Morphological control and luminescent properties of CeF3 nanocrystals

The nanocrystals of CeF3 with the hexagonal structure and different morphologies such as the disk, the rod, and the dot have been successfully synthesized via a mild ultrasound assisted route from an aqueous solution of cerium nitrate and different fluorine sources (KBF4, NaF, NH4F). The use of different fluorine sources has a remarkable effect on the morphology of the final product. The luminescence and UV-vis absorption properties of CeF3 nanocrystals with different morphologies have been investigated. Compared with other shape nanocrystals, the luminescence intensity of the disklike nanocrystals is obviously enhanced. It is suggested that the function-improved materials could be obtained by tailoring the shape of the CeF3 nanocrystals.

Sonochemical synthesis and photoluminescent property of YVO4 : Eu nanocrystals

YVO4 nanocrystals doped with 10.0 mol% Eu3+ have been synthesized from an aqueous solution of ( Y, Eu)( NO3) (3) and NH4VO3 with or without ultrasonic irradiation. The ultrasonic irradiation has a strong effect on the morphology of the YVO4: Eu particles. The spindle-like particles with an equatorial diameter of 90 - 150 nm and a length of 250 - 300 nm could be obtained with ultrasonic irradiation, whereas only nanoparticles were produced without ultrasonic irradiation. The photoluminescence intensity of YVO4: Eu of the spindle-like particles was largely improved compared with that of the nanoparticles. The possible formation mechanism of the spindle-like particles of YVO4: Eu with the application of ultrasonic irradiation was discussed in this paper.

Controllable synthesis of highly luminescent and monodisperse CdS nanocrystals by a two-phase approach under mild conditions

Highly luminescent and monodisperse CdS nanocrystals (see Figure) have been synthesized using a two-phase approach. The synthesis of CdS nanocrystals at the liquid-liquid interface was easy, safe, and highly reproducible, and the reaction conditions were mild and controllable.

Synthesis of barium lithium fluoride nanocrystals using reverse micelles as microemulsion

Barium lithium fluoride nanocrystals were synthesized in cetyltrimethylammonium bromide (CTAB)/2-octanol/water microemulsion systems. The impurity peaks in XRD patterns were not determined. The result of SEM confirmed that the average sizes and shape of the BaLiF3 nanocrystals. The formation of BaLiF3 and particles size were strongly affected by water content. With increasing water content and reaction times, the size of the particle. increases. Meanwhile, the solvent was also found to play a key role in the synthesis of the BaLiF3 nanocrystals.

Synthesis of highly faceted multiply twinned gold nanocrystals stabilized by polyoxometalates

A novel and facile chemical synthesis of highly faceted multiply twinned gold nanocrystals is reported. The gold nanocrystals are hexagonal in transmission electron microscopy and icosahedral in scanning electron microscopy. Phosphotungstic acid (PTA), which was previously reduced, serves as a reductant and stabilizer for the synthesis of gold nanocrystals. The PTA-gold nanocomposites are quite stable in aqueous solutions, and electrochemically active towards the hydrogen evolution reaction.

Well-organized structures of ZnS semiconductor nanocrystals using amphiphilic triblock copolymer aggregates as templates

Ring- and rod-shaped P4VP-b-PS-b-P4VP ( PS, polystyrene; P4VP, poly( 4-vinylpyridine)) triblock copolymer aggregates are used as templates to synthesize ZnS nanocrystals. Herein, PVP serves as both a stabilizing agent and a structure- directing agent. The resulting ZnS nanocrystals could be aligned along the corona of the copolymer aggregates in near-perfect structures through control of both the molar ratio of Zn2+ to P4VP and the reaction time. The diameter of the as-synthesized ZnS layer on the surface of polymer template is approximate 2 - 3 nm. High-resolution transmission electron microscopy images reveal that the ZnS particles are single crystal in a zinc blende structure. This method provides a simple, reproducible route at room temperature to prepare assembled hybrid polymer - semiconductor nanocrystal nanocomposites.

Syntheses of Ag, PbSe, and PbTe nanocrystals and their binary self-assembly exploration at low size-ratio

Nanocrystals of Ag, PbSe, and PbTe were prepared via a high-temperature organic solution approach, respectively. Using a size-selection technique, the size-distribution of each set of nanocrystals could be fine-tuned and finally monodisperse products were achieved. Superlattice structure of binary self-assemblies in low size-ratio were also explored and characterized by transmission electron microscopy. It is realized that a success of achieving binary self-assembly pattern is greatly dependent on several key factors including particle size-distributions, relative concentrations of both components, as well as the size-ratios between Ag and PbSe (or PbTe) nanocrystals.

