• Title/Summary/Keyword: charge-transfer transition

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Magnetism during adsorption of oxygen in Pt segregated $Pt_3Ni$ (111): Density Functional Study

  • Kumar, Sharma Bharat;Kwon, O-Ryong;Odkhuu, Dorj;Hong, Soon-Cheol
    • Proceedings of the Korean Magnestics Society Conference
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    • 2011.12a
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    • pp.14-14
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    • 2011
  • Limited understanding of the surface properties of $Pt_3Ni$ for the oxygen reduction reaction (ORR) in polymer electrolyte membrane fuel cell (PEMFC) has motivated the study of magnetic properties and electronic structures of Pt segregated $Pt_3Ni$ (111) surface during adsorption of oxygen molecule on it. The first principle method based on density functional theory (DFT) is carried out. Nonmagnetic Pt has induced magnetic moment due to strong hybridization between Ni 3d and Pt 5d. It is found that an oxygen molecule prefers bridge site with Pt rich subsurface environment for adsorption on the surface of Pt segregated $Pt_3Ni$ (111). It is seen that there is very small charge transfer from $O_2$ to Pt. The curve of energy versus magnetic moment of the oxygen explains the magnetic moments in transition states. We found the dissociation barrier of 1.07eV significantly higher than dissociation barrier 0.77eV on Pt (111) suggesting that the dissociation is more difficult on Pt segregated $Pt_3Ni$ (111) surface. The spin polarized densities of states are presented in order to understand electronic structures of Pt and $O_2$ during the adsorption in detail.

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Synthesis and characterization of CaZrO3:Pr3+ phosphor by skull melting method (스컬용융법에 의한 CaZrO3:Pr3+ 형광체 합성 및 특성분석)

  • Choi, Hyunmin;Kim, Youngchool;Seok, Jeongwon
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.31 no.5
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    • pp.228-232
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    • 2021
  • Ca1-xZrO3:xPr phosphor with perovskite structure was successfully synthesized by using skull melting method. The crystal structure, morphology and optical properties of synthesized phosphor were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), ultraviolet fluorescence reaction and photoluminescence. The XRD results indicated that single crystals of CaZrO3:Pr3+ belongs to orthorhombic perovskite system. The synthesized phosphor could be excited by UV light (254 nm) and the emission spectra results indicated that green luminescence of CaZrO3:Pr3+ due to charge transfer transition 3P03H4, 3P13H5 and 3P03H5 at 506, 536 and 548 nm was dominant.

Effects of Flux and Ta5+ Substitution on the Photoluminescence of Lu(Nb,Ta)O4:Eu3+ Phosphors (융제 및 Ta5+ 치환이 Lu(Nb,Ta)O4:Eu3+ 형광체의 발광 특성에 미치는 영향)

  • Kim, Jiwon;Kim, Young Jin
    • Korean Journal of Materials Research
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    • v.29 no.9
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    • pp.559-566
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    • 2019
  • $Lu(Nb,Ta)O_4:Eu^{3+}$ powders are synthesized by a solid-state reaction process using LiCl and $Li_2SO_4$ fluxes. The photoluminescence (PL) excitation spectra of the synthesized powders consist of broad bands at approximately 270 nm and sharp peaks in the near ultraviolet region, which are assigned to the $Nb^{5+}-O^{2-}$ charge transfer of $[NbO_4]^{3-}$ niobates and the f-f transition of $Eu^{3+}$, respectively. The PL emission spectra exhibit red peaks assigned to the $^5D_0{\rightarrow}^7F_J$ transitions of $Eu^{3+}$. The strongest peak is obtained at 614 nm ($^5D_0{\rightarrow}^7F_2$), indicating that the $Eu^{3+}$ ions are incorporated into the $Lu^{3+}$ asymmetric sites. The addition of fluxes causes the increase in emission intensity, and $Li_2SO_4$ flux is more effective for enhancement in emission intensity than is LiCl flux. The substitution of $Ta^{5+}$ for $Nb^{5+}$ results in an increase or decrease in the emission intensity of $LuNb_{1-x}Ta_xO_4:Eu^{3+}$ powders, depending on amount and kind of flux. The findings are explained using particle morphology, modification of the $[NbO_4]^{3-}$ structure, formation of substructure of $LuTaO_4$, and change in the crystal field surrounding the $Eu^{3+}$ ions.

