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

  • 조신호
    • 한국진공학회지
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    • 제22권2호
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    • pp.79-85
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    • 2013
  • 희토류 이온 $Eu^{3+}$$Dy^{3+}$가 각각 도핑된 $CaMoO_4$ 광체 분말을 고상반응법으로 합성하였다. 모든 형광체 분말의 결정 구조는 활성제 이온의 종류와 농도비에 관계없이 주 회절 피크(112)를 갖는 정방 정계이었다. $Eu^{3+}$ 이온이 도핑된 형광체의 경우에, $Eu^{3+}$ 이온의 농도가 0.01~0.10 mol 영역에서 결정 입자의 크기는 전반적으로 증가하였고, 비교적 균일한 크기 분포를 가지면서 조약돌 형태를 나타내었으며, 흡광 스펙트럼은 311 nm를 정점으로 넓게 퍼져있는 전하 전달 밴드와 파장 영역 360~470nm에서 약한 피크를 갖는 다수의 흡수선이 관측되었으며, 주 발광 스펙트럼은 $Eu^{3+}$ 이온의 $^5D_0{\rightarrow}^7F_2$ 전이에 의한 618 nm에 피크를 갖는 강한 적색 발광이었다. $Dy^{3+}$ 이온이 도핑된 분말의 경우에, 흡광 스펙트럼은 303 nm에 피크를 갖는 전하 전달 밴드와 상대적으로 세기가 약한 다수의 $Dy^{3+}$ 이온의 전이 신호가 발생하였으며, 주 발광 스펙트럼은 $^4F_{9/2}{\rightarrow}^7H_{13/2}$ 전이에 의한 578 nm에 피크를 갖는 황색 발광 스펙트럼이 관측되었다.

다양한 활성제 이온이 도핑된 SrWO4:RE3+ (RE=Dy, Sm, Dy/Sm) 형광체의 특성과 위조 방지 응용 (Luminescent Properties and Anti-Counterfeiting Applications of SrWO4:RE3+ (RE=Dy, Sm, Dy/Sm) Phosphors Doped with Several Activator Ions)

  • 윤수환;조신호
    • 한국전기전자재료학회논문지
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    • 제33권5호
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    • pp.393-399
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    • 2020
  • A series of phosphors, SrWO4:5 mol% Dy3+, SrWO4:5 mol% Sm3+, and SrWO4:5 mol% Dy3+:x Sm3+ (x=1~15 mol%), were prepared using a facile co-precipitation. The crystal structure, morphology, photoluminescence properties, and application in anti-counterfeiting fields were investigated. The crystalline structures of the prepared phosphors were found to be tetragonal systems with the dominant peak occurring at the (112) plane. The excitation spectra of the Dy3+ singly-doped SrWO4 phosphors were composed of an intense charge-transfer band centered at 246 nm in the range of 210~270 nm and two weak peaks at 351 nm and 387 nm due to the 6H15/26P7/2 and 6H15/24I13/2 transitions of Dy3+ ions, respectively. The wavelength of 246 nm was optimum for exciting the luminescence of Dy3+ and Sm3+ co-doped SrWO4 phosphors. The emission spectra consisted of two intense blue and yellow emission bands at 480 nm and 573 nm corresponding to the 4F9/26H15/2 and 4F9/26H13/2 transitions of Dy3+, and two strong emission peaks at 599 nm and 643 nm originating from the 4G5/26H7/2 and 4G5/26H9/2 transitions of Sm3+, respectively. As the concentration of Sm3+ ions increased, the emission intensities of Dy3+ rapidly decreased, while the emission intensities of Sm3+ gradually increased. These results suggest that the color of the emission light can be tuned from yellow to white by changing the concentration of Sm3+ ions at a fixed 5 mol% Dy3+. Furthermore, the fluorescent security inks were synthesized for use in anti-counterfeiting applications.

