• Bulletin of the Korean Chemical Society
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• v.33 no.5
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• pp.1675-1680
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• 2012

Three new cyanide-bridged $Cr^{III}Mn^{II}$ binuclear complexes, $[Mn(phen)_2Cl][Cr(bpmb)(CN)_2]{\cdot}H_2O$ ($\mathbf{1}$) (phen = 1,10-phenanthroline, $bpdmb^{2-}$ = 1,2-bis(pyridine-2-carboxamido)-4-methyl-benzenate), $[Mn(phen)_2Cl][Cr(bpmb)-(CN)_2]{\cdot}H_2O$ ($\mathbf{2}$) ($bpdmb^{2-}$ = 1,2-bis(pyridine-2-carboxamido)-4,5-dimethyl-benzenate), and $[Mn(phen)_2Cl]-[Cr(bpClb)(CN)_2]{\cdot}CH_3OH{\cdot}H_2O$ ($\mathbf{3}$) ($bpClb^{2-}$ = 1,2-bis(pyridine-2-carboxamido)-4-chloro-benzenate) were obtained based on $Mn(phen)_2Cl_2$ and a series of dicyanidechromate(III) building blocks. Single crystal X-ray diffraction analysis shows the structures of the three complexes are dimeric type with two different metal centers linked by a cyanide group from corresponding dicyanidechromate(III) building block. Magnetic investigations indicate the existence of relatively weak antiferromagnetic coupling between Cr(III) and Mn(II) ions with best-fit constants $J_{CrMn}=-2.78(5)cm^{-1}$ for $\mathbf{1}$, $J_{CrMn}=-3.02(2)cm^{-1}$ for $\mathbf{2}$ and $J_{CrMn}=-2.27(3)cm^{-1}$ for $\mathbf{3}$ based on the spin exchange Hamiltonian = $-2J_{CrMn}\hat{S}_{Cr}\hat{S}_{Mn}$. The magneto-structural correlation of cyanide-bridged $Cr^{III}Mn^{II}$ complexes has been discussed at last.

• Proceedings of the Korean Vacuum Society Conference
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• 2012.08a
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• pp.218-218
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• 2012

Recently, hexagonal manganites have attracted much attention because of the coexistence of ferroelectricity and antiferromagnetic (AFM) order. The crystal structure of hexagonal manganites consists of $MnO_5$ polyhedra in which $Mn^{3+}$ ion is surrounded by three oxygen atoms in plane and two apical oxygen ions. The Mn ions within Mn-O plane form a triangular lattice and couple the spins through the AFM superexchange interaction. Due to incomplete AFM coupling between neighboring Mn ions in the triangular lattice, the system forms a geometrically-frustrated magnetic state. Among hexagonal manganites, $YMnO_3$, in particular, is the best known experimentally since the f states are empty. In addition, for applications, $YMnO_3$ thin films have been known as promising candidates for non-volatile ferroelectric random access memories. However, $YMnO_3$ has low magnetic order temperature (~70 K) and A-type AFM structure, which hinders its applications. We have synthesized $YMn1_{-x}Cr_xO_3$ (x = 0, 0.05 and 0.1) samples by the conventional solid-state reaction. The powders of stoichiometric proportions were mixed, and calcined at $900^{\circ}C$ for $YMn1_{-x}Cr_xO_3$ for 24 h. The obtained powders were ground, and pressed into 5-mm-thick disks of 1/2-inch diameter. The disks were directly put into the oven, and heated up to $1,300^{\circ}C$ and sintered in air for 24 h. The phase of samples was checked at room temperature by powder x-ray diffraction using a Rigaku Miniflex diffractometer with Cu $K{\alpha}$ radiation. All the magnetization measurements were carried out with a superconducting quantum-interference-device magnetometer. Our experiments point out that the Cr-doped samples show the characteristics of a spin-glass state at low temperatures.

• Korean Chemical Engineering Research
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• v.49 no.3
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• pp.277-284
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• 2011

In this study, UV-curing type organic - inorganic hybrid hard coating solutions were prepared from alumina sols and acrylate monomers. The mixture of alumina sols, prepared from aluminum isopropoxide, and a silane coupling agent, methacryloxypropyl trimethoxysilane(MPTMS), was used as an inorganic component. Also, the mixture of acrylate monomers, pentaerythritol triacrylate(PETA), 1,6-hexanediol diacrylate(HDDA) and dipentaerythritol hexaacrylate (DPEHA), was used as an organic component. The organic-inorganic hybrid coating solutions were obtained by mixing the inorganic component and organic component, deposited on polycarbonate substrates by spin coating and densified by UV-curing. The effect of the amount of MPTMS in the inorganic component and the irradiation time during UV-curing was studied on the properties of coating films. As a result, when 0.20 mole of MPTMS was used, the pencil hardness of coated films showed an excellent pencil hardness of 3H and also exhibited a good abrasion resistance of 2% in haze.