Structural, optical, and morphological properties of BaWO4:Sm3+ phosphor thin films grown at different deposition temperature (서로 다른 증착 온도에서 성장된 BaWO4:Sm3+ 형광체 박막의 구조, 광학, 표면 형상의 특성)

  • Cho, Shinho
    • Journal of the Korean institute of surface engineering
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    • v.55 no.2
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    • pp.96-101
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    • 2022
  • The effects of the growth temperature on the structural, optical, and morphological properties of BaWO4:Sm3+ phosphor thin films were investigated. The BaWO4:Sm3+ thin films were grown on quartz substrates at several growth temperatures by radio-frequency magnetron sputtering. All the thin films crystallized in a tetragonal structure with a main BaWO4 (112) diffraction peak. The 830 nm-thick BaWO4:Sm3+ thin films grown at 300 ℃ exhibited numerous polygon-shaped particles. The excitation spectra of BaWO4:Sm3+ thin films consisted of a broad excitation band in the 200-270 nm with a maximum at 236 nm due to the O2--Sm3+ charge transfer and two small bands peaked at 402 and 463 nm, respectively. Under 236 nm excitation, the BaWO4:Sm3+ thin films showed an intense red emission peak at 641 nm due to the 4G5/26H9/2 transition of Sm3+, indicating that the Sm3+ ions occupied sites of non-inversion symmetry in the BaWO4 host lattice. The highest emission intensity was observed for the thin film grown at 300 ℃, with a 51.8% transmittance and 5.09 eV bandgap. The average optical transmittance in the wavelength range of 500-1100 nm was increased from 53.2% at 200 ℃ to 60.8% after growing at 400 ℃. These results suggest that 300 ℃ is the optimum temperature for growing redemitting BaWO4:Sm3+ thin films.

Property of Optical Spectroscopy on the Lanthanum Tungstate doped Eu3+ Ion (Eu3+ 이온이 첨가된 란타넘텅스텐산화물의 분광학 특성)

  • Seo, Hyojin;Park, Cheolwoo
    • Journal of the Korean Society of Radiology
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    • v.9 no.1
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    • pp.39-45
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    • 2015
  • $La_2W_3O_{12}:Eu^{3+}$ phosphors were prepared by solid state reaction method. The crystal structure was characterized by XRD pattern and ICSD card (78180). Luminescence properties of $La_2W_3O_{12}:Eu^{3+}$ are investigated by optical and laser-excitation spectroscopy in which emission and excitation spectra and time-resolved spectra are measured. The 1 mol % $Eu^{3+}$-doped $La_2W_3O_{12}$ phosphor exhibits broad excitation band peaking at 286 nm due to the ligand-to-metal charge transfer transition. The excitation lines due to the $^7F_0{\rightarrow}{^5D_4},{^5D_4},{^5L_6},{^5G_4},{^5D_3},{^5D_2}$ transitions of $Eu^{3+}$ are observed in the wavelength region 350-500 nm. The strong line emission is observed at 618 nm corresponding to the due to the $^5D_0{\rightarrow}^7F_2$ transition. The lifetime of 618 nm emission decreases with increasing temperature as 7 K ($114{\mu}s$), 100 K ($94{\mu}s$), 200 K ($10{\mu}s$) and 300 K ($0.5{\mu}s$).

Synthesis and Optical Properties of CaMoO4:RE3+ (RE=Eu, Dy) Phosphors (CaMoO4:RE3+ (RE=Eu, Dy) 형광체의 제조와 광학 특성)

