Tuning the potentials of "extra" electrons in colloidal n-type ZnO nanocrystals via Mg2+ substitution

Colloidal reduced ZnO nanocrystals are potent reductants for one-electron or multielectron redox chemistry, with reduction potentials tunable via the quantum confinement effect. Other methods for tuning the redox potentials of these unusual reagents are desired. Here, we describe synthesis and characterization of a series of colloidal Zn(1-x)Mg(x)O and Zn(0.98-x)Mg(x)Mn(0.02)O nanocrystals in which Mg(2+) substitution is used to tune the nanocrystal reduction potential. The effect of Mg(2+) doping on the band-edge potentials of ZnO was investigated using electronic absorption, photoluminescence, and magnetic circular dichroism spectroscopies. Mg(2+) incorporation widens the ZnO gap by raising the conduction-band potential and lowering the valence-band potential at a ratio of 0.68:0.32. Mg(2+) substitution is far more effective than Zn(2+) removal in raising the conduction-band potential and allows better reductants to be prepared from Zn(1-x)Mg(x)O nanocrystals than can be achieved via quantum confinement of ZnO nanocrystals. The increased conduction-band potentials of Zn(1-x)Mg(x)O nanocrystals compared to ZnO nanocrystals are confirmed by demonstration of spontaneous electron transfer from n-type Zn(1-x)Mg(x)O nanocrystals to smaller (more strongly quantum confined) ZnO nanocrystals.     

Synthesis and spectroscopic characterization of water-soluble Mn-doped ZnO(x)S(1-x) quantum dots

A non-cadmium and water-soluble Mn-doped ZnO(x)S(1-x) QDs was synthesized with denatured bovine serum albumin (dBSA) as stabilizer under nitrogen atmosphere, and the as-prepared products were characterized by X-ray powder diffraction (XRD), UV-vis absorption spectroscopy, fluorescence (FL) emission spectroscopy, high resolution transmission electronmicroscopy (HRTEM) and Raman spectrum. XRD patterns indicate that the Mn-doped ZnO(x)S(1-x) QDs have a zinc-blende structure, and that manganese emerges in the form of divalent manganese (Mn(2+)) and trivalent manganese (Mn(3+)) (the intermediate of the reaction). The size of Mn-doped ZnO(x)S(1-x) QDs is about 3.2±0.7 nm according to HRTEM imaging. The FL spectra reveal that the Mn-doped ZnO(x)S(1-x) QDs have two distinct emission bands: the defect-related emission and the Mn(2+)-related emission, which exhibit a competing process. A good FL signal of the transition of Mn(2+) ((4)T(1)-(6)A(1)) is observed when the doping amounts are 1.0% and 20% respectively, and the as-prepared solutions are stable for more than 6 months at 4°C. This method has the advantages of good stability and environment-friendly stabilizer, for involving no heavy metal ions or toxic reagents.     

Thermal activated energy transfer between luminescent states of Mn2+-doped ZnTe nanoparticles embedded in a glass matrix

Zn(1-x)Mn(x)Te nanocrystals (NCs), at various concentrations x, were successfully grown in a host glass matrix by the fusion method after appropriate annealing. Growth of these NCs was evidenced by optical absorption (OA), X-Ray Diffraction (XRD), magnetic force microscopy (MFM) and photoluminescence (PL) measurements. From the room temperature OA spectra, it was possible to observe the formation of two well defined, different sized groups of NCs, one attributed to quantum dots (QDs) and the other to bulk-like nanocrystals (NCs). XRD results have confirmed that the cubic zincblend structure of nanoparticles is not altered by the substitutional incorporation of Mn(2+) ions into the ZnTe NCs. MFM images supported the OA spectra results and thus provided additional confirmation of the formation of Zn(1-x)Mn(x)Te magnetic nanoparticles in the host glass matrix. The two groups of NCs were also observed in the PL spectra as well as deep defects attributed to the presence of oxygen centers in the electronic structure of the Zn(1-x)Mn(x)Te NCs. Strong agreement between the fitting model, based on rate equation, and experimental PL intensity data at different temperatures demonstrates that this model adequately describes the energy transfer processes between the NCs and the defects of the Zn(1-x)Mn(x)Te system at different temperatures.     

