• Proceedings of the Korean Vacuum Society Conference
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• 2013.08a
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• pp.310.1-310.1
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• 2013

We show the novel hot electron based-solar energy conversion using tandem structured Schottky diode with double Schottky barriers. In this report, we show the effect of the double Schottky barriers on solar cell performance by enhancing both of internal photoemission and band-to-band excitation. The tandem structured Au/Si diode capped with TiO2 layer as second semiconductor exhibited improved ability for light harvesting. The proposed mechanisms consist of multiple reflections of hot electrons and additional pathway of solar energy conversion due to presence of multiple interfaces between thin gold film and semiconductors. Short-circuit photocurrent measured on the tandem structured Au/Si diodes under illumination of AM1.5 increased by approximately 70% from 3.1% to 5.3% and overall incident photon to electron conversion efficiency (IPCE) was enhanced in visible light, revealing that the concept of the double Schottky barriers have significant potential as novel strategy for light harvesting.

• Bulletin of the Korean Chemical Society
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• v.13 no.2
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• pp.166-172
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• 1992

Studies have been conducted to explore single electron transfer (SET) induced photocyclization reactions of N-(trimethylsilylmethoxyalkyl)phthalimides(alkyl=E thyl, n-propyl, n-butyl, n-pentyl, and n-octyl). Photocyclizations occur in methanol in high yields to produce cyclized products in which phthalimide carbonyl carbon is bonded to the carbon of side chain in place of the trimethylsilyl group. Mechanism for these photocyclizations involving intramolecular SET from oxygen in the $\alpha-silylmethoxy$ groups to the singlet excited state phthalimide moieties followed by desilylation of the intermediate $\alpha-silylmethoxy$ cation radicals and cyclization by radical coupling are proposed. In contrast, photoreaction of N-(trimethylsilylmethoxyethyl) phthalimide in acetone follows different reaction routes to produce two cyclized products in which carbon-carbon bond formation takes place between the phthalimide carbonyl carbon and the carbon $\alpha$ to silicon and oxygen atoms via triplet carbonyl hydrogen abstraction triplet carbonyl silyl group abstraction pathways. The normal singlet SET pathway dominates these triplet processes for photoreaction of this substance in methanol. The efficient and regioselective cyclization reactions observed for photolysis in methanol represent synthetically useful processes for construction of medium and large ring heterocyclic compounds.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.35 no.4
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• pp.342-347
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• 2022

In-situ analyzation and detection of real-time chemical reactions can be a significant part in interpreting the underlying mechanism in very reactive chemical reactions. To do this, first we have designed a microfluidic device (MFD) pattern for observation of synthesis of hierarchical nanostructures based on graphene oxide (GO), conjugating the well-known coupling reaction by which the solution of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC)-mediated coupling is enhanced in the presence of n-hydroxysuccinimide (NHS) to make amide bonding, hereafter called as the EDC coupling. Then, we have manufactured microfluidic devices with multiple tens of micrometer-sized channels that can circulate those nanomaterials to be chemically reacted in the channels. These microfluidic devices were made by negative photo lithography and soft lithography. We showed the possibility of using Raman spectroscopy to reveal the basic mechanism of the energy storage applications.

• Fire Science and Engineering
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• v.33 no.6
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• pp.80-86
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• 2019

In Korea, a total of 556 chemical accidents occurred from 2012 to 2018 caused by adverse reactions of two or more chemicals, which required significant amounts of time to identify the causative chemicals. Rapid analysis is required for effective incident response and probing. In this study, a quantum transition time-of-flight mass spectrometer was used to identify the causative agents of chemical accidents caused by adverse reactions. The analyzer enabled fast real-time analysis without the need for sample collection and pretreatment. Quantitative and qualitative analysis of most volatile organic compounds with high hydrogen affinity was performed to investigate the cause of the chemical accidents. In fact, in the month of 201◯, methanol and toluene were detected as causative agents of the accident using a quantum transition time mass spectrometer, and were also the cause of the reported odor.

