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Enhanced red luminescence of Ca_(3)Si_(2−x)M_(x)O_(7):Eu^(3+)(M=Al,P)phosphors via partial substitution of Si^(4+) for applications in white light-emitting diodes

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Rare Metals 2024年第2期43卷 736-748页

作者： Yu-Hao Ma Xi Gao Wen-Tao Zhang Zhen-Rui Yang Zhou Zhao Chen Qu College of Materials and Chemistry and Chemical Engineering Chengdu University of TechnologyChengdu610059China State Key Laboratory of Geohazard Prevention and Geoenvironment Protection Chengdu University of TechnologyChengdu610059China International Advanced Energy Science Research and Education Center Graduate School of Energy ScienceKyoto UniversityYoshida-HonmachiKyoto606-8501Japan

A red-emitting phosphor Ca_(2.91)Si_(2)O_(7):0.09Eu^(3+) with partial Al^(3+)/P^(5+) substitution on Si^(4+) was synthesized via a simple solid-state method,and the effects of the introduction of the M^(3+/5+)(M=Al,P)ions on the crystal structure and photoluminescence performance of Ca_(2.91)Si_(2−x)M_(x)O_(7):0.09Eu^(3+) phosphors were investigated.The X-ray diffraction(XRD),energy-dispersive X-ray spectroscopy(EDS),and X-ray photoelectron spectroscopy(XPS)results revealed that the structure of Ca_(3)Si_(2)O_(7) remained the same after the introduction of Al^(3+) and P^(5+) ions.The characteristic emission of Eu^(3+)-doped Ca_(3)Si_(2−x)M_(x)O_(7) phosphors exhibited two main peaks at 617 nm(red)and 593 nm(orange)under excitation at 394 nm,which originated from the^(5)D_(0)→^(7)F_(2)and^(5)D_(0)→^(7)F_(1) electron transitions of Eu^(3+) ions.After the partial substitution of Al^(3+) and P^(5+),the red emission intensities of the Ca_(2.91)Si_(2)O_(7):0.09Eu^(3+) phosphors were significantly enhanced by 1.88-and 1.42-fold,respectively,which is attributed to the crystal-field effect around Eu^(3+).Meanwhile,the luminescence intensities of the Ca_(2.91)Si_(1.96)Al_(0.04)O_(7):0.09Eu^(3+) and Ca_(2.91)Si_(1.94)P_(0.06)O_(7):0.09Eu^(3+) phosphors at 210℃ were 79.36%and 77.53%of those at 30°C,respectively,indicating their excellent thermal stability.Moreover,the as-prepared Ca_(2.91)Si_(1.96)Al_(0.04)O_(7):0.09Eu^(3+)and Ca_(2.91)Si_(1.94)P_(0.06)O_(7):0.09Eu^(3+) red-emitting phosphors were combined with a near-ultraviolet chip of 395 nm to fabricate red-light-emitting diode(LED)and white(w)-LED devices with excellent chromaticity features.In summary,Al^(3+)/P^(5+)-substituted Ca_(2.91)Si_(2)O_(7):0.09Eu^(3+) can serve as red-emitting phosphors for applications in w-LEDs.

关键词： Ca_(3)Si_(2)O_(7) Red-emitting phosphor structure substitution Luminescence enhancement Crystal-field effect White light-emitting diode

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Effective regulation of electronic structures and luminescence properties of LiGd_(9)(SiO_(4))6-x(GeO_(4))xO_(2):Dy^(3+)phosphors by tetrahedral substitution

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Journal of Rare Earths 2023年第5期41卷 673-681,I0002页

作者： Yuanyuan Zhang Lefu Mei Haikun Liu Sergey M.Aksenov Dina V.Deyneko Deliang Chen School of Materials Sciences and Technology Dongguan University of TechnologyDongguan 523808China School of Materials Science and Engineering Xi'an Jiaotong UniversityXi'an 710049China Beijing Key Laboratory of Materials Utilization of Nonmetallic Minerals and Solid Wastes National Laboratory of Mineral MaterialsSchool of Materials Sciences and TechnologyChina University of GeosciencesBeijing 100083China Department of Energy and Chemical Engineering Dongguan University of TechnologyDongguan 523808China Laboratory of Arctic Mineralogy and Material Sciences Kola Science CentreRussian Academy of Sciences14 Fersman StrApatity184209Russia Laboratory of Nature-Inspired Technologies and Environmental Safety of the Arctic Kola Science CentreRussian Academy of SciencesApatity18420 Russia Department of Chemistry Lomonosov Moscow State UniversityMoscow119991Russia School of Materials Science and Engineering Zhengzhou UniversityZhengzhou 450001China

A series of Dy^(3+)-activated phosphors with the general formula LiGd_(9)(SiO_(4))6-x(GeO_(4))xO_(2):Dy^(3+)(0≤x≤3)characterized by an apatite-type structure were successfully synthesized via a simple solid-state technique involving a partial substitution of[SiO_(4)]^(4-)with[GeO_(4)]^(4-)species.The effects of homovalent[GeO_(4)]^(4-)-[SiO_(4)]^(4-)substitution on the crystal structure,electronic structure,luminescence properties and thermal performance of LiGd_(9)(SiO_(4))6-x(GeO_(4))xO_(2):Dy^(3+)phosphors were studied in details.The phases and microstructure were performed by using X-ray diffraction(XRD)Rietveld refinement method and scanning electron microscopy(SEM)characterization.The substitution of smaller[SiO_(4)]^(4-)ions by larger[GeO_(4)]^(4-)ones makes their unit cell parameters increase gradually,and their band gaps decrease.The photoluminescence spectra of LiGd_(9)(SiO_(4))6-x(GeO_(4))xO_(2):Dy^(3+)(0≤x≤3)exhibit obvious emission peaks located at 477,573 and 675 nm within a visible wavelength region,resulting in an excellent white light.Furthermore,the I573nm/I477nm values of LiGd_(9)(SiO_(4))6-x(GeO_(4))xO_(2):Dy^(3+)(0≤x≤3)become larger with the partial substitution of[SiO_(4)]^(4-)by[GeO_(4)]^(4-),and their CIE chromaticity coordinates exhibit a yellow shift.

关键词： Apatite structure substitution Electronic structure White emitting Rare earths

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