Cd(1-x)Zn(x)O [0.05 ≤x≤ 0.26] synthesized by vapor-diffusion induced hydrolysis and co-nucleation from aqueous metal salt solutions

Nanoparticulate Cd(1-x)Zn(x)O (x = 0, 0.05-0.26, 1) is synthesized in a simple two-step synthesis approach. Vapor-diffusion induced catalytic hydrolysis of two molecular precursors at low temperature induces co-nucleation and polycondensation to produce bimetallic layered hydroxide salts (M = Cd, Zn) as precursor materials which are subsequently converted to Cd(1-x)Zn(x)O at 400 °C. Unlike ternary materials prepared by standard co-precipitation procedures, all products presented here containing < 30 mol% Zn(2+) ions are homogeneous in elemental composition on the micrometre scale. This measured compositional homogeneity within the samples, as determined by energy dispersive spectroscopy and inductively coupled plasma spectroscopy, is a testimony to the kinetic control achieved by employing slow hydrolysis conditions. In agreement with this observation, the optical properties of the materials obey Vegard's Law for a homogeneous solid solution of Cd(1-x)Zn(x)O, where x corresponds to the values determined by inductively coupled plasma analysis, even though powder X-ray diffraction shows phase separation into a cubic mixed metal oxide phase and a hexagonal ZnO phase at all doping levels.     

Effects of thermal annealing on the structural and optical properties of Mg(x)Zn(1-x)O nanocrystals

Mg(x)Zn(1-x)O ternary alloy nanocrystals with hexagonal wurtzite structures were fabricated by using the sol-gel method. X-ray diffraction patterns, UV-vis absorption spectra, and photoluminescence spectra were used to characterize the structural and optical properties of the nanocrystals. For as-prepared nanocrystals, the band gap increases with increasing Mg content. Weak excitonic emission with strong deep-level emission related to oxygen vacancy and interface defects is observed in the photoluminescence spectra at room temperature. Thermal annealing in oxygen was used to decrease the number of defects and to improve the quality of the nanocrystals. In terms of XRD results, the grain sizes of nanocrystals increase with increasing annealing temperature and the lattice constants of alloy are smaller than those of pure ZnO. The band gap becomes narrower with increasing annealing temperature. For Mg(x)Zn(1-x)O nanocrystals (x=0.03-0.15) annealed at temperatures ranging from 500 to 1000 degrees C, intense near-band-edge (NBE) emissions and weak deep-level (DL) emissions are observed. Consequently, the quality of Mg(x)Zn(1-x)O nanocrystals can be improved by thermal annealing.     

Control of metal-ion composition in the synthesis of ternary II-II'-VI nanoparticles by using a mixed-metal cluster precursor approach

The ternary molecular nanoclusters [Zn(x)Cd(10-x)Se4(SePh)12(PnPr3)4] (x = 1.8, 1 a; x = 2.6, 1 b) were employed as single-source precursors for the synthesis of high-quality hexagonal Zn(x)Cd(1-x)Se nanocrystals. The tellurium clusters [Zn(x)Cd(10-x)Te4(TePh)12(PnPr3)4] (x = 1.8, 2 a; x = 2.6, 2 b) are equally convenient precursors for the synthesis cubic Zn(x)Cd(1-x)E nanoparticles. The thermolysis of the cluster molecules in hexadecylamine provides an efficient system in which the inherent metal-ion stoichiometry of the clusters is retained in the nanocrystalline products, whilst also affording control of particle size within the 2-5 nm range. In all cases, the nanoparticles are monodisperse, and luminescence spectra exhibit emission energies close to the absorption edge. Analysis of the optical spectra and X-ray diffraction patterns of these materials indicates a metal-ion concentration gradient within the structures of the nanocrystals, with Zn(II) ions predominantly located near the surface of the particles.     