• Advances in nano research
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• v.10 no.3
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• pp.253-261
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• 2021

Polydimethylsiloxane (PDMS) is one of the most widely adopted silicon-based organic polymeric elastomers. Elastomeric nanostructures are normally required to accomplish an explicit mechanical role and correspondingly their mechanical properties are crucial to affect device and material performance. Despite its wide application, the mechanical properties of PDMS are yet fully understood. In particular, the time dependent mechanical response of PDMS has not been fully elucidated. Here, utilizing state-of-the-art PeakForce Quantitative Nanomechanical Mapping (PFQNM) together with Force Volume (FV) and Fast Force Volume (FFV), the elastic moduli of PDMS samples were assessed in a time-dependent fashion. Specifically, the acquisition frequency was discretely changed four orders of magnitude from 0.1 Hz up to 2 kHz. Careful calibrations were done. Force data were fitted with a linearized DMT contact mechanics model considering surface adhesion force. Increased Young's modulus was discovered with increasing acquisition frequency. It was measured 878 ± 274 kPa at 0.1 Hz and increased to 4586 ± 758 kPa at 2 kHz. The robust local probing of mechanical measurement as well as unprecedented high-resolution topography imaging open new avenues for quantitative nanomechanical mapping of soft polymers, and can be extended to soft biological systems.

• Proceedings of the Materials Research Society of Korea Conference
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• 2012.05a
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• pp.51-51
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• 2012

There is a growing interest in innovative chemical synthesis in microreactors owing to high efficiency, selectivity, and yield. In microfluidic systems, the low-volume spatial and temporal control of reactants and products offers a novel method for chemical manipulation and product generation. Glass, silicon, poly(dimethylsiloxane) (PDMS), and plastics have been used for the fabrication of miniaturized devices. However, these materials are not the best due to either of low chemical durability or expensive fabrication costs. In our group, we have recently addressed the demand for economical resistant materials that can be used for easy fabrication of microfluidic systems with reliable durability. We have suggested the use of various specialty polymers such as silicon-based inorganic polymers and fluoropolymer, flexible polyimide (PI) films that have not been used for microfluidic devices, although they have been used for other areas. And inexpensive lithography techniques were used to fabricate Lab-on-a-Chip type of microreactors with differently devised microchannel design. These microreactors were demonstrated for various synthetic reactions: liquid, liquid-gas organic chemical reactions in heterogeneous catalytic processes, syntheses of polymer and non-trivial inorganic materials. The microreactors were inert, and withstand even harsh conditions, including hydrothermal reaction. In addition, various built-in microstructures inside the microchannels, for example Pd decorated peptide nanowires, definitely enhance the uniqueness and performance of microreactors. These user-friendly Lab-on-a-Chip devices are useful alternatives for chemist and chemical engineer to conventional chemical tools such as glass.

• Journal of the Korean Applied Science and Technology
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• v.21 no.4
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• pp.359-363
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• 2004

Reaction conditions and catalysts were investigated for direct $CF_3I$ synthesis. Optimum reaction temperature was determined by pyrolysis of $CF_3H$ and catalytic reactions. Reactions with changing oxygen concentration were performed. As a result, yield of $CF_3I$ increased with decreasing oxygen concentration. Catalytic activity was changed with the weight ratio of the used metal salts. This result was stemmed from the change in the pore size of activated carbon by the metal salts. The optimum reaction conditions were: $600^{\circ}C$, space velocity of $45hr^{-1}$, and with 7wt% KF/AC catalyst.

