Dong Hee Son

Ultrasensitive Copper(II) Detection Using Plasmon-Enhanced and Photo-Brightened Luminescence of CdSe Quantum Dots

Here, we present a simple platform for the use of the enhanced emission of 16-mercaptohexadecanoic acid (16-MHA) capped CdSe quantum dots (QDs) as a probe for ultrasensitive copper(II) detection. In this study, the photoluminescence (PL) of the QDs was first enhanced by Ag nanoprisms which were self-assembled on Si surfaces and then further increased by photobrightening. Using this approach, the control and different analytes could be readily probed all on a single platform using fluorescence microscopy. The enhanced PL intensity of CdSe QDs was selectively quenched in the presence of Cu(2+), accompanied by the emergence of a new red-shifted luminescence band. The quenching mechanism was found to be due to a cation exchange mechanism as confirmed by X-ray photoelectron spectroscopy (XPS) measurements. Herein, we have demonstrated that this simple methodology can offer a rapid and reliable detection of Cu(2+) with a detection limit as low as 5 nM and a dynamic range up to 100 muM in a fixed fast reaction time of 5 min. The potential applications of this technique were tested in two ways, for mixed-ion solutions and in physiological fluids, and both experiments exhibited good selectivity toward Cu(2+).

Evaporation-Induced Assembly of Quantum Dots into Nanorings

Herein, we demonstrate the controlled formation of two-dimensional periodic arrays of ring-shaped nanostructures assembled from CdSe semiconductor quantum dots (QDs). The patterns were fabricated by using an evaporative templating method. This involves the introduction of an aqueous solution containing both quantum dots and polystyrene microspheres onto the surface of a planar hydrophilic glass substrate. The quantum dots became confined to the meniscus of the microspheres during evaporation, which drove ring assembly via capillary forces at the polystyrene sphere/glass substrate interface. The geometric parameters for nanoring formation could be controlled by tuning the size of the microspheres and the concentration of the QDs employed. This allowed hexagonal arrays of nanorings to be formed with thicknesses ranging from single dot necklaces to thick multilayer structures over surface areas of many square millimeters. Moreover, the diameter of the ring structures could be simultaneously controlled. A simple model was employed to explain the forces involved in the formation of nanoparticle nanorings.

Effects of Ion Solvation and Volume Change of Reaction on the Equilibrium and Morphology in Cation-Exchange Reaction of Nanocrystals

The effects of cation solvation and the volume change (Delta V) of reaction on the equilibrium and the morphology change in the cation-exchange reactions of metal chalcogenide nanocrystals, CdE --> M(x)E(y) (E = S, Se, Te; M = Pd, Pt), were investigated. Since the solvation of cations is an important controllable factor determining the free energy of the reaction, the effect of varying cation solvation conditions on the equilibrium of the reaction was examined. A two-phase solvent environment, where the cations involved in the exchange reaction were preferentially solvated in different phases by using selective cation complexing molecules, was particularly efficient in increasing the thermodynamic driving force. The effect of Delta V of reaction on the morphology of the product nanocrystals was also investigated. Depending on the stress developed in the lattice during the reaction, product nanocrystals underwent varying degrees of morphological changes such as void formation and fragmentation in addition to the preservation of the original morphology of the reactant nanocrystals. The knowledge of the effect of ion solvation and Delta V of reaction on the equilibrium and product morphology provides a new strategy and useful guides to the application of cation-exchange reactions for the synthesis of a broader range of inorganic nanocrystals.

Using Patterned Arrays of Metal Nanoparticles to Probe Plasmon Enhanced Luminescence of CdSe Quantum Dots

Here we present a simple platform for probing plasmon enhanced photoluminescence (PL) of quantum dots by confocal microscopy. In this study, self-assembled monolayers of silane-derivative molecules were patterned onto the oxidized GaAs surfaces to direct the attachment of Au or Ag nanoparticles onto the surface. Following the directed binding of metal nanoparticles (MNPs), a layer-by-layer deposition of oppositely charged polymers was used to create films with varying thickness by controlling the numbers of deposited layers. CdSe quantum dots (QDs) of ∼4 and 5.5 nm in diameter with 16-mercaptohexadecanoic acid as a surfactant were then adsorbed onto the outermost polymer layer via electrostatic interactions. Using confocal fluorescence microscopy, the enhanced PL from the CdSe over the Au or Ag nanoparticle patterns could be imaged directly and scaled against the regions with no Au or Ag nanoparticles, and the luminescence of the GaAs (as an internal standard) for different CdSe-metal separations. By using a pattern, PL enhancement as a function of particle-CdSe spacing can be readily probed all on a single platform, where the QDs over MNPs and not over MNPs can be directly compared in the same dielectric environment. The observed luminescence as a function of metal-QD separation can be readily fit to a combined model of metal-fluorophore fluorescence quenching and local electric field enhancement.

Doping location-dependent energy transfer dynamics in Mn-doped CdS/ZnS nanocrystals.