Synthesis of colloidal Mn2+:ZnO quantum dots and high-TC ferromagnetic nanocrystalline thin films

We report the synthesis of colloidal Mn(2+)-doped ZnO (Mn(2+):ZnO) quantum dots and the preparation of room-temperature ferromagnetic nanocrystalline thin films. Mn(2+):ZnO nanocrystals were prepared by a hydrolysis and condensation reaction in DMSO under atmospheric conditions. Synthesis was monitored by electronic absorption and electron paramagnetic resonance (EPR) spectroscopies. Zn(OAc)(2) was found to strongly inhibit oxidation of Mn(2+) by O(2), allowing the synthesis of Mn(2+):ZnO to be performed aerobically. Mn(2+) ions were removed from the surfaces of as-prepared nanocrystals using dodecylamine to yield high-quality internally doped Mn(2+):ZnO colloids of nearly spherical shape and uniform diameter (6.1 +/- 0.7 nm). Simulations of the highly resolved X- and Q-band nanocrystal EPR spectra, combined with quantitative analysis of magnetic susceptibilities, confirmed that the manganese is substitutionally incorporated into the ZnO nanocrystals as Mn(2+) with very homogeneous speciation, differing from bulk Mn(2+):ZnO only in the magnitude of D-strain. Robust ferromagnetism was observed in spin-coated thin films of the nanocrystals, with 300 K saturation moments as large as 1.35 micro(B)/Mn(2+) and T(C) > 350 K. A distinct ferromagnetic resonance signal was observed in the EPR spectra of the ferromagnetic films. The occurrence of ferromagnetism in Mn(2+):ZnO and its dependence on synthetic variables are discussed in the context of these and previous theoretical and experimental results.     

Controlled synthesis, characterization, and catalytic properties of Mn(2)O(3) and Mn(3)O(4) nanoparticles supported on mesoporous silica SBA-15

A method established in the present study has proven to be effective in the synthesis of Mn(2)O(3) nanocrystals by the thermolysis of manganese(III) acetyl acetonate ([CH(3)COCH=C(O)CH(3)](3)-Mn) and Mn(3)O(4) nanocrystals by the thermolysis of manganese(II) acetyl acetonate ([CH(3)COCH=C(O)-CH(3)](2)Mn) on a mesoporous silica, SBA-15. In particular, Mn(2)O(3) nanocrystals are the first to be reported to be synthesized on SBA-15. The structure, texture, and electronic properties of nanocomposites were studied using various characterization techniques such as N2 physisorption, X-ray diffraction (XRD), laser Raman spectroscopy (LRS), temperature-programmed reduction (TPR), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). The results of powder XRD at low angles show that the framework of SBA-15 remains unaffected after generation of the manganese oxide (MnO(x)) nanoparticles, whereas the pore volume and the surface area of SBA-15 dramatically decreased as indicated by N2 adsorption-desorption. TEM images reveal that the pores of SBA-15 are progressively blocked with MnO(x) nanoparticles. The formation of the hausmannite Mn(3)O(4) and bixbyite Mn(2)O(3) structures was clearly confirmed by XRD. The surface structures of MnO(x) were also determined by LRS, XPS, and TPR. The crystalline phases of MnO(x) were identified by LRS with corresponding out-of-plane bending and symmetric stretching vibrations of bridging oxygen species (M-O-M) of both MnO(x) nanoparticles and bulk MnO(x). We also observed the terminal Mn=O bonds corresponding to vibrations at 940 and 974 cm-1 for Mn(3)O(4)/SBA-15 and Mn(2)O(3)/SBA-15, respectively. These results show that the MnO(x) species to be highly dispersed inside the channels of SBA-15. The nanostructure of the particles was further identified by the TPR profiles. Furthermore, the chemical states of the surface manganese (Mn) determined by XPS agreed well with the findings of LRS and XRD. These results suggest that the method developed in the present study resulted in the production of MnO(x) nanoparticles on mesoporous silica SBA-15 by controlling the crystalline phases precisely. The thus-prepared nanocomposites of MnO(x) showed significant catalytic activity toward CO oxidation below 523 K. In particular, the MnO(x) prepared from manganese acetyl acetonate showed a higher catalytic reactivity than that prepared from Mn(NO(3))2.     

