WO2017052234A1 - Phosphore rouge fluorure métallique et élément électroluminescent l'utilisant - Google Patents

Phosphore rouge fluorure métallique et élément électroluminescent l'utilisant Download PDF

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WO2017052234A1
WO2017052234A1 PCT/KR2016/010596 KR2016010596W WO2017052234A1 WO 2017052234 A1 WO2017052234 A1 WO 2017052234A1 KR 2016010596 W KR2016010596 W KR 2016010596W WO 2017052234 A1 WO2017052234 A1 WO 2017052234A1
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phosphor
metal fluoride
red phosphor
sif
fluoride red
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PCT/KR2016/010596
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English (en)
Korean (ko)
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김창해
방보극
최강식
박준규
김민석
손기선
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한국화학연구원
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Priority claimed from KR1020160119738A external-priority patent/KR101854114B1/ko
Application filed by 한국화학연구원 filed Critical 한국화학연구원
Priority to US15/762,619 priority Critical patent/US10961450B2/en
Priority to EP16848959.9A priority patent/EP3354708B1/fr
Priority to CN201680060843.8A priority patent/CN108350356B/zh
Priority to JP2018515570A priority patent/JP6591054B2/ja
Publication of WO2017052234A1 publication Critical patent/WO2017052234A1/fr

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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
    • C09K11/57—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing manganese or rhenium
    • 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
    • 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 is usefully applied to light emitting devices such as light emitting diodes, laser diodes, surface emitting laser diodes, inorganic electroluminescent devices, organic electroluminescent devices because they are excited by ultraviolet or blue excitation sources and emit red wavelengths.
  • the present invention relates to a metal fluoride red phosphor having a tetragonal crystal structure having a novel composition, and to applying the phosphor as a light emitting device.
  • LEDs are next-generation light emitting devices, which consume less power than conventional light sources, and have high interest in light emission efficiency, high brightness, and fast response speed.
  • the technology for manufacturing a white light emitting diode can be largely divided into two methods.
  • the first method is a technique of manufacturing a white light emitting device using red, blue and green light emitting diodes. While the white light emitting diode fabricated by the first method has a very good color rendering index (CRI) and optical characteristics, it is expensive to manufacture and due to the technical problem of driving each LED separately, Only limited to the same special lighting.
  • CRI color rendering index
  • the second method is a technology that is currently commercially available to manufacture a white light emitting device by using a binary system (binary system) for applying a yellow phosphor on a blue light emitting diode chip.
  • Binary systems have the advantage of being able to make a simple structure of a white light emitting diode having very good optical characteristics, and low manufacturing cost, while a low color rendering index (CRI) due to the lack of light emission in the red region.
  • CRI color rendering index
  • various phosphors which exhibit excellent optical properties under about 450 nm excitation are not developed in various ways.
  • Patent Document 1 discloses a technique for manufacturing a white light emitting device using a binary system for coating a YAG: Ce yellow phosphor on a GaN light emitting diode chip emitting blue light at a wavelength region of 460 nm. It is. However, yttrium aluminum garnet (Y 3 Al 5 O 12 , YAG) -based phosphor has a weak emission intensity in the red region due to the light emission wavelength, and thus it is difficult to obtain excellent color rendering characteristics. There is an unsuitable problem.
  • Patent Document 2 discloses a silicate-based green of L 2 SiO 4 : Eu (where L is an alkaline earth metal element selected from Mg, Ca, Sr and Ba) on an InGaN light emitting diode chip.
  • L is an alkaline earth metal element selected from Mg, Ca, Sr and Ba
  • CRI color rendering index
  • Patent Document 3 discloses a phosphor having a composition of the formula (I).
  • A is selected from Li, Na, K, Rb, Cs and combinations thereof; M is Si, Ge, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta , Bi, Gd and combinations thereof; x is an absolute value determined from the charge of the MF y ions, y is 5, 6 or 7)
  • Patent Publication 3 only an example of preparing a K 2 SiF 6 : Mn 4 + phosphor is specifically described, and the A 3 MF 7 : Mn 4 + phosphor is not synthesized.
  • the metal fluoride phosphor containing the manganese (Mn) as a lubricant is determined to be useful in the manufacture of a white light emitting device because the red light emission intensity is strong, in the present invention
  • a 2 MF 6 : Mn 4 + phosphor is used as a raw material to prepare a red light emitting metal fluoride phosphor having a new composition.
  • Patent Document 1 Republic of Korea Patent Publication No. 10-0456430
  • Patent Document 2 Republic of Korea Patent Publication No. 10-0605211
  • Patent Document 3 International Publication No. WO 2012-128837
  • An object of the present invention is to provide a novel metal fluoride red phosphor having a light emission peak in a red region by an ultraviolet or blue excitation source.
