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Luminescent Lanthanide Complexes for Advanced Photonics Applications

  • Eom, Yu Kyung;Ryu, Jung Ho;Kim, Hwan Kyu
    • Rapid Communication in Photoscience
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    • v.1 no.1
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    • pp.1-9
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    • 2012
  • Luminescent lanthanide complexes have been overviewed for advanced photonics applications. Lanthanide(III) ions ($Ln^{3+}$) were encapsulated by the luminescent ligands such as metalloporphyrins, naphthalenes, anthracene, push-pull diketone derivatives and boron dipyrromethene(bodipy). The energy levels of the luminescent ligands were tailored to maintain the effective energy transfer process from luminescent ligands to $Ln^{3+}$ ions for getting a higher optical amplification gain. Also, key parameters for emission enhancement and efficient energy transfer pathways for the sensitization of $Ln^{3+}$ ions by luminescent ligands were investigated. Furthermore, to enhance the optophysical properties of novel luminescent $Ln^{3+}$ complexes, aryl ether-functionalized dendrons as photon antennas have been incorporated into luminescent $Ln^{3+}$ complexes, yielding novel $Ln^{3+}$-cored dendrimer complex such as metalloporphyrins, naphthalenes, and anthracenes bearing the Fr$\acute{e}$chet aryl-ether dendrons, namely, ($Er^{3+}-[Gn-Pt-Por]_3$ (terpy), $Er^{3+}-[Gn-Naph]_3$(terpy) and $Er^{3+}-[Gn-An]_3$(terpy)). These complexs showed much stronger near-IR emission bands at 1530 nm, originated from the 4f-4f electronic transition of the first excited state ($^4I_{13/2}$) to the ground state ($^4I_{15/2}$) of the partially filled 4f shell. A significant decrease in the fluorescence of metalloporphyrins, naphthalenes and anthracene ligand were accompanied by a strong increase in the near IR emission of the $Ln^{3+}$ ions. The near IR emission intensities of $Ln^{3+}$ ions in the lanthanide(III)-encapsulated dendrimer complexes were dramatically enhanced with increasing the generation number (n) of dendrons, due to the site-isolation and the light-harvesting(LH) effects. Furthermore, it was first attempted to distinguish between the site-isolation and the light-harvesting effects in the present complexes. In this review, synthesis and photophysical studies of inert and stable luminescent $Ln^{3+}$ complexes will be dealt for the advanced photonics applications. Also, the review will include the exploratory investigation of the key parameters for emission enhancement and the effective energy transfer pathways from luminescent ligands to $Ln^{3+}$ ions with $Ln^{3+}$-chelated prototype complexes.

Structural and Electrical Properties of Amorphous 2Ti4O12 Thin Films Grown on TiN Substrate (TiN 기판 위에 성장시킨 비정질 BaSm2Ti4O12 박막의 구조 및 전기적 특성 연구)

  • Park, Yong-Jun;Paik, Jong-Hoo;Lee, Young-Jin;Jeong, Young-Hun;Nahm, Sahn
    • Korean Journal of Materials Research
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    • v.18 no.4
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    • pp.169-174
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    • 2008
  • The structural and electrical properties of amorphous $BaSm_2Ti_4O_{12}$ (BSmT) films on a $TiN/SiO_2/Si$ substrate deposited using a RF magnetron sputtering method were investigated. The deposition of BSmT films was carried out at $300^{\circ}C$ in a mixed oxygen and argon ($O_2$ : Ar = 1 : 4) atmosphere with a total pressure of 8.0 mTorr. In particular, a 45 nm-thick amorphous BSmT film exhibited a high capacitance density and low dissipation factor of $7.60\;fF/{\mu}m2$ and 1.3%, respectively, with a dielectric constant of 38 at 100 kHz. Its capacitance showed very little change, even in GHz ranges from 1.0 GHz to 6.0 GHz. The quality factor of the BSmT film was as high as 67 at 6 GHz. The leakage current density of the BSmT film was also very low, at approximately $5.11\;nA/cm^2$ at 2 V; its conduction mechanism was explained by the the Poole-Frenkel emission. The quadratic voltage coefficient of capacitance of the BSmT film was approximately $698\;ppm/V^2$, which is higher than the required value (<$100\;ppm/V^2$) for RF application. This could be reduced by improving the process condition. The temperature coefficient of capacitance of the film was low at nearly $296\;ppm/^{\circ}C$ at 100 kHz. Therefore, amorphous BSmT grown on a TiN substrate is a viable candidate material for a metal-insulator-metal capacitor.