Structural, optical, and magnetic properties of Mn-doped ZnO thin film

The Zn(1-x)Mn(x)O (x = 0, 0.16, and 0.25) thin films were grown on fused quartz substrates by reactive magnetron cosputtering. X-ray-diffraction measurement revealed that all the films were single phase and had wurtzite structure with c-axis orientation. As Mn concentration increased in the Zn(1-x)Mn(x)O films, the c-axis lattice constant and band-gap energy increased gradually. In Raman-scattering studies, an additional Mn-related vibration mode appeared at 520 cm(-1). E(2H) phonon line of Zn(1-x)Mn(x)O alloy was broadened asymmetrically and redshifted as a result of microscopic structural disorder induced by Mn(2+) random substitution. The Zn(0.84)Mn(0.16)O film exhibited a ferromagnetic characteristic with a Curie temperature of approximately 62 K. However, with increasing Mn concentration to 25 at. %, ferromagnetism disappeared due to the enhanced antiferromagnetic superexchange interactions between neighboring Mn(2+) ions.     

New Mn12 clusters with tunable oxidation states via the use of N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine

Room-temperature reactions of N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine with manganese(II) salts yield a novel family of Mn(12) clusters incorporating the same Mn(12)O(4) core and tunable oxidation states of Mn(III)(x)Mn(II)(12-x) (x = 8, 10, and 12). Magnetic susceptibility data indicate that the spin of the ground state increases as the number of Mn(III) ions is increased, leading to increases in the magnitude of the out-of-phase ac susceptibility signal as the number of Mn(III) ions is increased.     

Overall water splitting on (Ga(1-x)Zn(x))(N(1-x)O(x)) solid solution photocatalyst: relationship between physical properties and photocatalytic activity

The physical and photocatalytic properties of a novel solid solution between GaN and ZnO, (Ga(1-x)Zn(x))(N(1-x)O(x)), are investigated. Nitridation of a mixture of Ga(2)O(3) and ZnO at 1123 K for 5-30 h under NH(3) flow results in the formation of a (Ga(1-x)Zn(x))(N(1-x)O(x)) solid solution with x = 0.05-0.22. With increasing nitridation time, the zinc and oxygen concentrations decrease due to reduction of ZnO and volatilization of zinc, and the crystallinity and band gap energy of the product increase. The highest activity for overall water splitting is obtained for (Ga(1-x)Zn(x))(N(1-x)O(x)) with x = 0.12 after nitridation for 15 h. The crystallinity of the catalyst is also found to increase with increasing the ratio of ZnO to Ga(2)O(3) in the starting material, resulting in an increase in activity.     

Stabilization and study of SrFe(1-x)Mn(x)O2 oxides with infinite-layer structure

A series of layered oxides of nominal composition SrFe(1-x)Mn(x)O(2) (x = 0, 0.1, 0.2, 0.3) have been prepared by the reduction of three-dimensional perovskites SrFe(1-x)Mn(x)O(3-δ) with CaH(2) under mild temperature conditions of 583 K for 2 days. The samples with x = 0, 0.1, and 0.2 exhibit an infinite-layer crystal structure where all of the apical O atoms have been selectively removed upon reduction. A selected sample (x = 0.2) has been studied by neutron powder diffraction (NPD) and X-ray absorption spectroscopy. Both techniques indicate that Fe and Mn adopt a divalent oxidation state, although Fe(2+) ions are under tensile stress whereas Mn(2+) ions undergo compressive stress in the structure. The unit-cell parameters progressively evolve from a = 3.9932(4) ? and c = 3.4790(4) ? for x = 0 to a = 4.00861(15) ? and c = 3.46769(16) ? for x = 0.2; the cell volume presents an expansion across the series from V = 55.47(1) to 55.722(4) ?(3) for x = 0 and 0.2, respectively, because of the larger effective ionic radius of Mn(2+) versus Fe(2+) in four-fold coordination. Attempts to prepare Mn-rich compositions beyond x = 0.2 were unsuccessful. For SrFe(0.8)Mn(0.2)O(2), the magnetic properties indicate a strong magnetic coupling between Fe(2+) and Mn(2+) magnetic moments, with an antiferromagnetic temperature T(N) above room temperature, between 453 and 523 K, according to temperature-dependent NPD data. The NPD data include Bragg reflections of magnetic origin, accounted for with a propagation vector k = ((1)/(2), (1)/(2), (1)/(2)). A G-type antiferromagnetic structure was modeled with magnetic moments at the Fe/Mn position. The refined ordered magnetic moment at this position is 1.71(3) μ(B)/f.u. at 295 K. This is an extraordinary example where Mn(2+) and Fe(2+) ions are stabilized in a square-planar oxygen coordination within an infinite-layer structure. The layered SrFe(1-x)Mn(x)O(2) oxides are kinetically stable at room temperature, but in air at ~170 °C, they reoxidize and form the perovskites SrFe(1-x)Mn(x)O(3-δ). A cubic phase is obtained upon reoxidation of the layered compound, whereas the starting precursor SrFeO(2.875) (Sr(8)Fe(8)O(23)) was a tetragonal superstructure of perovskite.     

