• Rapid Communication in Photoscience
• /
• v.4 no.1
• /
• pp.22-24
• /
• 2015

A new trinuclear complex $[Ru(TPrPc)(CO)]_2[Ru(pytpy)_2](PF_6)_2$ (TPrPc = 2,7,12,17-tetra-n-propylporphycenato dianion and pytpy = 4'-(4-pyridyl)-2,2':6',2"-terpyridine) has been synthesized and characterized as the first example of a discrete molecular wire containing metalloporohycenes as a building block. The trinuclear complex shows multiple-step redox behavior in 0.1 M n-$Bu_4NPF_6$-dichloromethane. The mononuclear $[Ru(pytpy)_2]^{2+}$ precursor shows emission at 640 nm (deaerated acetone, 298 K) upon illumination at the metal-to-ligand charge transfer (MLCT) band at 495 nm, but the trinuclear molecular wire is found to be non-emissive upon photoexcitation at the central $[Ru(pytpy)_2]^{2+}$ entity, indicating an efficient quenching ability of the axially-linked, ruthenium(II)-porphycene chromophores in an intramolecular fashion.

• Bulletin of the Korean Chemical Society
• /
• v.31 no.1
• /
• pp.92-99
• /
• 2010

Photoexcitation of a precursor ion inside a cell floated at high voltage installed in a tandem time-of-flight (TOF) mass spectrometer provides triple tandem mass spectrometric information and allows kinetic and mechanistic studies. In this work, the factors affecting, or downgrading, the performance of the technique were identified. Ion-optical and computational analyses showed that an optimum instrument could be designed by utilizing a reflectron with linear-plus-quadratic potential inside. Theoretical predictions were confirmed by tests with instruments built with different ion-optical layout. With optimized instruments, masses of intermediate ions in the consecutive dissociation of a precursor ion could be determined with the maximum error of $\pm5$ Da. We also observed excellent agreement in dynamical parameters (critical energy and entropy) for the dissociation of a model peptide ion determined by instruments with different ion-optical layout operated under optimum conditions. This suggests that these parameters can be determined reliably by the kinetic method developed previously when properly designed and operated tandem TOF instruments are used.

• Journal of the Korean Chemical Society
• /
• v.34 no.3
• /
• pp.255-259
• /
• 1990

The nitrogen-laser flash photolysis apparatus has been set up to detect directly the transient produced from the excited Benoxaprofen (BXP). The function of the instrument has been tested by using anthracene as a standard sample. The laser photoexcitation of BXP in ethanol has been carried out under a constant stream of $N_2$ gas and a transient absorption spectrurn has been recorded over the 400-600 nm. The effects of oxygen and ${\beta}-carotene$ on the transient spectrum reveal that thee maximum transient absorption at 415 nm is attributed to the triplet state of BXP and the triplet energy of BXP is above 22 Kcal/mole. In addition to the triplet state, another transient species has been observed to be produced, which is probably a radical form of BXP. The photosensitization mechanism of BXP is discussed based on these results.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
• /
• 1992.05a
• /
• pp.46-49
• /
• 1992

Cadmium sulfide thin films were deposited on glass substrate by Chemical Mist Deposition from solutions containing equimolar (0.1M) cadmium chloride and thiourea [(NH$_2$)$_2$CS] at a mist velocity of 1.6m/sec. Substrate temperatures were ranged between 200$^{\circ}C$ and 400$^{\circ}C$. The microstructure and semiconducting property of the films were investigated using SEM, X-ray diffraction, UV transmittance measurement and four point probe method. All the films have hexagonal structure and diffraction patterns indicate that the intensity of (112) and (101) reflections increase with increasing substrate temperature, whereas (002) reflection substrate temperature, whereas(002) reflection decrease for substrate temperatures between 250$^{\circ}C$ and 350$^{\circ}C$. The films prepared at lower temperature have a significant number of pinholes due probably to entrapped gaseous reaction. Optical transmittance of the films deposited at 350$^{\circ}C$ was about 75%. Optical bandgap of the films were 2.43eV regardless of substrate temperature. The dark resistivity of the films decreased with increasing substrate temperature up to 300$^{\circ}C$ and increased with further increasing substrate temperature. The films were photosensitive and had dark-to-light resistivity ratios of about 10 at room temperature for a white-light photoexcitation intensity of 50mw/$\textrm{cm}^2$.