Synthesis of Binuclear Bismacrocyclic Iron(II) Complex by the Aerobic Oxidation of Iron(II) Complex of 1,4,8,11-Tetraazacyclotetradecane

  • Myunghyun Paik Suh;Gee-Yeon Kong;Il-Soon Kim
    • Bulletin of the Korean Chemical Society
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    • v.14 no.4
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    • pp.439-444
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    • 1993
  • The aerobic oxidation of the Fe(II) complex of 1,4,8,11-tetraazacyclotetradecane, [Fe(cyclam)$(CH_3CN)_2](ClO_4)_2$, in MeCN in the presence of a few drops of $HClO_4$ leads to low spin Fe(III) species [Fe(cyclam)$(CH_3CN)_2](ClO_4)_3$. The Fe(III) cyclam complex is further oxidized in the air in the presence of a trace of water to produce the deep green binuclear bismacrocyclic Fe(II) complex $[Fe_2(C_{20}H_{36}N_8)(CH_3CN)_4](ClO_4)_4{\cdot}2CH_3CN$. The Fe(II) ions of the complex are six-coordinated and the bismacrocyclic ligand is extensively unsaturated. $[Fe_2(C_{20}H_{36}N_8)(CH_3CN)_4](ClO_4)_4{\cdot}2CH_3CN$ crystallizes in the monoclinic space group $P2_1/n$ with a= 13.099 (1) ${\AA}$, b= 10.930 (1) ${\AA}$, c= 17.859 (1) ${\AA}$, ${\beta}$= 95.315 $(7)^{\circ}$, and Z= 2. The structure was solved by heavy atom methods and refined anisotropically to R values of R= 0.0633 and $R_w$= 0.0702 for 1819 observed reflections with F > $4{\sigma}$ (F) measured with Mo K${\alpha}$ radiation on a CAD-4 diffractometer. The two macrocyclic units are coupled through the bridgehead carbons of ${\beta}$-diimitie moieties by a double bond. The double bonds in each macrocycle unit are localized. The average bond distances of $Fe(II)-N_{imine}$, $Fe(II)-N_{amine}$, and $Fe(II)-N_{MeCN}$ are 1.890 (5), 2.001 (5), and 1.925 (6) ${\AA}$, respectively. The complex is diamagnetic, containing two low spin Fe(II) ions in the molecule. The complex shows extremely intense charge transfer band in the near infrared at 868 nm with ${\varepsilon}$= 25,000 $M^{-1}cm^{-1}$. The complex shows a one-electron oxidation wave at +0.83 volts and two one-electron reduction waves at -0.43 and-0.72 volts vs. Ag/AgCl reference electrode. The complex reacts with carbon monoxide in $MeNO_2$ to form carbonyl adducts, whose $v_{CO}$ value (2010 $cm^{-1}$) indicates the ${\pi}$-accepting property of the present bismacrocyclic ligand.

The Interfacial Nature of TiO2 and ZnO Nanoparticles Modified by Gold Nanoparticles

  • Do, Ye-Ji;Choi, Jae-Soo;Kim, Seoq-K.;Sohn, Young-Ku
    • Bulletin of the Korean Chemical Society
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    • v.31 no.8
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    • pp.2170-2174
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    • 2010
  • The surfaces of $TiO_2$ and ZnO nanoparticles have been modified by gold (Au) nanoparticles by a reduction method in solution. Their interfacial electronic structures and optical absorptions have been studied by depth-profiling X-ray photoelectron spectroscopy (XPS) and UV-vis absorption spectroscopy, respectively. Upon Au-modification, UV-vis absorption spectra reveal a broad surface plasmon peak at around 500 nm. For the as-prepared Au-modified $TiO_2$ and ZnO, the Au $4f_{7/2}$ XPS peaks exhibit at 83.7 and 83.9 eV, respectively. These are due to a charge transfer effect from the metal oxide support to the Au. For $TiO_2$, the larger binding energy shift from that (84.0 eV) of bulk Au could indicate that Au-modification site of $TiO_2$ is different from that of ZnO. On the basis of the XPS data with sputtering depth, we conclude that cationic (1+ and 3+) Au species, plausibly $Au(OH)_x$ (x = 1-3), commonly form mainly at the Au-$TiO_2$ and Au-ZnO interfaces. With $Ar^+$ ion sputtering, the oxidation state of Ti dramatically changes from 4+ to 3+ and 2+ while that (2+) of Zn shows no discernible change based on the binding energy position and the full-width at half maximum (FWHM).