Growth kinetic on the optical properties of the Pb(1-x)Mn(x)Se nanocrystals embedded in a glass matrix: thermal annealing and Mn2+ concentration

Semimagnetic Pb(1-x)Mn(x)Se nanocrystals were synthesized by a fusion method in a glass matrix and characterized by optical absorption (OA), atomic/magnetic force microscopy (AFM/MFM), and photoluminescence techniques. MFM images strongly indicated the formation of Pb(1-x)Mn(x)Se magnetic phases in the glass system. Quantum dot size was manipulated by tuning annealing time. It was shown that Mn(2+) impurity affects nucleation, where Mn(2+)-doped samples present a redshift of the OA peak after a short annealing time and a blueshift after long annealing time compared to undoped PbSe NCs. This behavior was linked to the dependence of band-gap energy and the absorption selection rule on Mn(2+) concentration. Photoluminescence in the Pb(1-x)Mn(x)Se nanocrystals increases as the temperature rises up to a point and then decreases at higher temperatures. Anomalous increases in emission efficiency were analyzed by considering temperature induced carrier-transfer in semimagnetic Pb(1-x)Mn(x)Se quantum dots nanocrystals of different sizes.     

Magnetic and high rate adsorption properties of porous Mn(1-x)Zn(x)Fe2O4 (0 ≤ x ≤ 0.8) adsorbents

Porous spinel ferrites Mn(1-x)Zn(x)Fe(2)O(4) (0 ≤ x ≤ 0.8) are synthesized by a simple sol-gel method with egg white. All samples exhibit porous morphologies and large BET surface area (S(BET)). The substitution of Zn(2+) affects the magnetic properties of ferrites and the adsorption properties of methylene blue (MB) on ferrites, obviously. The saturation magnetization (Ms) of Mn(1-x)Zn(x)Fe(2)O(4) increases before x=0.4, and decreases with further increase of Zn(2+) substitution. This can be ascribed to the changes of the cationic distribution and the variation of spin arrangement in A-site and B-site of spinel structure. All samples show high adsorption capacity and the removal efficiencies of MB reach up to >90% within 3 h. The Zn(2+) substitution accelerates the adsorption rate and capacity of MB on Mn(1-x)Zn(x)Fe(2)O(4). The quickest adsorption occurred at x=0.2 and the largest adsorption capacity occurred at x=0.8.     

Zinc chalcogenolate complexes as precursors to ZnE and Mn/ZnE (E = S, Se) clusters