Optical spectroscopy properties of KMgF3 : Eu2+ nanocrystals and powder synthesized by microemulsion and solvothermal process

Nanocrystals and powders of KMgF3 doped with Eu2+ were synthesized by the microemulsion method and the solvothermal process, respectively. The emission and excitation spectra of KMgF3:Eu2+ phosphors were measured and compared with those of the samples synthesized through a solid. state reaction, Bridgman-Stockbarger method, and mild hydrothermal technique. The KMgF3: Eu2+ samples synthesized by means of the microemulsion method and the solvothermal process show only a sharp emission peak located at 360 nm, in the emission spectra, which arises from the f -> f(P-6(1/2)-> S-8(1/2)) transition of Eu2+. The broad emission bands appear at 420 nm,,which arises from Eu2+ <- O2- cannot be observed(in the mild hydrothermal and single crystal samples, the emission peak at 420 nm besides the emission of Eu2+ at 360 nm is observed). In the excitation spectrum of the KMgF3: Eu2+ samples synthesized by the microemulsion method and the solvothermal process, the excitation peaks show an intensive blue shift. The blue shift can he attributed to the lower oxygenic content in the KMgF3: Eu2+ samples synthesized by the microemulsion method and the solvothermal process.

Catalytic oxidation of cyclohexane to cyclohexanol and cyclohexanone over Co3O4 nanocrystals with molecular oxygen

Co3O4 nanocrystals with average particle sizes of 30 and 50 run were synthesized using cobalt nitrate as precursor, and were characterized by X-ray diffraction (XRD), nitrogen adsorption, transmission electron microscopy (TEM), and Fourier transform infrared (FT-IR) spectroscopy. Catalytic oxidation of cyclohexane with molecular oxygen was studied over Co3O4 nanocrystals. These catalysts showed obviously higher activities as compared to Co3O4 prepared by the conventional methods, Co3O4/Al2O3, or homogeneous cobalt catalyst under comparable reaction conditions. The 89.1% selectivity to cyclohexanol and cyclohexanone at 7.6% conversion of cyclohexane was realized over 50 nm sized Co3O4 nanocrystals at 393 K for 6 h. (c) 2005 Elsevier B.V. All rights reserved.

Nanoscale electronic properties of conjugated polymers and nanocrystals

The objective of this thesis is the exploration and characterisation of the nanoscale electronic properties of conjugated polymers and nanocrystals. In Chapter 2, the first application of conducting-probe atomic force microscopy (CP-AFM)-based displacement-voltage (z-V) spectroscopy to local measurement of electronic properties of conjugated polymer thin films is reported. Charge injection thresholds along with corresponding single particle gap and exciton binding energies are determined for a poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] thin film. By performing measurements across a grid of locations on the film, a series of exciton binding energy distributions are identified. The variation in measured exciton binding energies is in contrast to the smoothness of the film suggesting that the variation may be attributable to differences in the nano-environment of the polymer molecules within the film at each measurement location. In Chapter 3, the CP-AFM-based z-V spectroscopy method is extended for the first time to local, room temperature measurements of the Coulomb blockade voltage thresholds arising from sequential single electron charging of 28 kDa Au nanocrystal arrays. The fluid-like properties of the nanocrystal arrays enable reproducible formation of nanoscale probe-array-substrate junctions, allowing the influence of background charge on the electronic properties of the array to be identified. CP-AFM also allows complementary topography and phase data to be acquired before and after spectroscopy measurements, enabling comparison of local array morphology with local measurements of the Coulomb blockade thresholds. In Chapter 4, melt-assisted template wetting is applied for the first time to massively parallel fabrication of poly-(3-hexylthiophene) nanowires. The structural characteristics of the wires are first presented. Two-terminal electrical measurements of individual nanowires, utilising a CP-AFM tip as the source electrode, are then used to obtain the intrinsic nanowire resistivity and the total nanowire-electrode contact resistance subsequently allowing single nanowire hole mobility and mean nanowire-electrode barrier height values to be estimated. In Chapter 5, solution-assisted template wetting is used for fabrication of fluorene-dithiophene co-polymer nanowires. The structural characteristics of these wires are also presented. Two-terminal electrical measurements of individual nanowires indicate barrier formation at the nanowire-electrode interfaces and measured resistivity values suggest doping of the nanowires, possibly due to air exposure. The first report of single conjugated polymer nanowires as ultra-miniature photodetectors is presented, with single wire devices yielding external quantum efficiencies ~ 0.1 % and responsivities ~ 0.4 mA/W under monochromatic illumination.