Effects of $SiO_2$ Particle-size on Fabrication Properties of LPS-SiC Ceramics (LPS-SiC 세라믹스의 제조특성에 미치는 $SiQ_2$ 입자크기의 영향)

  • Kim, Seong-Hoon;Yoon, Han-Ki;Kim, Bu-An
    • Proceedings of the Korea Committee for Ocean Resources and Engineering Conference
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    • 2006.11a
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    • pp.162-165
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    • 2006
  • In this study, Liquid Phase Sintered SiC (LPS-SiC) was fabricated by hot pressing method with $\beta$-SiC powder whose a particle size is 30nm and less on the average in argon condition at 1780 and $1800^{\circ}C$ under 20MPa. Alumina ($Al_2O_3$), yttria ($Y_2O_3$) and silica ($SiO_2$) were used for sintering additives. To investigate effects of particle-size and temperature on $SiO_2$, LPS-SiC was fixed $Al_2O_3$, $Y_2O_3$ and then particle-size of $SiO_2$ were changed as two kinds. The system of particle-size and temperature on sintering additives which affects a property of sintering os well os the influence depending on particle-size and temperature of sintering additives were investigated by measurement of sintering properties. Such as measurement of sintering density, vikers hardness and observing of microstructure were investigated to make sure of the optimum condition which is about matrix of $SiC_f/SiC$ composites. Base on the composition of sintering additives, microstructure and sintering property correlation, the effect of particle-size of sintering additives are discussed. An experimental method to investigate the dynamic characteristics of bums in extreme environmental condition is established.

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Surface Chemical Properties of the Youngdong Illite Ore:the pH of Zero Proton Charge and Surface Site Density (영동 일라이트 광석의 표면 화학특성:영 전하점과 표면전하 밀도)

  • 조현구;김은영;정기영
    • Journal of the Mineralogical Society of Korea
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    • v.14 no.1
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    • pp.12-20
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    • 2001
  • 충북 영동군 동창광산에서 산출되는 일라이트(illite)광선의 표면화학특성을 전위차 적정 실험과 FITEQL3.2 프로그램을 이용하여 연구하였다. 정량 Xtjs 회절 분석에 의한 일라이트 광석의 광물조석은 석영 46.6% 일라이트 41.6% 카올리나이트(kaolinite) 11.8%이며 $N_2$BET 방법에 의하여 구한 비표면적은 $6.52 m^2$g이다. 전위차 적정 실험결과를 그란(Gran)법을 적용하여 구한 일라이트광석의 영전하점($pH_{pznpc}$ )은 pH 3.9 총표면 자리 밀도는 21.24 sites/$nm^2$이다. 표면 복합체 모델중 일정 용량 모델을 적용해 일라이트 광석의 표변 특성에 알맞는 모델을 찾아보았다. 일라이트 광석의 표면을 사면체 자리와 팔면체 자리로 나누어 설정한 2sites$-3pK_{ a}$s 모델은 변수값이 수렴되지않았으므로 부적절하다고 판단된다. 일라이트 광석의 표면을 하나의 균질한 흡착표면으로 가정해서 설정한 1 site -1 $K_{a}$ 와 1 site -2 $pK_{a}$ s 모델 사이에는 뚜렷한 차이는 없지만, 1 site -1 $pK_{a}$ 모델의 WSOS/DF 값이 17, 1 site - 2 $pK_a{s}$ 모델은 26으로서 앞 모델이 보다 적절하다. 이 결과는 일라이트 광석 표면에서 수소의 해리와 첨가 반응 중 첨가 반응을 무시하여도 표면반응을 설명하는 데 큰 무리가 없음을 시사한다. 가장 적절하다고 판단되는 1 site -1 $pK_{a}$ 모델의 $pK_{a}$ 값은 4.17, specific capacitance는 $6F/m^2$ 표면 자리 농도는 $1.15\Times10^{-3}$ mol/L 이다.