Dy3+와 Eu3+ 이온이 동시 도핑된 CaMoO4 형광체의 합성과 발광 특성 (Synthesis and Photoluminescence Properties of Dy3+- and Eu3+-codoped CaMoO4 Phosphors)

  • 김준한;조신호
    • 한국표면공학회지
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    • 제48권3호
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    • pp.82-86
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    • 2015
  • $Dy^{3+}$- and $Eu^{3+}$-codoped $CaMoO_4$ Phosphors were synthesized by using the solid-state reaction method. The crystal structure, morphology, and optical properties of the resulting phosphor particles were investigated by using the X-ray diffraction, field-emission scanning electron microscopy, and photoluminescence spectroscopy. XRD patterns exhibited that all the synthesized phosphors showed a tetragonal system with a main (112) diffraction peak, irrespective of the content of $Eu^{3+}$ ions. As the content of $Eu^{3+}$ ions increased, the grains showed a tendency to agglomerate. The excitation spectra of the synthesized powders were composed of one strong broad band centered at 305 nm in the range of 220 - 350 nm and several weak peaks in the range of 350 - 500 nm resulting from the 4f transitions of activator ions. Upon ultraviolet excitation at 305 nm, the yellow emission line due to the $^4F_{9/2}{\rightarrow}^6H_{13/2}$ transition of $Dy^{3+}$ ions and the main red emission spectrum resulting from the $^5D_0{\rightarrow}^7F_2$ transition of $Eu^{3+}$ ions were observed. With the increase of the content of $Eu^{3+}$, the intensity of the yellow emission band gradually decreased while that of the red emission increased. These results indicated that the emission intensities of yellow and red emissions could be modulated by changing the content of the $Dy^{3+}$ and $Eu^{3+}$ ions incorporated into the host crystal.

위조 방지 분야에 응용 가능한 다양한 희토류 이온이 도핑된 SrMoO4 형광체의 제조 및 특성 (Synthesis and Properties of SrMoO4 Phosphors Doped with Various Rare Earth Ions for Anti-Counterfeiting Applications)

  • 문태옥;정재용;조신호
    • 한국재료학회지
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    • 제30권8호
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    • pp.406-412
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    • 2020
  • SrMoO4:RE3+ (RE=Dy, Sm, Tb, Eu, Dy/Sm) phosphors are prepared by co-precipitation method. The effects of the type and the molar ratio of activator ions on the structural, morphological, and optical properties of the phosphor particles are investigated. X-ray diffraction data reveal that all the phosphors have a tetragonal system with a main (112) diffraction peak. The emission spectra of the SrMoO4 phosphors doped with several activator ions indicate different multicolor emissions: strong yellow-emitting light at 573 nm for Dy3+, red light at 643 nm for Sm3+, green light at 545 nm for Tb3+, and reddish orange light at 614 nm for Eu3+ activator ions. The Dy3+ singly-doped SrMoO4 phosphor shows two dominant emission peaks at 479 and 573 nm corresponding to the 4F9/26H15/2 magnetic dipole transition and 4F9/26H13/2 electric dipole transition, respectively. For Dy3+ and Sm3+ doubly-doped SrMoO4 phosphors, two kinds of emission peaks are observed. The two emission peaks at 479 and 573 nm are attributed to 4F9/26H15/2 and 4F9/26H13/2 transitions of Dy3+ and two emission bands centered at 599 and 643 nm are ascribed to 4G5/26H7/2 and 4G5/26H9/2 transitions of Sm3+. As the concentration of Sm3+ increases from 1 to 5 mol%, the intensities of the emission bands of Dy3+ gradually decrease; those of Sm3+ slowly increase and reach maxima at 5 mol% of Sm3+ ions, and then rapidly decrease with increasing molar ratio of Sm3+ ions due to the concentration quenching effect. Fluorescent security inks based on as-prepared phosphors are synthesized and designed to demonstrate an anti-counterfeiting application.