• Bulletin of the Korean Chemical Society
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• v.31 no.5
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• pp.1199-1203
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• 2010

Second-order rate constants ($k_N$) have been measured spectrophotometrically for Michael-type reactions of 1-(X-substituted phenyl)-2-propyn-1-ones (2a-f) with a series of alicyclic secondary amines in MeCN at $25.0{\pm}0.1^{\circ}C$. The $k_N$ value increases as the incoming amine becomes more basic and the substituent X changes form an electron-donating group (EDG) to an electron-withdrawing group (EWG). The Br${\o}$nsted-type plots are linear with ${\beta}_{nuc}$ = 0.48 - 0.51. The Hammett plots for the reactions of 2a-f exhibit poor correlations but the corresponding Yukawa-Tsuno plots result in much better linear correlations with ${\rho}$ = 1.57 and r = 0.46 for the reactions with piperidine while ${\rho}$ = 1.72 and r = 0.39 for those with morpholine. The amines employed in this study are less reactive in MeCN than in water for reactions with substrates possessing an EDG, although they are ca. 8 pKa units more basic in the aprotic solvent. This indicates that the transition state (TS) is significantly more destabilized than the ground state (GS) in the aprotic solvent. It has been concluded that the reactions proceed through a stepwise mechanism with a partially charged TS, since such TS would be destabilized in the aprotic solvent due to the electronic repulsion between the negative-dipole end of MeCN and the negative charge of the TS. The fact that primary deuterium kinetic effect is absent supports a stepwise mechanism in which proton transfer occurs after the rate-determining step.

• Bulletin of the Korean Chemical Society
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• v.32 no.spc8
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• pp.2955-2959
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• 2011

Second-order rate constants for nucleophilic substitution reactions of 2,4-dinitrophenyl benzenesulfonate 1a with a series of alicyclic secondary amines in MeCN have been measured spectrophotometrically and compared with those reported previously for the corresponding reactions performed in aqueous medium to investigate the effect of medium on reactivity and reaction mechanism. The amines employed in this study are found to be more reactive in the aprotic solvent than in $H_2O$. The reactions of 1a in MeCN result in a linear Br${\o}$nsted-type plot with ${\beta}_{nuc}$ = 0.58, which contrasts to the curved Br${\o}$nsted-type plot reported previously for the corresponding reactions performed in the aqueous medium (i.e., ${\beta}_2$ = 0.86 and ${\beta}_1$ = 0.38). Accordingly, it has been concluded that the reaction mechanism changes from a stepwise mechanism to a concerted pathway upon changing the medium from $H_2O$ to MeCN. Reactions of Y-substituted phenyl benzenesulfonates 1a-c with piperidine in MeCN result in a linear Br${\o}$nsted-type plot with ${\beta}_{lg}$ = -1.31, indicating that expulsion of the leaving group is significantly more advanced than bond formation in the transition state. The trigonal bipyramidal intermediate ($TBPy^{\pm}$) proposed previously for the reactions in $H_2O$ would be highly unstable in MeCN due to strong repulsion between the negative charge in $TBPy^{\pm}$ and the negative dipole end of MeCN. Thus, destabilization of $TBPy^{\pm}$ in MeCN has been concluded to change the reaction mechanism from a stepwise mechanism to a concerted pathway.

• Bulletin of the Korean Chemical Society
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• v.34 no.7
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• pp.2023-2028
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• 2013

A kinetic study is reported for the nucleophilic substitution reactions of phenyl Y-substituted-phenyl carbonates (5a-5k) with piperidine in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The plots of $k_{obsd}$ vs. [piperidine] for the reactions of substrates possessing a strong electron-withdrawing group (EWG) in the leaving group (i.e., 5a-5i) are linear and pass through the origin. In contrast, the plots for the reactions of substrates bearing a weak EWG or no substituent (i.e., 5j or 5k) curve upward, indicating that the electronic nature of the substituent Y in the leaving group governs the reaction mechanism. Thus, it has been suggested that the reactions of 5a-5i proceed through a stepwise mechanism with a zwitterionic tetrahedral intermediate (i.e., $T^{\pm}$) while those of 5j and 5k proceed through a stepwise mechanism with two intermediates (i.e., $T^{\pm}$ and its deprotonated form $T^-$). The slope of the Br${\o}$nsted-type plot for the second-order rate constants (i.e., $k_N$ or $Kk_2$) changes from -0.41 to -1.89 as the leaving-group basicity increases, indicating that a change in the rate-determining step (RDS) occurs. The reactions of 5a-5k with piperidine result in larger $k_1$ values than the corresponding reactions with ethylamine.