The ternary clusters (tmeda)(6)Zn(14-x)Mn(x)S(13)Cl(2) (1a-d) and (tmeda)(6)Zn(14-x)Mn(x)Se(13)Cl(2) (2a-d), (tmeda = N,N,N',N'-tetramethylethylenediamine; x ≈ 2-8) and the binary clusters (tmeda)(6)Zn(14)E(13)Cl(2) (E = S, 3; Se, 4;) have been isolated by reacting (tmeda)Zn(ESiMe(3))(2) with Mn(II) and Zn(II) salts. Single crystal X-ray analysis of the complexes confirms the presence of the six "(tmeda)ZnE(2)" units as capping ligands that stabilize the clusters, and distorted tetrahedral geometry around the metal centers. Mn(II) is incorporated into the ZnE framework by substitution of Zn(II) ions in the cluster. The polynuclear complexes (tmeda)(6)Zn(12.3)Mn(1.7)S(13)Cl(2)1a, (tmeda)(6)Zn(12.0)Mn(2.0)Se(13)Cl(2)2a, and (tmeda)(6)Zn(8.4)Mn(5.6)Se(13)Cl(2)2d represent the first examples of "Mn/ZnE" clusters with structural characterization and indications of the local chemical environment of the Mn(II) ions. The incorporation of higher amounts of Mn into 1d and 2d has been confirmed by elemental analysis. Density functional theory (DFT) calculations indicate that replacement of Zn with Mn is perfectly feasible and at least partly allows for the identification of some sites preferred by the Mn(II) metals. These calculations, combined with luminescence studies, suggest a distribution of the Mn(II) in the clusters. The room temperature emission spectra of clusters 1c-d display a significant red shift relative to the all zinc cluster 3, with a peak maximum centered at 730 nm. Clusters 2c-d display a peak maximum at 640 nm in their emission spectra.     

Magneto-optical properties of Cd(1-x)Mn(x)S nanoparticles: influences of magnetic doping, Mn2+ ions localization, and quantum confinement

Cd(1-x)Mn(x)S nanoparticles (NPs) were successfully grown in a glass matrix and investigated by optical absorption (OA), magnetic circularly polarized photoluminescence (MCPL) measurements, and magnetic force microscopy (MFM). The room temperature OA spectra have revealed the formation of two groups of Cd(1-x)Mn(x)S NPs with different sizes: bulk-like nanocrystals (NCs) and quantum dots (QDs). The MCPL spectra were recorded at 2.0 K with several magnetic fields up to 15 T, allowing a detailed comparison between the degrees of circular polarization of the two groups of NPs. The different behaviours of magneto-optical properties of bulk-like NCs and QDs were explained by taking into account a considerable alteration of exchange interaction between the carrier spins and the substitutional doping magnetic ions incorporated into the NPs. As a main result, we have demonstrated that self-purification is the dominant mechanism that controls the doping in semiconductor QDs grown by the melting-nucleation synthesis approach due to the relatively high temperature that was used in thermal annealing of samples.     

Formation of Zn(1-x)MnxS nanowires within mesoporous silica of different pore sizes

Arrays of highly ordered Zn(1-x)MnxS quantum wires with x ranging from 0.01 to 0.3 and with lateral dimensions of 3, 6, and 9 nm were synthesized within mesoporous SiO2 host structures of the MCM-41 and SBA-15 type. The hexagonal symmetry of these arrays (space group p6m) and the high degree of order was confirmed by X-ray diffraction and transmission electron microscopy (TEM) studies. Physisorption measurements show the progressive filling of the pores of the SiO2 host structures, while TEM and Raman studies reveal the wire-like character of the incorporated Zn(1-x)MnxS nanostructures. X-ray absorption near-edge structure, extended X-ray absorption fine structure, photoluminescence excitation (PLE), and electron paramagnetic resonance studies confirm the good crystalline quality of the incorporated Zn(1-x)MnxS guest species and, in particular, that the Mn2+ ions are randomly distributed and are situated on tetrahedrally coordinated cation sites of the Zn(1-x)MnxS wires for all x up to 0.3. The amount of Mn2+ ions loosely bound to the surface of the Zn(1-x)MnxS nanowires is less than 4% of the total Mn content even for the 3 nm nanostructures up to the highest Mn content of x = 0.3. The effects of the reduction of the lateral dimensions on electronic properties of the diluted magnetic semiconductor were studied by PLE spectroscopy. Due to the quantum confinement of the excitons in the wires an increase of the direct band gap with decreasing particle size is observed.     

