WO2017069455A1 - 산질화물 형광체와 그 제조방법 및 백색 발광소자 - Google Patents

산질화물 형광체와 그 제조방법 및 백색 발광소자 Download PDF

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WO2017069455A1
WO2017069455A1 PCT/KR2016/011476 KR2016011476W WO2017069455A1 WO 2017069455 A1 WO2017069455 A1 WO 2017069455A1 KR 2016011476 W KR2016011476 W KR 2016011476W WO 2017069455 A1 WO2017069455 A1 WO 2017069455A1
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Prior art keywords
formula
metal selected
phosphor
oxynitride phosphor
oxynitride
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PCT/KR2016/011476
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English (en)
French (fr)
Korean (ko)
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이성훈
김영식
이환섭
이상준
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주식회사 효성
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Publication of WO2017069455A1 publication Critical patent/WO2017069455A1/ko

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/55—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing beryllium, magnesium, alkali metals or alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/59—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps

Definitions

  • the present invention relates to an oxynitride phosphor, a method of manufacturing the same, and a white light emitting device. More specifically, the light emitting wavelength is 500 to 550 nm using a UV LED and a blue LED as a light source, and the half width is about 48 to 80 nm.
  • the present invention relates to an oxynitride phosphor characterized by a narrow oxynitride phosphor, having an excellent absorption region of 380 to 480 nm, and having an easy wavelength shift to 500 to 550 nm, a method of manufacturing the same, and a white light emitting device including the phosphor.
  • ⁇ -SiAlON Green
  • La 3 Si 6 N 11 Ce 3+ (G-Yellow) nitrides.
  • ⁇ -SiAlON is a green oxynitride phosphor, which has a narrow half width, but is not easy to shift in wavelength.
  • the green oxynitride phosphor is synthesized at high temperature and high pressure, and there is an economic disadvantage in that the manufacturing process is very complicated and the cost is high.
  • La 3 Si 6 N 11 has a wide half-width of green-yellow area, and emits rich colors to green and yellow areas, which have advantages in terms of luminance.
  • the two phosphors used in the related art have a disadvantage in that the manufacturing method is performed at high temperature and high pressure, and the nitride used as the basic raw material is unstable and expensive, and the wavelength of the phosphor is not shifted.
  • the mother is a pure nitride, when a slight oxygen inflow from the process and the raw material, its properties are deteriorated and another phase is formed, so it is necessary to work in a closed box, which results in a poor productivity.
  • the light emitting properties of the green and yellow-orange regions include a lot of color regions that cannot be used in actual display, they are not efficient.
  • the problem of the structure of the base matrix causes a decrease in reliability and needs to be improved.
  • Korean Patent Nos. 10-1297619 and 10-1235179 describe oxynitride phosphors of Formulas A and B, respectively.
  • M is at least one or more alkaline earth metal ions selected from the group consisting of Ba, Sr, Ca, Mg and Be, 0 ⁇ x ⁇ 2, 0.003 ⁇ a ⁇ 0.75.
  • M is at least one or more alkaline earth metal ions selected from the group consisting of Ba, Sr, Ca, Mg and Be, 0.01 ⁇ a ⁇ 5, 1 ⁇ b ⁇ 7, 2 ⁇ c ⁇ 13, 1 ⁇ d ⁇ 18 and 0 ⁇ e ⁇ 16.
  • ⁇ -sialon crystals (where x1 is high capacity of Li in the sialon unit lattice, x2 is high capacity of A element in the sialon unit lattice, x3 is high capacity of M element in the sialon unit lattice)
  • the parameters in the ranges of 1.2 ⁇ x1 ⁇ 2.4, 0.001 ⁇ x2 ⁇ 0.4, and 0 ⁇ x3 ⁇ 1.0 emit light of fluorescence having peaks at wavelengths in the range of 400 nm to 700 nm by irradiating the excitation source. It has been proposed with respect to a phosphor having a ⁇ -sialon crystal as a main component.
  • Patent Document 1 Korean Registered Patent No. 10-1297619
  • Patent Document 2 Korean Patent Registration No. 10-1235179
  • Patent Document 3 Korean Patent Publication No. 10-2008-0047316
  • the present invention can economically produce a phosphor having an excellent light absorption region and a wavelength shift characteristic as well as a narrow half-value width, high luminance and high color reproducibility as an oxynitride phosphor.
  • the challenge is to present a solution.
  • an object of the present invention is to provide an oxynitride phosphor having easy wavelength control and high luminance and high color reproducibility.
  • another object of the present invention is to provide an oxynitride phosphor whose half width is as narrow as 48 to 80 nm and has an excellent absorption area of 380 to 480 nm and is easy to shift wavelengths to 500 to 550 nm.
  • Another object of the present invention is to provide a novel phosphor with further improved brightness and reliability.
  • Another object of the present invention is to provide a method for efficiently preparing the oxynitride phosphors having excellent physical properties as described above.
  • the present invention provides an oxynitride phosphor represented by the following formula (1).
  • A is at least one metal selected from Li, Na, K and Rb
  • M is at least one metal selected from Ba, Sr, Ca, Mg or Zn
  • D is Gd, Y, Lu, La
  • R is one or more metals selected from Eu, Ce, Tm, Pr, Ho, Dy and Mn, 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, 0.01 ⁇ z ⁇ 3.
  • A is at least one metal selected from Li, Na, K and Rb
  • M is a mixture of at least one oxide or nitride of a divalent metal selected from Ba, Sr, Ca, Mg or Zn
  • D is at least one mixture of oxides or nitrides of a trivalent metal selected from Gd, Y, Lu, La, Al or Ga
  • R is at least one selected from Eu, Ce, Tm, Pr, Ho, Dy and Mn.
  • the oxynitride phosphor according to the present invention emits light having a light emission wavelength of 500 to 550 nm using a UV LED and a blue LED as a light source, and has a half width of 48 to 80 nm narrow, particularly having an excellent absorption area of 380 to 480 nm. It has the characteristic of easily reproducing wavelengths from 500 to 550 nm while having high color rendering effect.
  • the oxynitride phosphor of the present invention is closer to the reference light in the white implementation in UV and blue LED, and realizes excellent cyan-green light emission and high efficiency suitable for commercialization.