Dynamics of energy transfer and charge carrier localization in Mn-doped CdS/ZnS core/shell nanocrystals correlated with doping location and concentration are studied via transient absorption measurement of exciton relaxation dynamics. The strong dependence of exciton-Mn energy transfer rate on doping location was directly resolved in the transient bleach recovery and electron intraband absorption data by using layer-by-layer synthesized Mn-doped nanocrystals. With 1.2 nm decrease in doping radius in the ZnS shell, energy transfer rate increases by 6 fold. We identified that hole trapping is the major competing process that inhibits the energy transfer in Mn-doped CdS/ZnS nanocrystals. From the branching ratio of the energy transfer and hole trapping, combined with luminescence quantum yield measurement, we also obtained doping location-dependent radiative relaxation quantum yield of Mn(2+) ions that is as high as 0.95.

Photoinduced Anion Exchange in Cesium Lead Halide Perovskite Nanocrystals

Cesium lead halide (CsPbX3) perovskite nanocrystals (NCs) possess the unique capability of post-synthesis anion exchange providing facile tunability of the optical properties, which is usually achieved by mixing NCs with reactive anion precursors. In this work, we show that the controllable anion exchange can be achieved in a dihalomethane solution of CsPbX3 NC in the absence of any spontaneously reacting anion source using photoexcitation of CsPbX3 NCs as the triggering mechanism for the halide ion exchange. The reaction begins with the photoinduced electron transfer from CsPbX3 NCs to dihalomethane solvent molecules producing halide ions via reductive dissociation, which is followed by anion exchange. The reaction proceeds only in the presence of excitation light and the rate and extent of reaction can be controlled by varying the light intensity. Furthermore, the asymptotic extent of reaction under continuous excitation can be controlled by varying the wavelength of light that self-limits the reaction when light becomes off-resonance with the absorption of NCs. The light-controlled anion exchange demonstrated here can be utilized to pattern the post-synthesis chemical transformation of CsPbX3 NCs, not readily achievable using typical methods of anion exchange.

Surfactant effect on the formation of CuInSe2 nanowires in solution phase synthesis

Solution-phase synthesis of CuInSe2 nanowires without using metal nanocrystal catalysts has been demonstrated. The morphology of chalcopyrite CuInSe2 nanoparticles could be varied from spheres to highly anisotropic nanowires by varying the relative amount of strong and weak binding surfactants passivating the surface. For CuInSe2 nanowires, weakly binding dioctylphosphine oxide (DOPO) was found to be the key surfactant that enables the anisotropic 1-dimensional growth. Detailed analysis of the structure of the nanowires indicates that they grow perpendicular to (112) planes, with twinning around the growth axis by ∼60° rotation. The nanowires of CuInSe2 synthesized in this study exhibit saw-tooth surface morphology resembling a stack of truncated tetrahedra which show a continuous growth mechanism.

One-photon UV detrapping of the hydrated electron

Direct 1-photon excitation of the hydrated electron from the ground state to the conduction band is achieved with 400 nm excitation. This provides a unique method for investigating the femtosecond dynamics and spectroscopy of the conduction band hydrated electron without interference from other states. The assignment of the 400 nm excited state to the conduction band is supported by the observation of >35 A spatial migration of the hydrated electron, as manifested in complete supression of geminate recombination. Similar dynamics and electron scavenging yields are observed for the 400 nm state and that produced by 2-photon 800 nm excitation.

Size-dependent ultrafast magnetization dynamics in iron oxide (Fe3O4) nanocrystals.

Optically induced ultrafast demagnetization and its recovery in superparamagnetic colloidal iron oxide (Fe3O4) nanocrystals have been investigated via time-resolved Faraday rotation measurements. Optical excitation with near-infrared laser pulse resulted in ultrafast demagnetization in approximately 100 fs via the destruction of ferrimagnetic ordering. The degree of demagnetization increased with the excitation density, and the complete demagnetization reached at approximately 10% excitation density. The magnetization recovered on two time scales, several picoseconds and hundreds of picoseconds, which can be associated with the initial reestablishment of the ferrimagnetic ordering and the electronic relaxation back to the ground state, respectively. The amplitude of the slower recovery component increased with the size of the nanocrystals, suggesting the size-dependent ferrimagnetic ordering throughout the volume of the nanocrystal.

Ratiometric temperature imaging using environment-insensitive luminescence of Mn-doped core–shell nanocrystals

We report a ratiometric temperature imaging method based on Mn luminescence from Mn-doped CdS-ZnS nanocrystals (NCs) with controlled doping location, which is designed to exhibit strong temperature dependence of the spectral lineshape while being insensitive to the surrounding chemical environment. Ratiometric thermometry on the Mn luminescence spectrum was performed by using Mn-doped CdS-ZnS core-shell NCs that have a large local lattice strain on the Mn site, which results in the enhanced temperature dependence of the bandwidth and peak position. The Mn luminescence spectral lineshape is highly robust with respect to the change in the polarity, phase and pH of the surrounding medium and aggregation of the NCs, showing great potential in temperature imaging under chemically heterogeneous environment. The temperature sensitivity (ΔIR/IR = 0.5%/K at 293 K, IR = intensity ratio at two different wavelengths) is highly linear in a wide range of temperatures from cryogenic to above-ambient temperatures. We demonstrate the surface temperature imaging of a cryo-cooling device showing a temperature variation of >200 K by imaging the luminescence of the NC film formed by simple spin coating, taking advantage of the environment-insensitive luminescence.