  • Cho, Shinho
    • Journal of the Korean Vacuum Society
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    • v.22 no.2
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    • pp.79-85
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    • 2013
  • Rare earth ions, either $Eu^{3+}$ or $Dy^{3+}$-doped $CaMoO_4$ phosphors were synthesized by using the solid-state reaction method. The crystalline structure of all the phosphor powders, irrespective of the type and concentration of activator ions, was found to be a tetragonal system with the main diffraction peak at (112) plane. For $Eu^{3+}$-doped $CaMoO_4$ phosphors, the grain particles showed an increasing tendency and the pebble-like patterns with a very homogeneous size distribution in the range of 0.01~0.10 mol of $Eu^{3+}$ ions concentration, and the excitation spectra were composed of a broad band centered at 311 nm and weak multiline peaked in the range of 360~470 nm. The dominant emission spectrum was the strong red emission centered at 618 nm due to the $^5D_0{\rightarrow}^7F_2$ transition of $Eu^{3+}$ ions. For $Dy^{3+}$-doped $CaMoO_4$ powders, excitation spectra showed a charge transfer band centered at 303 nm and relatively weak bands resulting from the transitions of $Dy^{3+}$ ions and the main yellow emission spectrum was observed at 578 nm, which was assigned to the $^4F_{9/2}{\rightarrow}^7H_{13/2}$ transition of $Dy^{3+}$ ions.

Synthesis and Anaiysis of Photohnninescence Properties of $^5D_1$$^7F_1$ Transition in $LaGaO_3$:$Eu^{3+}$ Red Phosphor ($LaGaO_3$:$Eu^{3+}$형광체의 합성 및 발광 특성)

  • Kim, Kyoung Hwa;Choi, Yoon Young;Sohn, Kee Sun;Kim, Chang Hae;Park, Hee Dong;Choe, Se Young
    • Journal of the Korean Chemical Society
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    • v.44 no.5
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    • pp.453-459
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    • 2000
  • FED has deserved an intensive attentioD as a new flat panel display. The present investigationaims at undemtanding the photoluminescence and cathodoluminescent properties of hGaO$_3$: $Eu^{3+}$ phosphor bytaking into account the possibility that this phosphor could be applied for FED. In onler to investigate on.sucha detailed behavior; 8everM experimental skil18 Je conducted to the LaGaO$_3$:$Eu^{3+}$ phosphoL The excimtion srectrum artd emission spectmn were rnezsured in the UV range and then decay curve of $^5D_0$+$^7F_j$transitions\vas examined. The decay behavior of $^5D_0$ emission was anMyzed by a newly Iuoposed cross-relaxation mech-ani8In in asswiation with inteFwnter di1ffision (or migration). The cross-mlaxation from $^5D_0$ to CTB (Cha'geTransfer Band) wuld be a quite retsonable by considering the excitation spectrum. It could be also found thatthe quenching type was changed from ditfrsion controlled process to the direct quenching process -s inJeasing $Eu^{3+}$ oncntration.

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Study on Formation and Properties of Dioxomolybdenum Complexes (디옥소몰리브덴 착물의 합성과 그 성질에 대한 연구)

  • Sang-Oh Oh;Bon-Kweon Koo
    • Journal of the Korean Chemical Society
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    • v.30 no.5
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    • pp.441-448
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    • 1986
  • Dioxobis(sub.-salicylaldiminato) molybdenum (VI) complexes, $MoO_2\;(X-sal-N-R)_2,\;(X=H,\;5-CH_3,\;R=C_6H_5,\;p-F-C_6H_4,\;m-Cl-C_6H_4,p-I-C_6H_4\;and\;p-C_2H_5-C_6H_4)$, have been prepared by reactions of dioxobis(sub.-salicylaldehydato) molybdenum (VI), $MoO_2(X-sal)_2$ with primary amines, in which $MoO_2(X-sal)_2$ complexes were obtained by acidification of a mixture solution of ammonium paramolybdate in water and appropriate salicylaldehyde in methanol. All these complexes show two strong Mo=O stretching imodes in the 900-940$cm^{-1}$ and p.m.r. spectra exhibited only one signal for the azomethine group. These results confirmed that the complexes are six-coordinated octahedron with a $cis-MoO_2$ group and the geometrical configurations of the complexes possess a C2 axis of symmetry. From the mass analyses of the complexes, it found that the composition ratios of $MoO_2$ : ligand are 1 : 2. The charge transfer transition corresponding to N-Mo, and O-Mo occured at 29,000$cm^{-1}$ and 32,000$cm^{-1}$ respectively. Where, the complexes were found to be non-ionic materials by conductivity measurements in dimethylformamide.