  • the oxynitride phosphor according to the present invention can be implemented in blue green, and is suitable for high color rendering, and can be preferably applied to a display since high brightness and high color reproduction are possible.
  • the high temperature and high pressure are not required compared to the nitride phosphor under general application, there is an advantage in that the price is excellent.
  • Figure 1 shows the XRD pattern for the compound prepared in Example 3 according to the present invention.
  • Figure 2 shows a comparison of the XRD pattern for each compound according to the content of nitrogen in the experimental example according to the present invention.
  • Figure 3 shows a comparison of the wavelength change for each compound according to the content of nitrogen in the experimental example according to the present invention.
  • the present invention relates to a phosphor that emits light at a wavelength of 500 to 550 nm using a UV LED and a blue LED as a light source, and has a half width of about 48 to 80 nm.
  • the oxynitride phosphor according to the present invention is a phosphor represented by the following formula (1).
  • A is at least one metal selected from Li, Na, K and Rb
  • M is at least one metal selected from Ba, Sr, Ca, Mg or Zn
  • D is Gd, Y, Lu, La
  • R is one or more metals selected from Eu, Ce, Tm, Pr, Ho, Dy and Mn, 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, 0.01 ⁇ z ⁇ 3.
  • the phosphor has an excellent absorption region of 380 ⁇ 480 nm and has the property of easy wavelength shifting to 500 ⁇ 550 nm.
  • the compound of Formula 1 may be prepared as a novel phosphor with further improved brightness and reliability.
  • the present invention includes a manufacturing method for controlling the wavelength, high brightness and high color reproducible oxynitride phosphors by substituting nitrogen in place of the nitridation and oxygen of the phosphor to the compound of the formula (1) through the synthetic process control.
  • M is at least one oxide or nitride of a divalent metal selected from Ba, Sr, Ca, Mg or Zn and D is Gd, Y, Lu, La, At least one oxide or nitride of a trivalent metal selected from Al or Ga, R is mixed with at least one metal selected from Eu, Ce, Tm, Pr, Ho, Dy, and Mn, followed by hydrogen mixed gas or nitrogen
  • An oxynitride phosphor having a composition represented by Chemical Formula 1 may be prepared by heat treatment under a reducing atmosphere of gas.
  • in order to replace the nitrogen in the manufacturing process it can be carried out by the process of heat treatment by maintaining at 900 °C 1 hour to 4 hours.
  • each element of M, Si may be used by mixing nitrogen as about 0 to 80 wt% of the raw material properties of two or more kinds of nitride raw material or the total content ratio.
  • the method for preparing a high color oxynitride phosphor according to the present invention comprises the following steps.
  • A is at least one metal selected from Li, Na, K and Rb and M is selected from Ba, Sr, Ca, Mg or Zn
  • D is at least one mixture of oxides or nitrides of trivalent metals selected from Gd, Y, Lu, La, Al or Ga
  • R is Eu, Ce, Tm, Pr, Mixing oxides or nitrides including at least one rare earth or transition metal selected from Ho, Dy and Mn
  • Charging the mixed precursor into an alumina / carbon crucible Maintaining the temperature in a reducing environment to 900 ° C. for 1 to 4 hours; After the temperature is raised to 1000 to 1400 °C in a nitrogen or hydrogen environment it can be prepared for the oxynitride phosphor of Formula 1 including the step of maintaining for 1 to 12 hours.
  • the oxynitride phosphor represented by the formula (1) having an excellent absorption region of 380 ⁇ 480 nm and easy wavelength shift to 500 ⁇ 550 nm.
  • the present invention also provides a white light emitting device comprising a UV / blue light emitting diode (LED) and an oxynitride green phosphor according to the present invention.
  • a white light emitting device comprising a UV / blue light emitting diode (LED) and an oxynitride green phosphor according to the present invention.
  • the larger the nitrogen substitution rate of the phosphor the light emission peak shifts from the blue green region to the green region. Therefore, the phosphor of the present invention can easily control the color control and brightness through the control of the light emission peak. In addition, the phosphor according to the present invention has a remarkable effect of maximizing the color control of each device according to the substitution of nitrogen.
  • by adjusting the substitution rate of nitrogen in the manufacturing process of Formula 1 includes controlling the wavelength and half width of the phosphor.
  • the oxynitride phosphor prepared according to the embodiment of the present invention has a property closer to the reference light in the white implementation in UV and blue LEDs, and can implement excellent cyan-green and high efficiency suitable for commercialization.
  • the molar ratio of sodium, barium, europium, scandinium and silicon and silicon nitride was fixed at 1: 0.9: 0.1: 1: 2, and the ratio of silicon nitride and silicon oxide was set at 2:98.
  • the prepared mixed sample was dried at 120 ° C. for 1 hour using an oven. After heated in a later reduction in the environment up to 900 °C after 4 hours, by heating the mixture to a high temperature electric furnace in a reducing atmosphere at 1200 o C for 4 hours, using the title compound corresponding to the formula (1) was prepared.
  • Example 2 Na (Ba 0.9 , Eu 0.1 ) ScSi 2 O 6 . 95 N 0 .05 production of the oxynitride phosphors
  • Example 3 Na (Ba 0.9 , Eu 0.1 ) ScSi 2 O 6 . 9 N 0 .1 production of the oxynitride phosphors
  • the wavelength change was compared and analyzed for the compounds having different nitrogen content and the compounds containing no nitrogen, such as the compounds obtained in Examples 1-3. The results are shown in FIG.
  • the XRD pattern of the phosphor prepared according to the present invention was moved to a high angle (High angle shift) as the nitrogen content ratio was increased, it was confirmed that nitrogen is structurally substituted with oxygen.
  • the phosphor of the present invention was found to be a phosphor emitting a main wavelength of 500 ⁇ 550 nm as the content ratio of nitrogen (Nitrogen) is increased by the excitation light of 380 ⁇ 480 nm light, thereby high color rendering It was confirmed that the phosphor having excellent physical properties that can be reproduced.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Luminescent Compositions (AREA)
PCT/KR2016/011476 2015-10-21 2016-10-13 산질화물 형광체와 그 제조방법 및 백색 발광소자 WO2017069455A1 (ko)