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Laser Damage Threshold Increase of A/R Coating Films for 200MHz AOM (A/R 코팅 변화에 따른 200MHz AOM의 laser damage threshold 증가)

  • Kim, Yong-Hun;Lee, Hang-Hun;Lee, Jin-Ho;Park, Yeong-Jun;Park, Jeong-Ho
    • Korean Journal of Materials Research
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    • v.7 no.3
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    • pp.213-217
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    • 1997
  • AOhf(Hcousto-r)l)tic niodulator) with :!OOlIiz freclucncl- and Sfi(;(Seconrl harmonic generation) green lasel-Lvith 53% nm wavelength were used for Il\'IIII~Dii.it,ii v~ilco disk recorder) FOI rhe appli~aptin of high densit]. optical recording, a high po\ver I ~ c r is r c ~ ~ l i ~ i l - u l ic I !tic. s\-sti,m a n d optic.,~I io;iting l,t)c>rs of each optical device must have a high laser damage threshoid hie rn;itie ant] retlwtive coatings on a $TeO_{2}$ singlc crystal. which is used as an acoustooptic material, by E-beam evaporation method. Laser damage threshold \vas nicdsureci hy Ar laser with the input power oi 0.55LV 1,aser damage threiholti 01 $ZrO_{2}$ and $SiO_{2}$. filn-is were higher than $AI_{2}O_{3}$ f i l m U'e also investigated a long--tern1 stability of the output po\ver of St{(; green laser

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Schottky Contact Application을 위한 Yb Germanides 형성 및 특성에 관한 연구

  • Na, Se-Gwon;Gang, Jun-Gu;Choe, Ju-Yun;Lee, Seok-Hui;Kim, Hyeong-Seop;Lee, Hu-Jeong
    • Proceedings of the Korean Vacuum Society Conference
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    • 2013.02a
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    • pp.399-399
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    • 2013
  • Metal silicides는 Si 기반의microelectronic devices의 interconnect와 contact 물질 등에 사용하기 위하여 그 형성 mechanism과 전기적 특성에 대한 연구가 많이 이루어지고 있다. 이 중 Rare-earth(RE) silicides는 저온에서 silicides를 형성하고, n-type Si과 낮은 Schottky Barrier contact (~0.3 eV)을 이룬다. 또한 낮은 resistivity와 Si과의 작은 lattice mismatch, 그리고 epitaxial growth의 가능성, 높은 thermal stability 등의 장점을 갖고 있다. RE silicides 중 ytterbium silicide는 가장 낮은 electric work function을 갖고 있어 n-channel schottky barrier MOSFETs의 source/drain으로 주목받고 있다. 또한 Silicon 기반의 CMOSFETs의 성능 향상 한계로 인하여 germanium 기반의 소자에 대한 연구가 이루어져 왔다. Ge 기반 FETs 제작을 위해서는 낮은 source/drain series/contact resistances의 contact을 형성해야 한다. 본 연구에서는 저접촉 저항 contact material로서 ytterbium germanide의 가능성에 대해 고찰하고자 하였다. HRTEM과 EDS를 이용하여 ytterbium germanide의 미세구조 분석과 면저항 및 Schottky Barrier Heights 등의 전기적 특성 분석을 진행하였다. Low doped n-type Ge (100) wafer를 1%의 hydrofluoric (HF) acid solution에 세정하여 native oxide layer를 제거하고, 고진공에서 RF sputtering 법을 이용하여 ytterbium 30 nm를 먼저 증착하고, 그 위에 ytterbium의 oxidation을 방지하기 위한 capping layer로 100 nm 두께의 TiN을 증착하였다. 증착 후, rapid thermal anneal (RTA)을 이용하여 N2 분위기에서 $300{\sim}700^{\circ}C$에서 각각 1분간 열처리하여 ytterbium germanides를 형성하였다. Ytterbium germanide의 미세구조 분석은 transmission electron microscopy (JEM-2100F)을 이용하였다. 면 저항 측정을 위해 sulfuric acid와 hydrogen peroxide solution (H2SO4:H2O2=6:1)에서 strip을 진행하여 TiN과 unreacted Yb을 제거하였고, 4-point probe를 통하여 측정하였다. Yb germanides의 면저항은 열처리 온도 증가에 따라 감소하다 증가하는 경향을 보이고, $400{\sim}500^{\circ}C$에서 가장 작은 면저항을 나타내었다. HRTEM 분석 결과, deposition 과정에서 Yb과 Si의 intermixing이 일어나 amorphous layer가 존재하였고, 열처리 온도가 증가하면서 diffusion이 더 활발히 일어나 amorphous layer의 두께가 증가하였다. $350^{\circ}C$ 열처리 샘플에서 germanide/Ge interface에서 epitaxial 구조의 crystalline Yb germanide가 형성되었고, EDS 측정 및 diffraction pattern을 통하여 안정상인 YbGe2-X phase임을 확인하였다. 이러한 epitaxial growth는 면저항의 감소를 가져왔으며, 열처리 온도가 증가하면서 epitaxial layer가 증가하다가 고온에서 polycrystalline 구조의 Yb germanide가 형성되어 면저항의 증가를 가져왔다. Schottky Barrier Heights 측정 결과 또한 면저항 경향과 동일하게 열처리 증가에 따라 감소하다가 고온에서 다시 증가하였다.