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Synthesis and Structural Characterization of Main Group 15 Organometallics R3M and R(Ph)2P(=N-Ar)(M = P, Sb, Bi; R = phenanthrenyl; Ar = 2,6-iPr2-C6H3)

  • Lee, Eun-Ji;Hong, Jin-Seok;Kim, Tae-Jeong;Kang, Young-Jin;Han, Eun-Me;Lee, Jae-Jung;Song, Ki-Hyung;Kim, Dong-Uk
    • Bulletin of the Korean Chemical Society
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    • v.26 no.12
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    • pp.1946-1952
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    • 2005
  • New group 15 organometallic compounds, M$(phenanthrenyl)_3$ (M = P (1), Sb (2), Bi (3)) have been prepared from the reactions of 9-phenanthrenyllithium with $MCl_3$. A reaction of 9-(diphenylphosphino)phenanthrene with 2,6-diisopropylphenyl azide led to the formation of (phenanthrenyl)${(Ph)}_2P$=N-(2,6-$^iPr_2C_6H_3$) (4). The crystal structures of 2 and 4 have been determined by single-crystal X-ray diffractions, both of which crystallize with two independent molecules in the asymmetric unit. Compound 2 shows a trigonal pyramidal geometry around the Sb atom with three phenanthrenyl groups being located in a screw-like fashion with an approximately $C_3$ symmetry. A significant amount of CH- -$\pi$ interaction exists between two independent molecules of 4. The phosphorus center possesses a distorted tetrahedral environment with P-N bond lengths of 1.557(3)$\AA$ (P(1) N) and 1.532(3)$\AA$ (P(2)-N), respectively, which are short enough to support a double bond character. One of the most intriguing structural features of 4 is an unusually diminished bond angle of C-N-P, attributable to the hydrogen bonding of N(1)-H(5A) [ca. 2.49$\AA$ between two adjacent molecules in crystal packing. The compounds 1-3 show purple emission both in solution and as films at room temperature with emission maxima ($\lambda_{max}$) at 349, 366, and 386 nm, respectively, attributable to the ligand centered $\pi$ $\rightarrow$ $\pi^\ast$ transition in phenanthrene contributed by the lone pair electrons of the Gp 15 elements. Yet the nature of luminescence observed with 4 differs in that it originates from $\pi$ (diisopropylbenzene)-$\pi^\ast$ (phenanthrene) transitions with the $\rho\pi$contribution from the nitrogen atom. The emission maximum of 4 is red-shifted ranging 350-450 nm due to the internal charge transfer from the phenanthrenyl ring to the N-arylamine group as deduced from the ab initio calculations.

Luminescence characterization of $EU^{3+}$ and $Bi^{3+}$ co-doped in ${Y_2}{SiO_5}$ red emitting phosphor by solid state reaction method (고상 반응법으로 합성한 ${Y_2}{SiO_5}:\;EU^{3+}$, $Bi^{3+}$ 적색 형광체의 발광 특성)

  • Moon, J.W.;Song, Y.H.;Park, W.J.;Yoon, D.H.
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.19 no.1
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    • pp.15-18
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    • 2009
  • To enhance near UV-visible absorption region and to applied phosphor convert-white LEOs (PC-WLEDs), a red phosphor composed of ${Y_2}{SiO_5}:\;EU^{3+}$, $Bi^{3+}$ compounds was prepared by the conventional solid-state reaction. The photoluminescence (PL) shown that samples were excited by near UV light 395 nm for measurement of PL spectra. Emission spectra of samples have shown red emissions at 612 nm ($^5D_0{\to}^7F_2$). The enhanced near $UV{\sim}$ visible excitation spectrum with a broad band centered at 258 nm and 282 nm originated in the transitions toward the charge transfer state (CTS) due to the $Eu^{3+}-Bi^{3+}-O^{2-}$ interaction. The other excitation band at $350\;nm{\sim}480\;nm$, corresponding to the transitions $^7F_0{\to}^5L_9$ (364 nm), $^7F_0{\to}^5G_3$ (381 nm), $^7F_0{\to}^5L_6$ (395 nm), $^7F_0{\to}^5D_3$, (415 nm) and $^7F_0{\to}^5D_2$ (466 nm), occurred due to enhanced the f-f transition increasing $Bi^{3+}$ and $Eu^{3+}$ ions. The PL intensity increased with increased as concentration of $Bi^{3+}$ and the emission intensity becomes with a maximum at 0.125 mol.