• Current Optics and Photonics
• /
• v.3 no.2
• /
• pp.164-171
• /
• 2019

Photoluminescence (PL) properties of GaN-based light-emitting diodes (LEDs) were analyzed to study the effects of carrier leakage on the luminescence properties at room temperature. The electrical leakage and PL properties were compared for LEDs showing leakages at forward bias and an LED with an intentional leakage path formed by connecting a parallel resistance of various values. The leakages at the forward bias, which could be observed from the current-voltage characteristics, resulted in an increase in the excitation laser power density for the maximum PL efficiency (ratio of PL intensity to excitation power) as well as a reduction in the PL intensity. The effect of carrier leakages on PL properties was similar to the change in PL properties owing to a reduction of the photovoltage by a reverse current since the direction of the carrier movement under photoexcitation is identical to that of the reverse current. Valid relations between PL properties and electrical properties were observed as the PL properties deteriorated with an increase in the carrier leakage. The results imply that the PL properties of LED chips can be an indicator of the electrical properties of LEDs.

• Polymer(Korea)
• /
• v.24 no.2
• /
• pp.211-219
• /
• 2000

Fluorene-based light emitting polymer blends with liquid crystalline characteristics were studied on effective energy transfer and dichroic characteristics. Incorporating 0.5 wt% of the non-liquid crystalline into the liquid crystalline polymer suppressed the PL emission at 420 nm on photoexcitation at 360 nm, but generated a new PL emission of the non-liquid crystalline polymer at 480 nm. The highest PL intensity at 480 nm, which was 13 times stronger than those of the two polymers before blending, was observed for a blend with 2.0 wt% of the non-liquid crystalline polymer. When the molecules of the blends were aligned on a rubbed polyimide surface by a heating-cooling process, the dichroic ratio and the order parameter were 2.0 and 0.25, respectively. Time-correlated single photon counting (TCSPC) study revealed that the time required for energy transfer between the two chromophores was shortened by 93 ps when the blends were aligned on the rubbed polyimide surface by the heating-cooling process. The thermal treatment also enhanced the energy transfer efficiency by 9%.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
• /
• 2010.03a
• /
• pp.21-21
• /
• 2010

(Ba,Sr)$TiO_3$ (BST) thin film with a perovskite structure has potential for the practical application in various functional devices such as nonvolatile-memory components, capacitor, gate insulator of thin-film transistors, and electro-optic devices for display. Normally, the BST thin films derived from sol-gel and sputtering are amorphous or partially crystalline when processed below $600^{\circ}C$. For the purpose of integrating BST thin film directly into a Si-based read-out integrated circuit (ROIC), it is necessary to process the BST film below $400^{\circ}C$. The microstructural and electrical properties of low-temperature crystallized BST film were studied. The BST thin films have been fabricated at $350^{\circ}C$ by UV-assisted rapidly thermal annealing (RTA). The BST films are in a single perovskite phase and have well-defined electrical properties such as high dielectric constant, low dielectric loss, low leakage current density, and high breakdown voltage. Photoexcitation of the organics contained in the sol-gel-derived films by high-intensity UV irradiation facilitates elimination of the organics and formation of the single-crystalline phase films at low temperatures. The amorphous BST thin film was transformed to a highly (h00)-oriented perovskite structure by high oxygen pressure processing (HOPP) at as low as $350^{\circ}C$. The dielectric properties of BST film were comparable to (or even better than) those of the conventionally processed BST films prepared by sputtering or post-annealing at temperature above $600^{\circ}C$. When external pressure was applied to the well-known contractive BST system during annealing, the nucleation energy barrier was reduced; correspondingly, the crystallization temperature decreased. The UV-assisted RTA and HOPP, as compatible with existing MOS technology, let the BST films be integrated into radio-frequency circuit and mixed-signal integrated circuit below the critical temperature of $400^{\circ}C$.

• Bulletin of the Korean Chemical Society
• /
• v.15 no.10
• /
• pp.857-860
• /
• 1994

