Magnetic properties of doped II-VI semiconductor nanocrystals

We investigate the magnetic properties of two typical II-VI semiconducting nanocrystals, namely, ZnS and ZnO, doped with various concentrations of a transition metal ion, Mn. A wide range of dopant concentrations was explored without changing the size of the nanocrystal, thereby allowing us to study the concentration dependence of various properties independent of any size variation of the host. However, only small doping concentrations could be realized in each case. All the studies were thus carried out with ZnS and ZnO nanocrystals with their respective average sizes fixed at about 1.6 and 4.7 nm. We show that the magnetic properties of such doped systems, remaining paramagnetic down to the lowest temperature (<3 K), can provide important and accurate information concerning the dopant level in such samples.     

Syntheses and applications of Mn-doped II-VI semiconductor nanocrystals

Luminescent Mn-doped II-VI semiconductor nanocrystals have been intensively investigated over the last ten years. Several semiconductor host materials such as ZnS, CdS, and ZnSe have been used for Mn-doped nanocrystals with different synthetic routes and surface passivation. Beyond studies of their fundamental properties including photoluminescence and size, these luminescent nanocrystals have now been tested for practical applications such as electroluminescent displays and biological labeling agents (biomarkers). Here, we first review ZnS:Mn, CdS:Mn/ZnS core/shell, and ZnSe:Mn nanocrystal systems in terms of their synthetic chemistries and photoluminescent properties. Second, based on ZnS:Mn and CdS:Mn/ZnS core/shell nanocrystals as electroluminescent components, direct current electroluminescent devices having a hybrid organic/inorganic multilayer structure are reviewed. Highly luminescent and photostable CdS:Mn/ZnS nanocrystals can further be used as the luminescent biomarkers and some preliminary results are also discussed here.     

The length distribution function of semiconductor filamentary nanocrystals

The length distribution function of semiconductor filamentary nanocrystals is analyzed based on the adsorption–diffusion growth model. It is demonstrated that the asymptotic distribution has a Gaussian shape. If the diffusion flux to the apex comes from the entire lateral surface, the average length increases exponentially with time, and the mean-square deviation is proportional to the average length (exponential growth regime). If the diffusion collection of adatoms is limited to the top of the crystal, the average length increases linearly and the mean-square deviation equals the square root of average length (linear Poisson growth regime). In real-world systems, transition from exponential to Poisson growth occurs at lengths of the order of the diffusion length of adatoms. The dispersion of the distribution is actually defined at the exponential stage. The general classification of length distributions of various crystals is given. It is demonstrated that self-induced GaN- and Ga-catalytic III–V filamentary nanocrystals should be more homogeneous than Au-catalytic ones.     

Determination of size distributions in nanosized powders by TEM,XRD, and SAXS

Crystallite size distributions and particle size distributions were determined by transmissions electron microscopy (TEM), X-ray powder diffraction (XRD), and small-angle X-ray scattering (SAXS) for three commercially available TiO₂ powders (P25, UV100, and TiO2_5?nm) and one SSEC produced powder (SSEC78). The theoretical Guinier model was fitted to the experimental obtained XRD data and compared to analytical expressions. Modeling of the XRD spectra showed a difference between the analytical size dependent expressions and the theoretical Guinier model. Primary particle size distributions were extracted from SAXS measurements by the hard sphere model including an interparticle interference factor. The sizes obtained from SAXS were smaller than the sizes obtained from the XRD experiments; however, a good agreement was obtained between the two techniques. Electron microscopy confirmed the primary particle sizes and the shapes obtained by XRD and SAXS. The SSEC78 powder and the commercially available powders showed different morphologies, but SSEC78, UV100, and TiO2_5?nm all consisted of both primary particles as well as a secondary structure comprised of nanosized primary particles agglomeration into larger clusters. P25 showed the largest primary particle size, but did not show a secondary structure.     

General synthesis of manganese-doped II-VI and III-V semiconductor nanowires

A general approach for the synthesis of manganese-doped II-VI and III-V nanowires based on metal nanocluster-catalyzed chemical vapor deposition has been developed. High-resolution transmission electron microscopy and energy-dispersive X-ray spectroscopy studies of Mn-doped CdS, ZnS, and GaN nanowires demonstrate that the nanowires are single-crystal structures and homogeneously doped with controllable concentrations of manganese ions. Photoluminescence measurements of individual Mn-doped CdS and ZnS nanowires show characteristic pseudo-tetrahedral Mn2+ ((4)T1-->(6)A1) transitions that match the corresponding transitions in bulk single-crystal materials well. Photoluminescence studies of Mn-doped GaN nanowires suggest that manganese is incorporated as a neutral (Mn3+) dopant that partially quenches the GaN band-edge emission. The general and controlled synthesis of nanowires doped with magnetic metal ions opens up opportunities for fundamental physical studies and could lead to the development of nanoscale spintronic devices.     