백색광 소자 응용을 위한 Gd2WO6:RE3+ (RE = Dy, Sm, Dy/Sm) 형광체의 구조 및 발광 특성 (Structural and Luminescent Properties of Gd2WO6:RE3+ (RE = Dy, Sm, Dy/Sm) Phosphors for White Light Emitting Devices)

  • 박기원;정재용;조신호
    • 한국표면공학회지
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    • 제53권4호
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    • pp.131-137
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    • 2020
  • A series of Dy3+, Sm3+, and Dy3+/Sm3+ doped Gd2WO6 phosphors were synthesized by the conventional solid-state reaction. The X-ray diffraction patterns revealed that all of the diffraction peaks could be attributed to the monoclinic Gd2WO6 crystal structure, irrespective of the type and the concentration of activator ions. The photoluminescence (PL) excitation spectra of Dy3+-doped Gd2WO6 phosphors contained an intense charge transfer band centered at 302 nm in the range of 240-340 nm and two weak peaks at 351 and 386 nm. Under an excitation wavelength of 302 nm, the PL emission spectra consisted of two strong blue and yellow bands centered at 482 nm and 577 nm. The PL emission spectra of the Sm3+-doped Gd2WO6 phosphors had a series of three peaks centered at 568 nm, 613 nm, and 649 nm, corresponding to the 6G5/26H5/2, 6G5/26H9/2, and 6G5/26H11/2 transitions of Sm3+, respectively. The PL emission spectra of the Dy3+- and Sm3+-codoped Gd2WO6 phosphors showed the blue and yellow emission lines originating from the 4F9/26H15/2 and 4F9/24H13/2 transitions of Dy3+ and reddish-orange and red emission bands due to the 4G5/26H7/2 and 4G5/26H9/2 transitions of Sm3+. As the concentration of Sm3+ increased from 1 to 15 mol%, the intensities of two PL spectra emitted by the Dy3+ ions gradually decreased, while those of the three emission bands due to the Sm3+ ions slowly increased, thus producing the color change from white to orange. The CIE color coordinates of Gd2WO6:5 mol% Dy3+, 1 mol% Sm3+ phosphors were (0.406, 0.407), which was located in the warm white light region.

Eu2+/Dy3+ 이온이 도핑된 Sr2MgSi2O7 분말 합성 및 발광 특성 (Synthesis and Luminescent Characterization of Eu2+/Dy3+-Doped Sr2MgSi2O7 Powders)

  • 박재한;김영진
    • 한국재료학회지
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    • 제24권12호
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    • pp.658-662
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    • 2014
  • $Eu^{2+}/Dy^{3+}$-doped $Sr_2MgSi_2O_7$ powders were synthesized using a solid-state reaction method with flux ($NH_4Cl$). The broad photoluminescence (PL) excitation spectra of $Sr_2MgSi_2O_7:Eu^{2+}$ were assigned to the $4f^7-4f^65d$ transition of the $Eu^{2+}$ ions, showing strong intensities in the range of 375 to 425 nm. A single emission band was observed at 470 nm, which was the result of two overlapping subbands at 468 and 507 nm owing to Eu(I) and Eu(II) sites. The strongest emission intensity of $Sr_2MgSi_2O_7:Eu^{2+}$ was obtained at the Eu concentration of 3 mol%. This concentration quenching mechanism was attributable to dipole-dipole interaction. The $Ba^{2+}$ substitution for $Sr^{2+}$ caused a blue-shift of the emission band; this behavior was discussed by considering the differences in ionic size and covalence between $Ba^{2+}$ and $Sr^{2+}$. The effects of the Eu/Dy ratios on the phosphorescence of $Sr_2MgSi_2O_7:Eu^{2+}/Dy^{3+}$ were investigated by measuring the decay time; the longest afterglow was obtained for $0.01Eu^{2+}/0.03Dy^{3+}$.