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KR1020150146846A KR101737230B1 (ko) 2015-10-21 2015-10-21 산질화물 형광체와 그 제조방법 및 백색 발광소자
KR10-2015-0146846 2015-10-21

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111434613A (zh) * 2019-01-10 2020-07-21 北京理工大学 一种稀土系复合材料及其制备方法和应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080296596A1 (en) * 2007-05-30 2008-12-04 Anant Achyut Setlur Novel green emitting phosphors and blends thereof
WO2012073887A1 (ja) * 2010-11-30 2012-06-07 パナソニック株式会社 蛍光体及び発光装置
KR101215300B1 (ko) * 2011-03-29 2012-12-26 순천대학교 산학협력단 산질화물계 형광체
KR101389089B1 (ko) * 2011-06-16 2014-04-29 한국화학연구원 금속실리콘산질화물계 형광체를 이용한 실리콘질화물계 형광체의 제조 방법
KR20150055594A (ko) * 2013-11-13 2015-05-21 엘지이노텍 주식회사 청녹색 형광체, 이를 포함하는 발광 소자 패키지 및 조명 장치

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080296596A1 (en) * 2007-05-30 2008-12-04 Anant Achyut Setlur Novel green emitting phosphors and blends thereof
WO2012073887A1 (ja) * 2010-11-30 2012-06-07 パナソニック株式会社 蛍光体及び発光装置
KR101215300B1 (ko) * 2011-03-29 2012-12-26 순천대학교 산학협력단 산질화물계 형광체
KR101389089B1 (ko) * 2011-06-16 2014-04-29 한국화학연구원 금속실리콘산질화물계 형광체를 이용한 실리콘질화물계 형광체의 제조 방법
KR20150055594A (ko) * 2013-11-13 2015-05-21 엘지이노텍 주식회사 청녹색 형광체, 이를 포함하는 발광 소자 패키지 및 조명 장치

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111434613A (zh) * 2019-01-10 2020-07-21 北京理工大学 一种稀土系复合材料及其制备方法和应用
CN111434613B (zh) * 2019-01-10 2021-09-28 北京理工大学 一种稀土系复合材料及其制备方法和应用

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KR101737230B1 (ko) 2017-05-18
KR20170046863A (ko) 2017-05-04

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