Luminescent CdTe and CdSe semiconductor nanocrystals: preparation, optical properties and applications

The novel optical and electrical properties of luminescent semiconductor nanocrystals are appealing for ultrasensitive multiplexing and multicolor applications in a variety of fields, such as biotechnology, nanoscale electronics, and opto-electronics. Luminescent CdSe and CdTe nanocrystals are archetypes for this dynamic research area and have gained interest from diverse research communities. In this review, we first describe the advances in preparation of size- and shape-controlled CdSe and CdTe semiconductor nanocrystals with the organometallic approach. This article gives particular focus to water soluble nanocrystals due to the increasing interest of using semiconductor nanocrystals for biological applications. Post-synthetic methods to obtain water solubility, the direct synthesis routes in aqueous medium, and the strategies to improve the photoluminescence efficiency in both organic and aqueous phase are discussed. The shape evolution in aqueous medium via self-organization of preformed nanoparticles is a versatile and powerful method for production of nanocrystals with different geometries, and some recent advances in this field are presented with a qualitative discussion on the mechanism. Some examples of CdSe and CdTe nanocrystals that have been applied successfully to problems in biosensing and bioimaging are introduced, which may profoundly impact biological and biomedical research. Finally we present the research on the use of luminescent semiconductor nanocrystals for construction of light emitting diodes, solar cells, and chemical sensors, which demonstrate that they are promising building blocks for next generation electronics.     

Electrical and optical properties of semiconductor nanocrystals

Application of semiconductor nanocrystals in optoelectronic devices requires an understanding not only of their emission and absorption properties, but also of the processes of charge injection and transport in nanocrystalline films. Here, we present measurements of the electrical properties of nanocrystalline films and of blends of nanocrystals with conjugated polymers. We also describe the attachment of nanocrystals to semiconductor surfaces, and we investigate the emission of nanocrystalline films in microcavity structures and at high excitation intensities.     

Orientational distribution of parent–daughter structure of isotactic polypropylene: a study using simultaneous synchrotron WAXS and SAXS

The molecular and lamellar orientations of injection-moulded isotactic polypropylene were investigated using simultaneous wide- and small-angle X-ray scatterings. In order to obtain the meaningful degree of molecular orientation with respect to the flow direction, the axis orientations of parent and daughter lamellae were separately calculated. The molecular orientation of thin material is consistent with the lamellar orientation. However, the decrease in the lamellar orientation of thick material is associated with a constant degree of molecular orientation, which would indicate an intra slip between parent lamellae along the flow direction.     

Alloyed Mn-Cu-In-S nanocrystals: a new type of diluted magnetic semiconductor quantum dots

A new type of Mn-Cu-In-S diluted magnetic semiconductor quantum dots was synthesized and reported for the first time. The quantum dots, with no highly toxic elements, not only show the same classic diluted magnetic behavior as Mn-doped CdSe, but also exhibit tunable luminescent properties in a relatively large window from 542 to 648?nm. An absolute photoluminescence quantum yield up to 20% was obtained after the shell growth of ZnS. This kind of magnetic/luminescent bi-functional Mn-Cu-In-S/ZnS core/shell quantum dot might serve as promising nanoprobes for use in dual-mode optical and magnetic resonance imaging techniques.     

Track membranes with embedded semiconductor nanocrystals: structural and optical examinations

We studied the optical properties of poly(ethylene terephthalate) ion track membranes of 1.5, 0.5 and 0.05?μm?pores impregnated with luminescent semiconductor CdSe/ZnS nanocrystals of different diameters (2.5 and 5?nm). The nanocrystals were embedded from their colloidal solutions in toluene by the immersion of a membrane in a colloidal solution. Localization of quasi-isolated weakly interacting CdSe/ZnS nanocrystals in a loosened layer on the track pore wall surface along with the existence of empty pores was demonstrated. We observed also the spatial separation of nanocrystals of 2.5 and 5?nm in size along the 50?nm pores.     