BiNbO4:RE3+ (RE = Dy, Eu, Sm, Tb) 형광체의 광학 특성 (Photoluminescence Properties of BiNbO4:RE3+ (RE = Dy, Eu, Sm, Tb) Phosphors)

  • 이상운;조신호
    • 한국표면공학회지
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    • 제50권3호
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    • pp.206-211
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    • 2017
  • $BiNbO_4:RE^{3+}$ (RE = Dy, Eu, Sm, Tb) phosphors were prepared by solid-state reaction at $1100^{\circ}C$ and their structural, photoluminescent, and morphological properties were investigated. XRD patterns exhibited that all the synthesized phosphors exhibited a triclinic system with a dominant (210) diffraction peak, irrespective of the type of activator ions. The surface morphologies of rare-earth-ion-doped $BiNbO_4$ phosphors were found to depend strongly on the type of activator ions. The $Eu^{3+}$ and $Dy^{3+}$ doped $BiNbO_4$ phosphors revealed a strong red (613 nm) emission resulting from the $^5D_0{\rightarrow}^7F_2$ transition of $Eu^{3+}$ and a dominant yellow (575 nm) emission originating from the $^4F_{9/2}{\rightarrow}^6H_{13/2}$ transition of $Dy^{3+}$ respectively, which were the electric dipole transitions, indicating that the activator ions occupy sites of non-inversion symmetry in the $BiNbO_4$ phosphor. The main reddish-orange emission spectra of $Sm^{3+}$-doped $BiNbO_4$ phosphors were due to the $^4G_{5/2}{\rightarrow}^6H_{7/2}$ (607 nm) magnetic dipole transition, indicating that the $Sm^{3+}$ ions were located at inversion symmetry sites in the $BiNbO_4$ host lattice. As for $Tb^{3+}$-doped phosphors, green emission was obtained under excitation at 353 nm and its CIE chromaticity coordinates were (0.274, 0.376). These results suggest that multicolor emission can be achieved by changing the type of activator ions incorporated into the $BiNbO_4$ host crystal.

증착 온도에 따른 La2MoO6:Dy3+,Eu3+ 형광체 박막의 광학 특성 (Effect of Deposition Temperature on the Optical Properties of La2MoO6:Dy3+,Eu3+ Phosphor Thin Films)

  • 조신호
    • 한국전기전자재료학회논문지
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    • 제32권5호
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    • pp.387-392
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    • 2019
  • $Dy^{3+}$ and $Eu^{3+}$-co-doped $La_2MoO_6$ phosphor thin films were deposited on sapphire substrates by radio-frequency magnetron sputtering at various growth temperatures. The phosphor thin films were characterized using X-ray diffraction (XRD), scanning electron microscopy, ultraviolet-visible spectroscopy, and fluorescence spectrometry. The optical transmittance, absorbance, bandgap, and photoluminescence intensity of the $La_2MoO_6$ phosphor thin films were found to depend on the growth temperature. The XRD patterns demonstrated that all the phosphor thin films, irrespective of growth temperatures, had a tetragonal structure. The phosphor thin film deposited at a growth temperature of $100^{\circ}C$ indicated an average transmittance of 85.3% in the 400~1,100 nm wavelength range and a bandgap energy of 4.31 eV. As the growth temperature increased, the bandgap energy gradually decreased. The emission spectra under ultraviolet excitation at 268 nm exhibited an intense red emission line at 616 nm and a weak emission line at 699 nm due to the $^5D_0{\rightarrow}^7F_2$ and $^5D_0{\rightarrow}^7F_4$ transitions of the $Eu^{3+}$ ions, respectively, and also featured a yellow emission band at 573 nm, resulting from the $^4F_{9/2}{\rightarrow}^6H_{13/2}$ transition of the $Dy^{3+}$ ions. The results suggest that $La_2MoO_6$ phosphor thin films can be used as light-emitting layers for inorganic thin film electroluminescent devices.