  • the metal fluoride red phosphor provided by the present invention has not been synthesized to date, but was synthesized for the first time by the present inventors, and it was confirmed for the first time that the crystal structure of the phosphor is a tetragonal structure.
  • Another object of the present invention is to provide a method for producing a novel metal fluoride red phosphor by a solid phase method or a liquid phase method using the phosphor disclosed in Patent Document 3 as a raw material.
  • Another object of the present invention is to provide a white light emitting device including a novel metal fluoride red phosphor.
  • the present invention is characterized by a metal fluoride red phosphor having a composition of the formula (1).
  • A is selected from K, Rb, NH 4 and combinations thereof; M is a metal element selected from Si, Ge, Ti, and combinations thereof, and x is 0 ⁇ x ⁇ 0.15.
  • A is potassium (K)
  • M is silicon (Si) or titanium (Ti), characterized in that the metal fluoride red phosphor.
  • the metal fluoride red phosphor having a tetragonal crystal structure having the composition of Chemical Formula 1 is characterized by the above-mentioned.
  • K 3 SiF 7 : Mn x 4 + composition, the Bragg angle (2 ⁇ ) in the powder X-ray diffraction pattern is 28.60 ⁇ 0.50, 32.70 ⁇ 0.50, 26.69 ⁇ 0.50, 41.62 ⁇ 0.50, It is characterized by a metal fluoride red phosphor having a tetragonal crystal structure mainly comprising a phase exhibiting a diffraction peak of at least 5% relative intensity in the range of 46.51 ⁇ 0.50 °.
  • the composition has a composition of (NH 4 ) 3 SiF 7 : Mn x 4 + , and the Bragg angle (2 ⁇ ) in the powder X-ray diffraction pattern is 15.57 ⁇ 0.50, 21.79 ⁇ 0.50, 26.90 ⁇ 0.50, 31.45 It is characterized by a metal fluoride red phosphor having a tetragonal crystal structure including, as a main phase, a phase exhibiting a diffraction peak of 5% or more in relative intensity in a range of ⁇ 0.50 and 39.71 ⁇ 0.50 °.
  • the composition has a composition of (NH 4 ) 3 GeF 7 : Mn x 4 + , and the Bragg angle (2 ⁇ ) in the powder X-ray diffraction pattern is 15.25 ⁇ 0.50, 21.31 ⁇ 0.50, 26.31 ⁇ 0.50, 30.78 It is characterized by a metal fluoride red phosphor having a tetragonal crystal structure including, as a main phase, a phase exhibiting a diffraction peak of 5% or more in the relative intensity of ⁇ 0.50 and 43.40 ⁇ 0.50 °.
  • the composition of Rb 2 KSiF 7 : Mn x 4 + , the Bragg angle (2 ⁇ ) in the powder X-ray diffraction pattern is 27.45 ⁇ 0.50, 32.09 ⁇ 0.50, 36.00 ⁇ 0.50, 40.57 ⁇ 0.50, It is characterized by a metal fluoride red phosphor having a tetragonal crystal structure mainly comprising a phase exhibiting a diffraction peak of 5% or more relative intensity in the range of 45.38 ⁇ 0.50 °.
  • K 3 TiF 7 : Mn x 4 + composition, the Bragg angle (2 ⁇ ) in the powder X-ray diffraction pattern is 18.50 ⁇ 0.50, 25.50 ⁇ 0.50, 27.50 ⁇ 0.50, 28.50 ⁇ 0.50, A metal fluoride red phosphor comprising as a main phase a phase exhibiting a diffraction peak of at least 5% relative intensity in the range of 45.00 ⁇ 0.50 °.
  • the excitation wavelength is 365 to 480 nm
  • the emission center wavelength is 610 to 670 nm, characterized in that the metal fluoride red phosphor having the composition of Formula 1 above.
  • the present invention is characterized by a method for producing a metal fluoride red phosphor by a solid-phase method comprising the following steps one, two and three:
  • Step 1 weighing and physically mixing a raw material consisting of A precursor, M precursor and manganese (Mn) precursor;
  • Step 2 drying the raw material mixture in an 80 ⁇ 150 °C oven
  • Step 3 heat-treating the dried mixture to 100 ⁇ 500 °C in a hydrogen gas, nitrogen gas or a mixed gas atmosphere, to prepare a metal fluoride red phosphor having a composition ratio of the formula (1).
  • the present invention is characterized by a method for producing a metal fluoride red phosphor by a liquid phase method comprising the following steps i, ii, iii and iv:
  • Step (iv) heat-treated the dried solid at 200 ⁇ 1,000 °C in a hydrogen gas, nitrogen gas or a mixed gas atmosphere, to prepare a metal fluoride red phosphor having a composition ratio of the formula (1).