• Bulletin of the Korean Chemical Society
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• v.23 no.2
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• pp.281-285
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• 2002

The photophysical properties and the singlet oxygen generation efficiencies of meso-tetraphenyl-trithiasapphyrin $(S_3TPS)$ and meso-tetmkis(p-methoxy phenyl)-trithiasapphy rin ((p-MeO)-$S_3TPS$) have been investigated, utilizing steady-state and time-resolved spectroscopic methods to elucidate the possibility of their use as photosensitizers for photodynamic therapy (PDT). The observed photophysical properties were compared with those of other porphyrin-like photosensitizers in geometrical and electronic structural aspects, such as extended ${\pi}$ conjugation, structural distortion, and internal heavy atoms. The steady-state electronic absorption and fluorescence spectra were both red-shifted due to the extended ${\pi}$-conjugation. The fluorescence quantum yields were measured as very small. Even though intersystem crossing rates were expected to increase due to the increment of spin orbital coupling, the triplet quantum yields were measured as less than 0.15. Such characteristics can be ascribed to the more enhanced internal conversion rates compared with the intersystem crossing rates. Furthermore, the triplet state lifetimes were shortened to -1.0 ${\mu}s$ as expected. Therefore, the singlet oxygen quantum yields were estimated to be near zero due to the fast triplet state decay rates and the inefficient energy transfer to the oxygen molecule as well as the low triplet quantum yields. The low efficiencies of energy transfer to the oxygen molecule can be attributed to the lower oxidation potential and/or the energetically low lying triplet state. Such photophysical factors should be carefully evaluated as potential photosensitizers that have extended ${\pi}$-conjugation and heavy core atoms synthesized for red-shifted absorption and high triplet state quantum yields.

• Proceedings of the Materials Research Society of Korea Conference
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• 2003.11a
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• pp.158-158
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• 2003

수평 전기로에서 CuGaTe2 다결정을 합성하여 HWE 방법으로 CuGaTe2 단결정 박막을 반절연성 GaAs(100) 위에 성장하였다. CuGaTe2 단결정 박막은 증발원과 기판의 온도를 각각 67$0^{\circ}C$, 41$0^{\circ}C$로 성장하였다. 이때 단결정 박막의 결정성이 10K에서 측정한 광발광 스펙트럼은 954.5nm (1.2989eV) 근처에서 exciton emission 스펙트럼이 가장 강하게 나타났으며, 또한 이중결정 X-선 요동곡선(DCRC)의 반폭치(FWHM)도 139arcsec로 가장 작게 측정되어 최적 성장 조건임을 알 수 있었다. Hall 효과는 van der Paw방법에 의해 측정되었으며, 온도에 의존하는 운반자 농도와 이동도는 293K에서 각각 8.72$\times$$10^{23}$개/㎥, 3.42$\times$$10^{-2}$$m^2$/V.s였다. 상온에서 CuGaTe2 단결정 박막의 광흡수 특성으로부터 에너지 띠간격이 1.22 eV였다 Band edge에 해당하는 광전도도peak의 온도 의존성은 Varshni 관계식으로 설명되었으며, Varshni 관계식의 상수값은 Eg(0) = 1.3982 eV, $\alpha$= 4.27$\times$$10^{-4}$ eV/K, $\beta$= 265.5 K로 주어졌다. CuGaTe2 단결정 박막의 광전류 단파장대 봉우리들로부터 10K에서 측정된 $\Delta$cr (crystal Field splitting)은 0.0791eV, $\Delta$s.o (spin orbit coupling)는 0.2463eV였다. 10K에서 광발광 봉우리의 919.8nm (1.3479eV)는 free exciton(Ex), 954.5nm (1.2989eV)는 donor-bound exciton 인 I2(DO,X)와 959.5nm (1.2921eV)는 acceptor-bound exciton 인 I1(AO,X) 이고, 964.6nm(1.2853eV)는 donor-acceptor pair(DAP) 발광, 1341.9nm (0.9239eV)는 self activated(SA)에 기인하는 광발광 봉우리로 고찰되었다.