We have calculated the ${\pi}$-electron density, atom self-polarizability, and free valence on each atom of N-(2-chlorobenzyl)-pyridinium, N-(benzyl)-2-chloropyridinium, and N-(2-chlorobenzyl)-2-chloropyridinium salts using a simple Huckel method in order to discuss their intramolecular photocyclization reaction in a qualitative method. Our calculation qualitatively predicts that photocyclization occurs through forming radicals as a reaction intermediate by breaking a C-Cl bond after photoexcitation into a triplet state via intersystem crossing from an initially excited singlet state. We noticed that this C-Cl bond breaking is aided by ${\pi}$-complex formation between a chlorine atom and the ${\pi}$ -electrons of the neighboring ring in the triplet state and a stronger ${\pi}$-complex bond makes C-Cl bond breaking, i.e., radical formation, much easier. A chlorine atom will form a stronger ${\pi}$ -complex bond to a benzyl ring of N-(benzyl)-2-chloropyridinium than a pyridinium ring of N-(2-chlorobenzyl)-pyridinium because the former can donate its ${\pi}$-electron more easily than the latter. The chlorine at position 15 of N-(2-chlorobenzyl)-2-chloropyridinium salt in the excited state also provides its ${\pi}$-electron to the benzyl ring. So this ${\pi}$-electron can increase the bond strength of the $\pi-complex.$ Therefore, the strength of ${\pi}$-complex follows the order of N-(2-chlorobenzyl)-2-chloropyridinium, N-(benzyl)-2-chloropyridinium, and N-(2-chlorobenzyl)-pyridinium salts and thus the radical formation rate. This provides us with an intramolecular photocyclization reaction rate of the same order as given above.

• Molecules and Cells
• /
• v.46 no.8
• /
• pp.513-525
• /
• 2023

Orange carotenoid protein (OCP) of photosynthetic cyanobacteria binds to ketocarotenoids noncovalently and absorbs excess light to protect the host organism from light-induced oxidative damage. Herein, we found that mutating valine 40 in the α3 helix of Gloeocapsa sp. PCC 7513 (GlOCP1) resulted in blue- or red-shifts of 6-20 nm in the absorption maxima of the lit forms. We analyzed the origins of absorption maxima shifts by integrating X-ray crystallography, homology modeling, molecular dynamics simulations, and hybrid quantum mechanics/molecular mechanics calculations. Our analysis suggested that the single residue mutations alter the polar environment surrounding the bound canthaxanthin, thereby modulating the degree of charge transfer in the photoexcited state of the chromophore. Our integrated investigations reveal the mechanism of color adaptation specific to OCPs and suggest a design principle for color-specific photoswitches.

• 한국신재생에너지학회:학술대회논문집
• /
• 2010.06a
• /
• pp.89.1-89.1
• /
• 2010

Since Gratzel and co-workers developed a new type of solar cell based on the nanocrystalline $TiO_2$ electrode, dye-sensitized solar cells (DSSCs) have attracted considerable attention on account of their high solar energy-to-conversion efficiencies (11%), their easy manufacturing process with low cost production compared to conventional p-n junction solar cells. The mechanism of DSSC is based on the injection of electrons from the photoexcited dye into the conduction band of nanocrystalline $TiO_2$. The oxidized dye is reduced by the hole injection process from either the hole counter or electrolyte. Thus, the electronic structures, such as HOMO, LUMO, and HOMO-LUMO gap, of dye molecule in DSSC are deeply related to the electron transfer by photoexcitation and redox potential. To date, high performance and good stability of DSSC based on Ru-dyes as a photosensitizer had been widely addressed in the literatures. DSSC with Ru-bipyridyl complexes (N3 and N719), and the black ruthenium dye have achieved power conversion efficiencies up to 11.2% and 10.4%, respectively. However, the Ru-dyes are facing the problem of manufacturing costs and environmental issues. In order to obtain even cheaper photosensitizers for DSSC, metal-free organic photosensitizers are strongly desired. Metal-free organic dyes offer superior molar extinction coefficients, low cost, and a diversity of molecular structures, compared to conventional Ru-dyes. Recently, novel photosensitizers such as coumarin, merocyanine, cyanine, indoline, hemicyanine, triphenylamine, dialkylaniline, bis(dimethylfluorenyl)-aminophenyl, phenothiazine, tetrahydroquinoline, and carbazole based dyes have achieved solar-to-electrical power conversion efficiencies up to 5-9%. On the other hand, organic dye molecules have large ${\pi}$-conjugated planner structures which would bring out strong molecular stacking in their solid-state and poor solubility in their media. It was well known that the molecular stacking of organic dyes could reduce the electron transfer pathway in opto-electronic devices, significantly. In this paper, we have studied on synthesis and characterization of dendritic organic dyes with different number of electron acceptor/anchoring moieties in the end of dendrimer. The photovoltaic performances and the incident photon-to-current (IPCE) of these dyes were measured to evaluate the effects of the dendritic strucuture on the open-circuit voltage and the short-circuit current.