Synthesis, characterisation and applications of group IV nanocrystals

Group IV materials such as silicon nanocrystals (Si NCs) and carbon quantum dots (CQDs) have received great attention as new functional materials with unique physical/chemical properties that are not found in the bulk material. This thesis reports the synthesis and characterisation of both types of nanocrystal and their application as fluorescence probes for the detection of metal ions. In chapter 2, a simple method is described for the size controlled synthesis of Si NCs within inverse micelles having well defined core diameters ranging from 2 to 6 nm using inert atmospheric synthetic methods. In addition, ligands with different molecular structures were utilised to reduce inter-nanocrystal attraction forces and improve the stability of the NC dispersions in water and a variety of organic solvents. Regulation of the Si NCs size is achieved by variation of the surfactants and addition rates, resulting high quality NCs with standard deviations (σ = Δd/d) of less than 10 %. Large scale production of highly mondisperse Si NC was also successfully demonstrated. In chapter 3, a simple solution phase synthesis of size monodisperse carbon quantum dots (CQDs) using a room temperature microemulsion strategy is demonstrated. The CQDs are synthesized in reverse micelles via the reduction of carbon tetrachloride using a hydride reducing agent. CQDs may be functionalised with covalently attached alkyl or amine monolayers, rendering the CQDs dispersible in wide range of polar or non-polar solvents. Regulation of the CQDs size was achieved by utilizing hydride reducing agents of different strengths. The CQDs possess a high photoluminescence quantum yield in the visible region and exhibit excellent photostability. In chapter 4, a simple and rapid assay for detection of Fe3+ ions was developed, based on quenching of the strong blue-green Si NC photoluminescence. The detection method showed a high selectivity, with only Fe3+ resulting in strong quenching of the fluorescence signal. No quenching of the fluorescence signal was induced by Fe2+ ions, allowing for solution phase discrimination between the same ion in different charge states. The optimised sensor system showed a sensitive detection range from 25- 900 μM and a limit of detection of 20.8 μM

Synthesis, functionalisation and characterisation of germanium nanocrystals & their applications

In the last two decades, semiconductor nanocrystals have been the focus of intense research due to their size dependant optical and electrical properties. Much is now known about how to control their size, shape, composition and surface chemistry, allowing fine control of their photophysical and electronic properties. However, genuine concerns have been raised regarding the heavy metal content of these materials, which is toxic even at relatively low concentrations and may limit their wide scale use. These concerns have driven the development of heavy metal free alternatives. In recent years, germanium nanocrystals (Ge NCs) have emerged as environmentally friendlier alternatives to II-VI and IV-VI semiconductor materials as they are nontoxic, biocompatible and electrochemically stable. This thesis reports the synthesis and characterisation of Ge NCs and their application as fluorescence probes for the detection of metal ions. A room-temperature method for the synthesis of size monodisperse Ge NCs within inverse micelles is reported, with well-defined core diameters that may be tuned from 3.5 to 4.5 nm. The Ge NCs are chemically passivated with amine ligands, minimising surface oxidation while rendering the NCs dispersible in a range of polar solvents. Regulation of the Ge NCs size is achieved by variation of the ammonium salts used to form the micelles. A maximum quantum yield of 20% is shown for the nanocrystals, and a transition from primarily blue to green emission is observed as the NC diameter increases from 3.5 to 4.5 nm. A polydisperse sample with a mixed emission profile is prepared and separated by centrifugation into individual sized NCs which each showed blue and green emission only, with total suppression of other emission colours. A new, efficient one step synthesis of Ge NCs with in situ passivation and straightforward purification steps is also reported. Ge NCs are formed by co-reduction of a mixture of GeCl4 and n-butyltrichlorogermane; the latter is used both as a capping ligand and a germanium source. The surface-bound layer of butyl chains both chemically passivates and stabilises the Ge NCs. Optical spectroscopy confirmed that these NCs are in the strong quantum confinement regime, with significant involvement of surface species in exciton recombination processes. The PL QY is determined to be 37 %, one of the highest values reported for organically terminated Ge NCs. A synthetic method is developed to produce size monodisperse Ge NCs with modified surface chemistries bearing carboxylic acid, acetate, amine and epoxy functional groups. The effect of these different surface terminations on the optical properties of the NCs is also studied. Comparison of the emission properties of these Ge NCs showed that the wavelength position of the PL maxima could be moved from the UV to the blue/green by choice of the appropriate surface group. We also report the application of water-soluble Ge NCs as a fluorescent sensing platform for the fast, highly selective and sensitive detection of Fe3+ ions. The luminescence quenching mechanism is confirmed by lifetime and absorbance spectroscopies, while the applicability of this assay for detection of Fe3+ in real water samples is investigated and found to satisfy the US Environmental Protection Agency requirements for Fe3+ levels in drinkable water supplies.

Universal Quake Statistics: From Compressed Nanocrystals to Earthquakes.

Slowly-compressed single crystals, bulk metallic glasses (BMGs), rocks, granular materials, and the earth all deform via intermittent slips or "quakes". We find that although these systems span 12 decades in length scale, they all show the same scaling behavior for their slip size distributions and other statistical properties. Remarkably, the size distributions follow the same power law multiplied with the same exponential cutoff. The cutoff grows with applied force for materials spanning length scales from nanometers to kilometers. The tuneability of the cutoff with stress reflects "tuned critical" behavior, rather than self-organized criticality (SOC), which would imply stress-independence. A simple mean field model for avalanches of slipping weak spots explains the agreement across scales. It predicts the observed slip-size distributions and the observed stress-dependent cutoff function. The results enable extrapolations from one scale to another, and from one force to another, across different materials and structures, from nanocrystals to earthquakes.