Optical properties of water-soluble Co:ZnS semiconductor nanocrystals synthesized by a hydrothermal process

Water-soluble ZnS:Co²⁺ nanocrystals (NCs) were synthesized by a low temperature hydrothermal process using 3-mercaptopropionic acid (MPA) as capping agent and the influence of doping on the optical properties of ZnS:Co²⁺ NCs was investigated. It was found that the ZnS:Co²⁺ NCs are highly crystalline and show zinc blende structure with an average particle size of about 7 nm. The lattice constant of the ZnS:Co²⁺ NCs decreases slightly by the introduction of Co²⁺. The Co dopants were well doped into the ZnS:Co²⁺ NCs, as confirmed by X-ray photoelectron spectroscopy(XPS) and the ⁴A₂(F) → ⁴T₁(P) transition of Co²⁺ was detected from the UV-vis absorption spectra. The absorption edge of the ZnS:Co²⁺ NCs is blue-shifted as compared with that of bulk ZnS, indicating the quantum confinement effect. The PL intensity of the NCs shows the maximum value when the Fe-doping concentration is 0.5 at.%.     

Self-assembly and alignment of semiconductor nanoparticles on cellulose nanocrystals

The synthesis of cadmium sulfide (CdS), zinc sulfide (ZnS), and lead sulfide (PbS) nanoparticle chains on cellulose nanocrystal (CNC) templates can be accomplished by the reaction of the precursor salts. The use of a cationic surfactant, cetyltrimethylammonium bromide (CTAB), was critical for the synthesis of well-defined semiconductor nanoparticle chains on the surface of the CNCs. The semiconductor nanoparticle particle size and packing density on CNC surface could be controlled by the variation of the precursor concentration and the pH of the salt solution.     

Correlating dynamics and selectivity in adsorption of semiconductor nanocrystals onto a self-organized pattern

Selective adsorption of semiconductor nanocrystals onto an organic self-organized pattern shows a time-dependent behavior. By studying the wetting behavior of delivered solvent (1-phenyloctane) on a lipid self-organized pattern and determining the adhesion energy between semiconductor nanocrystals and substrate, we obtain a correlation between dynamics and selectivity in adsorption of semiconductor nanocrystals onto the pattern by constructing a potential energy landscape. Two consecutive steps for selective adsorption of nanocrystals onto the self-organized pattern have been established: the first one is the molecule exchange of 1-phenyloctane and lipid molecules to form the adsorption sites for nanocrystals, and the second one is the adsorption of nanocrystals onto the adsorption sites due to the strong interaction between nanocrystals and substrate.     

Synthesis and characterization of semimagnetic semiconductor nanocrystals for spin electronics

The technique of pulsed laser deposition and colloidal chemistry methods have been applied for synthesis of semimagnetic semiconductor Cd_1−xMn_xTe nanocrystals embedded in dielectric matrix. The performed analysis suggests a narrower size distribution for the colloidal nanoparticles. Optical absorption, Faraday rotation and photoluminescence spectroscopy have been used to characterize the grown quantum dot structures. The magneto-optical spectra of the Cd_1−xMn_xTe nanocrystals exhibit peculiarities typical for bulk semimagnetic semiconductors due to the strong spin-exchange interaction between band carriers and magnetic ions and simultaneously manifest some features because of confinement effects in low dimensional structures.     

Fe：ZnSe/ZnS核-壳纳米晶的微乳液法合成及光学性能研究

在环己烷/Triton X-100/水/异丙醇W/O型微乳液体系中制备了Fe：ZnSe/ZnS核-壳纳米晶。采用X射线衍射仪（XRD）分析了产物的结构,利用透射电子显微镜（TEM）观察了产物的形貌,采用光致发光（PL）谱、紫外-可见（UV-Vis）吸收谱测试了产物的光学性能。着重研究了水与表面活性剂的摩尔比（R值）对合成产物的光学性能的影响。并对相关现象潜在的机理进行了讨论。     

Raman and XRD studies of Ge nanocrystals in alumina films grown by RF-magnetron sputtering

Germanium (Ge) nanocrystals (NCs) embedded in alumina thin films were produced by deposition on fused silica and silicon (111) substrates using radio-frequency (RF) magnetron sputtering. The films were characterised by both Raman and X-ray diffraction (XRD) spectroscopy. The deposition conditions were optimised in order to obtain crystalline Ge nanoparticles. In as-deposited films, the typical NC size was ∼3 nm as estimated by means of X-ray diffraction. Raman spectra taken from as-deposited films revealed both amorphous and crystalline semiconductor phases. Annealing was performed in order to improve the crystallinity of the semiconductor phase in the films. After a 1 h annealing at 800 °C the mean NC size estimated from the XRD data and Raman spectra increased to ∼6.5 nm. An increase in the crystallinity of the Ge phase was also confirmed by the Raman spectroscopy data.     

