Jing-Jong Shyue

A New and Facile Method To Prepare Uniform Hollow MnO/Functionalized mSiO2 Core/Shell Nanocomposites

Trifunctional uniform nanoparticles comprising a manganese nanocrystal core and a functionalized mesoporous silica shell (MnO@mSiO(2)(Ir)@PEG, where Ir is an emissive iridium complex and PEG is polyethylene glycol) have been strategically designed and synthesized. The T(1) signal can be optimized by forming hollow core (H-MnO@mSiO(2)(Ir)@PEG) via a novel and facile etching process, for which the mechanism has been discussed in detail. Systematic investigation on correlation for longitudinal relaxation (T(1)) versus core shapes and shell silica porosity of the nanocomposites (MnO, H-MnO, MnO@SiO(2), MnO@mSiO(2), H-MnO@mSiO(2)) has been carried out. The results show that the worm-like nanochannels in the mesoporous silica shell not only increase water permeability to the interior hollow manganese oxide core for T(1) signal but also enhance photodynamic therapy (PDT) efficacy by enabling the free diffusion of oxygen. Notably, the H-MnO@mSiO(2)(Ir)@PEG nanocomposite with promising r(1) relaxivity demonstrates its versatility, in which the magnetic core provides the capability for magnetic resonance imaging, while the simultaneous red phosphorescence and singlet oxygen generation from the Ir complex are capable of providing optical imaging and inducing apoptosis, respectively.

High-efficiency blue organic light-emitting diodes using a 3,5-di(9H-carbazol-9-yl)tetraphenylsilane host via a solution-process

We present a solution-processed blue organic light-emitting diode (OLED) with markedly high current efficiency of 41.2 cd A−1 at 100 cd m−2 and 31.1 cd A−1 at 1000 cd m−2. The high efficiency was partly attributed to the use of a molecular host, 3,5-di(9H-carbazol-9-yl)tetraphenylsilane, which possesses a wide triplet band gap, high carrier mobility, ambipolar transport property and high glass transition temperature. Besides the intrinsically good physical properties, the solution-process also played an important role in fabricating the high-efficiency device, since it could make the molecular distribution of host and guest homogeneous in the emissive layer. Moreover, the device efficiency at higher brightness could be markedly enhanced by using an electron-blocking layer. As the microlens was introduced on the glass substrate to enhance the light outcoupling, the resultant device efficiency of the blue OLED further increased to 50.1 cd A−1 at 100 cd m−2 and 37.3 cd A−1 at 1000 cd m−2.

Depth Profiling of Organic Films with X-ray Photoelectron Spectroscopy Using C60+ and Ar+ Co-Sputtering

By sputtering organic films with 10 kV, 10 nA C60+ and 0.2 kV, 300 nA Ar+ ion beams concurrently and analyzing the newly exposed surface with X-ray photoelectron spectroscopy, organic thin-film devices including an organic light-emitting diode and a polymer solar cell with an inverted structure are profiled. The chemical composition and the structure of each layer are preserved and clearly observable. Although C60+ sputtering is proven to be useful for analyzing organic thin-films, thick organic-devices cannot be profiled without the low-energy Ar+ beam co-sputtering due to the nonconstant sputtering rate of the C60+ beam. Various combinations of ion-beam doses are studied in this research. It is found that a high dosage of the Ar+ beam interferes with the C60+ ion beam, and the sputtering rate decreases with increasing the total ion current. The results suggest that the low-energy single-atom projectile can disrupt the atom deposition from the cluster ion beams and greatly extend the application of the cluster ion-sputtering. By achievement of a steady sputtering rate while minimizing the damage accumulation, this research paves the way to profiling soft matter and organic electronics.

Facile synthesis of wurtzite copper–zinc–tin sulfide nanocrystals from plasmonic djurleite nuclei

The present research demonstrates a facile one-pot heating process without injection to synthesize an important light harvesting quaternary nanocrystal: wurtzite copper–zinc–tin sulfide (w-CZTS). High quality w-CZTS nanocrystals can be easily obtained by mixing all the precursors and simply heating to the reaction temperature. The nano-crystal formation mechanism is thoroughly investigated and resolved by X-ray diffraction spectroscopy (XRD), transmission electron microscopy (TEM) and electron energy loss spectroscopy (EELS). It starts with the nucleation of plasmonic djurleite Cu1.94S, subsequent growth of CZTS–Cu1.94S heterostructures and inter-diffusion of cations and then finally leads to single phase and single crystal w-CZTS nanocrystals. The mechanism of nanocrystal formation can be applied universally regardless of the type of zinc and tin precursor for high quality w-CZTS nanocrystals. The in-depth interpretations of the reaction mechanism of this process significantly advance the current knowledge of multi-component nanocrystal formation. The developed method is scalable for high throughput and low cost w-CZTS suspensions which await practical photovoltaic applications.

2D self-bundled CdS nanorods with micrometer dimension in the absence of an external directing process.

In the absence of an external direction-controlling process, exclusive self-bundled arrays of CdS nanorods are formed using a facile solution-based method involving trioctylphosphine (TOP) and tetradecylphosphonic acids (TDPA) as cosurfactants. CdS self-bundled arrays with an area of as large as 2.0 microm(2) could be obtained. A detailed mechanistic investigation leads us to conclude that the matching in nanorod concentration, intrinsic properties of CdS, and the hydrocarbon chains of the surfactants between adjacent CdS rods play key roles in the self-assembly. In sharp contrast to the defect dominant emission in solutions, the self-bundled CdS nanorods exhibit optical emission nearly free from the defect-states, demonstrating their potential for applications in luminescence and photovoltaic devices.

