchair single-walled InN nanotubes (InNNTs).The results indicate that the H atom is strongly bounded to the exterior wall of (4, 4) InNNTs compared with the (7, 0) InNNTs, while the chemisorption energies corresponding to the most stable configuration of H₂ dissociation and a single H atom are found to be–3.85 and–3.26 eV, respectively. Furthermore, the effect of the hydrogen storage on the geometries and electronic properties of related InN nanotubes were also discussed. The computed density of states (DOS) indicates that the energy gap of the zigzag and armchair InN nanotubes on hydrogen adsorptions are significantly decreased which can increase the electrical conductance of the tubes. Therefore, InN nanotubes due to the high binding energy can be used for hydrogen storage.     

聚合物-二氧化硅复合基材中CdS纳米晶的合成

本文报道在Sol-gel基材中制备由聚合物稳定的CdS纳米晶的新方法， 即通过甲基丙烯酸镉与甲基丙烯酸羟乙酯共聚合合成了含有Cd 2+的聚合物微凝胶, 在聚合物微凝胶网络中原位聚合正硅酸乙酯形成聚合物互穿的Sol-gel复合基材. 再向该聚合物/二氧化硅复合基材中通入H2S气体得到CdS纳米晶. 在聚合物网络中原位聚合正硅酸乙酯可以降低纯二氧化硅材料的脆性; 另一方面, 二氧化硅可以作为增强剂增加聚合物材料的强度. 因此, 在我们合成的聚合物/二氧化硅复合基材中制备的CdS纳米晶将具有很好的应用前景.     

Temperature-triggered self-assembly of ZnO: from nanocrystals to nanorods to tablets

ZnO nanocrystals, nanorods, and tablets were prepared at 110, 140, and 180 degrees C in a water-ethanol system. Nanorods (~2 x 40 nm) arranged in serpentine morphologies formed by the oriented coalescence of anhedral ZnO nanocrystals (~3.5 nm diameter), while tabular ZnO grew by [1210] textural attachment of the nanorods. The development of these crystal habits is believed to proceed via a dissolution and growth mechanism mediated by a transient amorphous phase. Materials synthesized at intermediate temperatures (125 and 160 degrees C) possessed microstructures containing mixed crystal forms in the expected orientation relationship. Photoluminescent spectra of the nanocrystals and nanorods showed blue shifts of 0.16 and 0.13 eV with respect to the bulk ZnO band gap (3.26 eV) due to quantum confinement, with the narrow emission peaks typical of particles possessing uniform size and shape. The larger tablets displayed a less energetic emission (3.10 eV) ascribed to exciton-exciton collisions.     

Capillary electrophoretic separation of nanoparticles

In the present work, CdSe nanocrystals (NCs) synthesized with a trioctylphosphine surface passivation layer were modified using amphiphilic molecules to form a surface bilayer capable of providing stable NCs aqueous solutions. Such modified nanocrystals were used as a test solute in order to analyze new electrophoretic phenomena, by applying a micellar plug as a separation tool for discriminating nanocrystals between micellar and micelle-free zones during electrophoresis. The distribution of NCs between both zones depended on the affinity of nanocrystals towards the micellar zone, and this relies on the kind of surface ligands attached to the NCs, as well as electrophoretic conditions applied. In this case, the NCs that migrated within a micellar zone can be focused using a preconcentration mechanism. By modifying electrophoretic conditions, NCs were forced to migrate outside the micellar zone in the form of a typical CZE peak. In this situation, a two-order difference in separation efficiencies, in terms of theoretical plates, was observed between focused NCs (N ~ 10⁷) and a typical CZE peak for NCs (N ~ 10⁵). By applying the amino-functionalized NCs the preconcentration of NCs, using a micellar plug, was examined, with the conclusion that preconcentration efficiency, in terms of the enhancement factor for peak height (SEF_height) can be, at least 20. The distribution effect was applied to separate CdSe/ZnS NCs encapsulated in silica, as well as surface-modified with DNA, which allows the estimation of the yield of conjugation of biologically active molecules to a particle surface.