• Proceedings of the Materials Research Society of Korea Conference
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• 2003.11a
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• pp.156-156
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• 2003

수평 전기로에서 ZnIn$_2$S$_4$ 다결정을 합성하여 HWE(Hot Wall Epitaxy)방법으로 2nIn2S4단결정 박막을 반절연성 GaAs(100)기판 위에 성장시켰다. ZnIn2S4 단결정 박막은 증발원의 온도를 610 $^{\circ}C$, 기판의 온도를 450 $^{\circ}C$로 성장시켰고 성장 속도는 0.5 $\mu\textrm{m}$/hr로 확인되었다. ZrIn2S4 단결정 박막의 결정성의 조사에서 10 K에서 광발광(photoluminescence) 스펙트럼이 433 nm (2.8633eV)에서 exciton emission스펙트럼이 가장 강하게 나타났으며, 또한 이중결정 X-선 요동곡선(DCRC)의 반폭치(FWHM)도 133 arcsec로 가장 작아 최적 성장 조건임을 알 수 있었다. Hall 효과는 van der Pauw방법에 의해 측정되었으며, 온도에 의존하는 운반자 농도와 이동도는 293K에서 각각 8.51$\times$$10^{17}$ electron/$cm^{-3}$ 291 $\textrm{cm}^2$/v-s였다. ZnIn2S4 단결정 박막의 광전류 단파장대 봉우리들로부터 10 K에서 측정된 $\Delta$Cr(crystal field splitting)은 0.1678 eV, $\Delta$So(spin orbit coupling)는 0.0148 eV였다. 10 K의 광발광 측정으로부터 고품질의 결정에서 볼 수 있는 free exciton 과 매우 강한 세기의 중성 주개 bound exciton등의 피크가 관찰되었다. 이때 중성 주개 bound exciton의 반치폭과 결합 에너지는 각각 9 meV와 26 meV 였다. 또한 Haynes rule에 의해 구한 불순물의 활성화 에너지는 130 meV 였다.다.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2001.07a
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• pp.533-538
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• 2001

The ZnSe sample grown by chemical bath deposition (CBD) method were annealed in Ar gas at 450$^{\circ}C$ Using extrapolation method of X-ray diffraction pattern, it was found to have zinc blend structure whose lattice parameter a$\_$o/ was 5.6687 ${\AA}$. From Hall effect, the mobility was likely to be decreased by impurity scattering at temperature range from 10 K to 150 K and by lattice scattering at temperature range from 150 K to 29 3K. The band gap given by the transmission edge changed from 2.7005 eV at 293 K to 2.8739 eV at 10 K. Comparing photocurrent peak position with transmission edge, we could find that photocurrent peaks due to excition electrons from valence band, $\Gamma$$\_$8/ and $\Gamma$$\_$7/ to conduction band $\Gamma$$\_$6/ were observed at photocurrent spectrum. From the photocurrent spectra by illumination of polarized light on the ZnSe thin film, we have found that values of spin orbit coupling splitting Δso is 0.0981 eV. From the PL spectra at 10 K, the peaks corresponding to free bound excitons and D-A pair and a broad emission band due to SA is identified. The binding energy of the free excitons are determined to be 0.0612 eV and the dissipation energy of the donor -bound exciton and acceptor-bound exciton to be 0.0172 eV, 0.0310 eV, respectively.

• Korean Journal of Crystallography
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• v.11 no.4
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• pp.212-223
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• 2000

A stochiometric mix of CuInTe₂ polycrystal was prepared in a honizonatal furnace. To obtain the single crystal thin films, CuInTe₂ mixed crystal was deposited on throughly etched GaAs(100) by the HWE system. The source and substrate temperatures were 610℃ and 450℃ respectively, and the thickness of the deposited single crystal thin film was 2.4㎛. CuInTe₂ single crystal thin film was proved to be the optimal growth condition when the excition emission spectrum was the strongest at 1085.3 nm(1.1424 eV) of photoluminescence spectrum at 10 K, and also FWHM of Double Crystal X-ray Rocking Curve (DCRC) was the smallest, 129 arcsec. The Hall effect on this sample was measured by the method of Van der Pauw, and the carrier density and mobility dependent on temperature were 9.57x10/sup 22/ electron/㎥, 1.31x10/sup -2/㎡/V·s at 293 K, respectively. The ΔCr(Crystal field splitting) and the ΔSo (spin orbit coupling splitting( measured at f10K from the photocurrent peaks in the short wavelength of the CuInTe₂ single crystal thin film were about 0.1200 eV, 0.2833 eV respectively. From the PL spectra of CuInTe₂ single crystal thin film at 10 K, the free exciton (E/sub x/) was determined to be 1064.5 nm(1.1647 eV) and the donor-bound exciton(D/sup 0/, X) and acceptor-bound exciton (A/sup 0/, X) were determined to be 1085.3 nm(1.1424 eV) and 1096.8 nm(1.1304 eV0 respectively. And also, the donor-acciptor pair (DAP)P/sub 0/, DAP-replica P₁, DAP-replica P₂ and self-activated (SA) were determined to be 1131 nm (1.0962 eV), 1164 nm(1.0651 eV), 1191.1 nm(1.0340 eV) and 1618.1 nm (0.7662 eV), respectively.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2002.07a
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• pp.273-280
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• 2002