Large scale synthesis of stable tricolor Zn(1-x)Cd(x)Se core/multishell nanocrystals via a facile phosphine-free colloidal method

Here we report a new "green" method to synthesize Zn(1-x)Cd(x)Se (x = 0-1) and stable red-green-blue tricolor Zn(1-x)Cd(x)Se core/shell nanocrystals using only low cost, phosphine-free and environmentally friendly reagents. The first excitonic absorption peak and photoluminescence (PL) position of the Zn(1-x)Cd(x)Se nanocrystals (the value of x is in the range 0.005-0.2) can be fixed to any position in the range 456-540 nm. There is no red or blue shift in the entire reaction process. Three similar sizes of alloyed Zn(1-x)Cd(x)Se nanocrystals with blue, green, and yellow emissions were successfully selected as cores to synthesize high quality blue, green, and red core/shell nanocrystal emitters. For the synthesis of core/shell nanocrystals with a high quantum yield (QY) and stability, the selection of shell materials has been proven to be very important. Therefore, alternative protocols have been used to optimize thick shell growth. ZnSe/ZnSe(x)S(1-x) and CdS/Zn(1-x)Cd(x)S have been found as an excellent middle multishell to overcoat between the alloyed Zn(1-x)Cd(x)Se core and ZnS outshell. The QYs of the as-synthesized core/shell alloyed Zn(1-x)Cd(x)Se nanocrystals can reach 40-75%. The Cd content is reduced to less than 0.1% for Zn(1 -x)Cd(x)Se core/shell nanocrystals with emissions in the range 456-540 nm. More than 15 g of high quality Zn(1-x)Cd(x)Se core/shell nanocrystals were prepared successfully in a large scale, one-pot reaction. Importantly, the emissions of such thick multishell nanocrystals are not susceptible to ligand loss and stability in various physiological conditions.     

Modulation of the intercalation properties of copper-zinc mixed-metal phosphonate materials

New layered mixed divalent metal vinylphosphonates Cu(II) (1-x)Zn(II) (x)(O(3)PC(2)H(3)).H(2)O have been prepared from a range of pre-formed copper-zinc oxides Cu(II) (1-x)Zn(II) (x)O obtained by isomorphous substitution of zinc into the tenorite-type structure of Cu(II)O. The corresponding mixed divalent copper-zinc vinylphosphonates have been characterised by powder X-ray diffraction, elemental analysis, infrared spectroscopy and thermogravimetric analysis. All compounds have been shown to consist of a single-phase solid solution that crystallises in an monoclinic unit cell, space group P2(1)/c with a=9.86-9.90, b=7.61-7.64, c=7.32-7.35 A and beta=95.9-96 degrees, with the exception of the pure zinc vinylphosphonate (x=1), the structure of which is comparable to other Zn(II)(O(3)PR).H(2)O materials. Studies of the intercalation of n-butylamine into the range of copper-zinc vinylphosphonates have demonstrated that significant modulation of the adsorption properties occurs; whereas one mole of amine is intercalated into the pure zinc vinylphosphonate to give Zn(II)(O(3)PC(2)H(3)).(C(4)H(9)NH(2)), for all other members of the series two moles of amine are coordinated to give intercalated compounds of composition Cu(II) (1-x)Zn(II) (x)(O(3)PC(2)H(3)).[(C(4)H(9)NH(2))(1-x)(C(4)H(9)NH(2))(x)](2) from which the amine can be sequentially removed from the different metal sites; this opens up possibilities for further applications of these materials.     

Soft X-ray characterization of Zn(1-x)Sn(x)O(y) electronic structure for thin film photovoltaics

Zinc tin oxide (Zn(1-x)Sn(x)O(y)) has been proposed as an alternative buffer layer material to the toxic, and light narrow-bandgap CdS layer in CuIn(1-x),Ga(x)Se(2) thin film solar cell modules. In this present study, synchrotron-based soft X-ray absorption and emission spectroscopies have been employed to probe the densities of states of intrinsic ZnO, Zn(1-x)Sn(x)O(y) and SnO(x) thin films grown by atomic layer deposition. A distinct variation in the bandgap is observed with increasing Sn concentration, which has been confirmed independently by combined ellipsometry-reflectometry measurements. These data correlate directly to the open circuit potentials of corresponding solar cells, indicating that the buffer layer composition is associated with a modification of the band discontinuity at the CIGS interface. Resonantly excited emission spectra, which express the admixture of unoccupied O 2p with Zn 3d, 4s, and 4p states, reveal a strong suppression in the hybridization between the O 2p conduction band and the Zn 3d valence band with increasing Sn concentration.