A facile and general approach to polynary semiconductor nanocrystals via a modified two-phase method

Cu(2)ZnSnS(4) nanocrystals were synthesized through a modified two-phase method and characterized with transmission electron microscopy (TEM), powder x-ray diffraction (XRD) and UV-vis spectroscopy. Inorganic metal salts were dissolved in the polar solvent triethylene glycol (TEG) and then transferred into the non-polar solvent 1-octadecene (ODE) by forming metal complexes between metal ions and octadecylamine (ODA). Since nucleation and growth occur in the single phase of the ODE solution, nanocrystals could be produced with qualities similar to those obtained through the hot-injection route. Balancing the reactivity of the metal precursors is a key factor in producing nanocrystals of a single crystalline phase. We found that increasing the reaction temperature increases the reactivity of each of the metal precursors by differing amounts, thus providing the necessary flexibility for obtaining a balanced reactivity that produces the desired product. The versatility of this synthesis strategy was demonstrated by extending it to the production of other polynary nanocrystals such as binary (CuS), ternary (CuInS(2)) and pentanary (Cu(2 - x)Ag(x)ZnSnS(4)) nanocrystals. This method is considered as a green synthesis route due to the use of inorganic metal salts as precursors, smaller amounts of coordinating solvent, shorter reaction time and simpler post-reaction treatment.     

Versatile synthesis of yolk/shell hybrid nanocrystals via ion-exchange reactions for novel metal/semiconductor and semiconductor/semiconductor conformations

Yolk/shell (Y–S) hybrid nanoarchitectures, owing to the interior voids created for individualized catalyst applications, have emerged as new candidates for effectively isolating catalytic species. However, the well-defined hollow interiors with flexible core and shell compositions—such as noble-metal cores, metal-oxide cores, and widespread semiconductor shells—and a flexible anisotropic shape are far from the requirements. In particular, the introduction of catalytic noble metals or metal-oxide nanocrystals (NCs) with isotropic or anisotropic shapes into various hollow semiconductor structures with well-defined morphologies has been rarely reported but is urgently needed. Herein, we propose a strategy involving the careful sulfuration of as-prepared cavity-free core/shell NCs or metal-oxide NCs followed by phosphine-initialized cation-exchange reactions for preparing metal@semiconductor and metal oxide@semiconductor (II-VI) Y–S NCs. The geometry, size, and conformations of the core and shell are fully and independently considered. New and unprecendented metal@semiconductor and metal oxide@semiconductor (II-VI) Y–S NCs are prepared via widespread phosphine-initialized cation-exchange reactions.

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Mineralization of semiconductor nanocrystals on peptide-coated bionanotubes and their pH-dependent morphology changes

While various mineralizing peptides have been applied to grow metal nanoparticles on bionanotube templates, the semiconductor nanoparticle growth on nanotubes has not extensively been explored yet. In this paper, various semiconductor nanocrystals were grown on the bionanotubes surfaces with controlled sizes. When three synthetic peptides, which recognize and selectively bind Ge, Ti, and Cu ions, respectively, were incorporated on template bionanotube surfaces, highly crystalline and monodisperse Ge, TiO2, and Cu2S nanocrystals were grown on the tube surfaces. The sizes of these nanocrystals could be tuned as a function of pH, and larger semiconductor nanocrystals were grown as the pH of growth solutions was increased. All of these nanocrystals from smaller sizes to larger sizes had the same crystallinity. This peptide-controlled nanocrystal growth technique will be very useful to prepare semiconductor nanowires as building blocks for future microelectronics, whose band gaps can be tuned by the sizes of coated semiconductor nanoparticles via their quantum confinement effect. The novelty of this approach in the electronic device fabrication is that the semiconductor nanocrystal size control can be achieved by controlling peptide configurations via pH change, and this control may tune electronic structures and band gaps of the resulting semiconductor nanowires.