The stochiometric mix of evaporating materials for the CuGaTe$_2$ single crystal thin films was prepared from horizontal furnance. For extrapolation method of X-ray diffraction patterns for the CuGaTe$_2$ polycrystal, it was found tetragonal structure whose lattice constant a$\_$0/ and c$\_$0/ were 6.025 ${\AA}$ and 11.931 ${\AA}$, respectively. To obtain the single crystal thin films, CuGaTe$_2$ mixed crystal was deposited on throughly etched semi-insulator GaAs(100) substrate by the Hot Wall Epitaxy (HWE) system. The source and substrate temperature were 670 $^{\circ}C$ and 410 $^{\circ}C$ respective1y, and the thickness of the single crystal thin films is 2.1 $\mu\textrm{m}$. The crystalline structure of single crystalthin films was investigated by the photoluminescence and double crystal X-ray diffraction (DCXD). Hall effect on this sample was measured by the method of van der Pauw and studied on carrier density and mobility dependence on temperature. The carrier density and mobility of CuGaTe$_2$ single crystal thin films deduced from Hall data are 8.72${\times}$10$\^$23/㎥, 3.42${\times}$10$\^$-2/㎡/V$.$s at 293K, respectively. From the photocurrent spectrum by illumination of perpendicular light on the c - axis of the CuGaTe$_2$ single crystal thin film, we have found that the values of spin orbit coupling Δs.o and the crystal field splitting Δcr were 0.0791 eV and 0/2463eV at 10K, respectively. From the PL spectra at 10K, the peaks corresponding to free bound excitons and D-A pair and a broad emission band due to SA is identified. The binding energy of the free excitons are determined to be 0.0470eV and the dissipation energy of the donor -bound exciton and acceptor-bound exciton to be 0.0490eV, 0.00558eV, respectively.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2004.11a
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• pp.230-233
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• 2004

The stochiometric mix of evaporating materials for the $CuInS_2$ single crystal thin films was prepared from horizontal furnance. Using extrapolation method of X-ray diffraction patterns for the $CuInS_2$ polycrystal, it was found tetragonal structure whose lattice constant $a_0$ and $c_0$ were $5.524\;{\AA}$ and $11.142\;{\AA}$, respectively. To obtain the single crystal thin films, $CuInS_2$ mixed crystal was deposited on throughly etched semi-insulator GaAs(100) substrate by the hot wall epitaxy (HWE) system. The source and substrate temperature were 640 t and 430 t, respectively and the thickness of the single crystal thin films was $2{\mu}m$. Hall effect on this sample was measured by the method of van dot Pauw and studied on carrier density and temperature dependence of mobility. The carrier density and mobility deduced from Hall data are $9.64{\times}10^{22}/m^3,\;2.95{\times}10^{-2}\;m^2/V{\cdot}s$ at 293 K, respectively The optical energy gaps were found to be 1.53 eV at room temperature. From the photocurrent spectrum by illumination of perpendicular light on the c - axis of the thin film, we have found that the values of spin orbit coupling splitting ${\Delta}So$ and the crystal field splitting ${\Delta}Cr$ were 0.0211 eV and 0.0045 eV at 10 K, respectively. From PL peaks measured at 10K, 807.7nm (1.5350ev) mean Ex peak of the free exciton emission, also 810.3nm (1.5301eV) expresses $I_2$ peak of donor-bound exciton emission and 815.6nm (1.5201eV) emerges $I_1$ peak of acceptor-bound exciton emission. In addition, the peak observed at 862.0nm (1.4383eV) was analyzed to be PL peak due to donor-acceptor pair(DAP).