Effect of fabrication parameters on three-dimensional nanostructures of bulk heterojunctions imaged by high-resolution scanning ToF-SIMS.

Solution processable fullerene and copolymer bulk heterojunctions are widely used as the active layers of solar cells. In this work, scanning time-of-flight secondary ion mass spectrometry (ToF-SIMS) is used to examine the distribution of [6,6]phenyl-C61-butyric acid methyl ester (PCBM) and regio-regular poly(3-hexylthiophene) (rrP3HT) that forms the bulk heterojunction. The planar phase separation of P3HT:PCBM is observed by ToF-SIMS imaging. The depth profile of the fragment distribution that reflects the molecular distribution is achieved by low energy Cs(+) ion sputtering. The depth profile clearly shows a vertical phase separation of P3HT:PCBM before annealing, and hence, the inverted device architecture is beneficial. After annealing, the phase segregation is suppressed, and the device efficiency is dramatically enhanced with a normal device structure. The 3D image is obtained by stacking the 2D ToF-SIMS images acquired at different sputtering times, and 50 nm features are clearly differentiated. The whole imaging process requires less than 2 h, making it both rapid and versatile.

Tuning the surface potential of gold substrates arbitrarily with self-assembled monolayers with mixed functional groups.

Alkanethiol anchored self-assembled monolayers (SAMs) on gold are widely used to immobilize and detect molecules including DNA and proteins. Most of these molecules are covalently bonded with the SAM on the Au surface and cannot be released easily. By using different functional groups, the interfacial charge of SAMs can be selected, and thus, they can be considered as adaptors for immobilizing and releasing materials selectively through electrostatic interaction under given conditions. In this work, as an additional factor to control the surface charge, SAMs with mixed functional groups are presented, and it is demonstrated that the isoelectric point (IEP) can be tailored by the ratio of functional groups. Using carboxylic acid- and amine-SAM on gold substrates as an example, isoelectric points (IEPs) from 3.5 to 6.5 can be obtained arbitrarily. The ratio between the functional groups on the surface was quantified by X-ray photoelectron spectrometry (XPS) and was found to be slightly different from the deposition solution. The homogeneous spatial distribution of the functional groups was determined with scanning electrical potential microscopy (SEPM). The interfacial charge of SAMs with mixed functional groups on gold was investigated by electrokinetic analysis in aqueous electrolyte solutions.

Highly efficient blue organic light-emitting diode with an oligomeric host having high triplet-energy and high electron mobility

We report a high-efficiency blue organic light-emitting diode (OLED) with a solution-processed emissive layer composed of an oligomeric host of poly[3-(carbazol-9-ylmethyl)-3-methyloxetane] (PCMO) that possesses high triplet-energy and high electron mobility. The device exhibited a current efficiency of 40.4 cd A−1 with an external quantum efficiency (EQE) of 21.6% and power efficiency of 28.2 lm W−1 at 230 cd m−2 or 24.7 cd A−1, 10.3%, and 15.5 lm W−1 at 1 000 cd m−2. The high efficiency may be attributed to the host possessing a high electron mobility and lower electron injection barrier, resulting in a more balanced carrier-injection. Moreover, the high electron-mobility favors the transport of electrons, resulting in a more balanced carrier-injection in the emissive layer. The device efficiency has been further enhanced to 42.6 cd A−1 (22.9%, 29.7 lm W−1) at 124 cd m−2 or 28.8 cd A−1 (15.4%, 17.8 lm W−1) at 1 000 cd m−2 by pre-heating the emissive solution at an elevated temperature before spin-coating.

Tailoring the surface potential of gold nanoparticles with self-assembled monolayers with mixed functional groups

Self-assembled monolayer (SAM)-modified gold nanoparticles can be used to immobilize and transport molecules including DNA and proteins. However, these molecules are usually covalently bound to the surface and chemical reactions are required to cleave and release them. Therefore, immobilizing molecules using electrostatic interactions might be beneficial. In this work, Au nanoparticles modified by SAMs with mixed carboxylic acid and amine functional groups are presented. The surface potential and the iso-electric point (IEP) of the nanoparticles can be tailored by the ratio of these functional groups and arbitrary IEPs between 3.2 and 7.3 can be achieved. As a result, based on electrostatic interactions, molecules could be triggered to adsorb/desorb by changing the environmental pH around this tunable IEP. These engineered nanoparticles were synthesized in a single-phase system based on the reduction of HAuCl4 by NaBH4 in ethanol with a mixture of 16-mercaptohexadecanoic acid and 8-amino-1-octanethiol that forms the SAM on the synthesized nanoparticles. Transmission electron microscopy, X-ray photoelectron spectroscopy, and electrophoresis light scattering revealed the particle size, ratio of the functional groups, and zeta-potential of the particles as a function of pH, respectively.

Highly efficient orange-red phosphorescent organic light-emitting diode using 2,7-bis(carbazo-9-yl)-9,9-ditolyfluorene as the host

We demonstrate an efficient orange-red organic light-emitting diode using a host, 2,7-bis(carbazo-9-yl)-9,9-ditolyfluorene, doped with tris(2-phenylquinoline) iridium(III). The device exhibits a high current efficiency of 44.8 cd/A at 1000 cd/m2. This may be attributed to the adoption of the host, which favors the injection of holes, as well as the emissive-layer architecture enabling excitons to form on host and hence favoring efficient energy-transfer from host to guest. Moreover, an electron-confining layer is used to modulate excessive holes to be injected into emissive layer and confine the electrons, which would in turn balance the injection of both carriers and improve efficiency.