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Elucidation of Anti-tumor Initiator and Promoter Derived from Seaweed-2: Investigation of Seaweed Extracts Suppressing Mutagenic Activity of PhIP and MeIQx (해조류 중의 anti-tumor initiator 및 promoter의 해석-2: PhIP와 MeIQx의 돌연변이원성을 억제하는 해조 추출물 소재의 연구)

  • PARK Young-Beom;KIM In-Soo;YOO Sung-Jae;AHN Jong-Khan;LEE Tae-Gee;PARK Douck-Chon;KIM Seon-Bong
    • Korean Journal of Fisheries and Aquatic Sciences
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    • v.31 no.4
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    • pp.581-586
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    • 1998
  • The present study was conducted to prepare seaweed extracts suppressing mutagenic activity of 2-amino-1-methyl-6-phenylimidazo[4,5-b] pyridine ( PhIP ) ana 2-amino-3,8-dimethylmidazo[4,5-f]quinoxaline (MeIQx) derived from cooked meat produce. The tumor initiation activity of PhIP and MeIQx was assayed with Ames method using Salmonella typhimurium TA98 in the presence of S-9 mixtures before and after addition of methanol-solubles of seaweed, such as, Phaeophyta; Undaria pinnatifida, Ecklonia stolonifera Ecklonia cava, Laminaia japonica Sargassum fulvellum, Sargassum hornezi, Sargassum miyabei, Sargassum thunbergii, Agarum cribrosum and Hizikia fusifomis, Rhodophpei Porphyra yezoensis, Grateloupia eiliptiut Lomentraria catenata, Ploemium telfairiae and Glarilaria verrucosa, Chlorophyta; Codium fragile, Enteromorpha compresa and Ulva pertusa. Among seaweed tested, Phaeophyta was shown the higher desmutagenic activity than Rhodophyta and Chlorophyta. E. stolonifera, E. cava and S. miyabei, among Phaeophyta exerted the stronger desmutagenic activity (above $90\%$/2 mg). The ethyl acetate, diethyl ether and chlomform extracts except water extracts from E. stolonifera exhibited a high desmutagenic activity. The ethyl acetate extract of E. stolonifera which showed highest activity was fractionated with Sephadex LH20 column chromatography to give active fraction A-7, which showed desmutagenicity of $90\%$/mg against PhIP and $80\%$/mg against MeIQx. The active fraction had the absorbance at 207.7 and 232nm.

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Study of Surface Alloying of TiC, TiB2 and VC with Carbon Steel Using High Energy Electron Beam Irradiation (고에너지 전자빔 투사를 이용한 TiC, TiB2 및 VC/ 탄소강 표면합금화 연구)

  • Yoo, Jung-Hoon;Shin, Kee-Sam;Yoon, Jae-Hong;Lee, Chan-Gyu;Hur, Sung-Gang;Lee, Je-Hyun;Oh, Jun-Chul;Lee, Sung-Hak;Euk, Kwang-Jun
    • Korean Journal of Materials Research
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    • v.12 no.12
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    • pp.904-910
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    • 2002
  • Surface alloying using TiC, $TiB_2$ and VC ceramic particles on carbon steel has been performed using high voltage electron beam. Each type of ceramic particles was mixed with flux of Al and $MgF_2$ in 1 to 4 ratio. The microstructures of the surface alloyed layers consisted of melted region, interface region. heat affected region and the unaffected matrix. The surface layer of the TiC surface alloyed had a cubed primary and a eutectic type of TiC. $TiB_2$ in surface layer of $TiB_2$ surface alloyed were incompletely melted with$ TiB_2$ particles as observed before the alloying. On the surface layer of the VC surface alloyed, very well defined cell structure was observed with VC on the cell boundary. In addition, ~50 nm in diameter VC particles in high density were ubiquitous in the matrix. Those fine VC particles prominently improved the hardness and wear resistance of the surface layer of the VC surface alloyed.