  • the metal fluoride red phosphor synthesized for the first time in the present invention has a tetragonal crystal structure, emits light by an ultraviolet or blue excitation source, and exhibits the highest emission luminance in the red wavelength region of 610 to 670 nm. Therefore, the metal fluoride red phosphor of the present invention is useful for manufacturing a white light emitting device.
  • the metal fluoride red phosphor of the present invention can be easily produced by a solid-phase method including the step of physically mixing using a conventional phosphor or a fluorescent parent as a raw material.
  • the metal fluoride red phosphor of the present invention can be easily produced by a liquid phase method including a process of dissolving a raw material in an acid such as HF.
  • K 3 SiF 7 Mn 4 + phosphor
  • K 2 SiF 6 Mn 4 + used as a raw material XRD analysis results for comparing the crystal structure of the phosphor.
  • K 3 TiF 7 Mn 4 + phosphor
  • K 2 TiF 6 Mn 4 + used as a raw material XRD analysis results for comparing the crystal structure of the phosphor.
  • FIG. 3A and 3B show the results of analyzing the crystals of K 3 SiF 7 : Mn 4 + phosphors by Rietveld refinement based on XRD analysis
  • FIG. 3A shows K 3 SiF 7 : Mn 4 +.
  • Figure 3b is a Rietveld structural analysis of the K 3 SiF 7 : Mn 4 + phosphor.
  • FIG. 13 is a result of comparing the decay time of phosphors.
  • FIG. (a) is a K 3 SiF 7 prepared in Examples 1, 2, 5 and 8: the result of measuring the decay time (decay time) of Mn 4+ phosphor
  • (b) is K 3 SiF 7: Mn 4 + K 2 SiF 6 : Mn 4 + used as phosphor and raw material It is the result of comparing the decay time of fluorescent substance.
  • Rb 2 KSiF 7 Mn x 4 + phosphor.
  • (a) is a photograph of Rb 2 KSiF 7 : Mn x 4 + phosphor crystal powder
  • the present invention relates to a novel metal fluoride red phosphor having a composition of the following Chemical Formula 1.
  • A is selected from K, Rb, NH 4 and combinations thereof; M is a metal element selected from Si, Ge, Ti, and combinations thereof, and x is 0 ⁇ x ⁇ 0.15.
  • the metal fluoride red phosphor having the composition of Formula 1 has a tetragonal crystal structure.
  • the K 3 ZrF 7 : Mn x 4 + phosphor has the composition A 3 MF 7 : Mn 4 + , but its crystal structure is cubic.
  • the phosphor of the present invention is a phosphor in which silicon (Si), germanium (Ge) or titanium (Ti) metal elements are substituted for zirconium (Zr), and its crystal structure is clearly different as a tetragonal structure. There is.
  • a phosphor in which A is potassium (K) may be preferable, and a phosphor in which M is silicon (Si) or titanium (Ti) may be preferable.
  • the metal fluoride red phosphor having the composition of Chemical Formula 1 has a property of emitting red light by an ultraviolet or blue excitation source. Specifically, the metal fluoride red phosphor having the composition of Chemical Formula 1 has an excitation wavelength of 365 to 480 nm and emission center wavelength of 610 to 670 nm.
  • the metal fluoride red phosphor of the present invention exhibiting light emission characteristics as described above may be applied to a white light emitting device. Therefore, the present invention is characterized by a white light emitting device comprising a metal fluoride red phosphor having the composition of Formula 1.
  • a conventional phosphor may be further included.
  • the conventional phosphor may be selected from YAG: Ce phosphors and L 2 SiO 4 : Eu phosphors, where L is an alkaline earth metal element selected from Mg, Ca, Sr and Ba.
  • L is an alkaline earth metal element selected from Mg, Ca, Sr and Ba.
  • a red phosphor commonly used for fabricating a white light emitting device may be appropriately included, and the selection and content of the conventional phosphor may be modified to suit the purpose.
  • the light emitting device may include a light emitting diode, a laser diode, a surface emitting laser diode, an inorganic electroluminescent device, an organic electroluminescent device, or the like. Can be applied.
  • the present invention is also characterized in the method for producing a metal fluoride red phosphor having a composition of the formula (1).
  • the method for producing a metal fluoride red phosphor according to the present invention may be performed by a solid phase method or a liquid phase method.
  • the manufacturing method of the metal fluoride red phosphor by the solid phase method As a first manufacturing method according to the present invention, the manufacturing method of the metal fluoride red phosphor by the solid phase method
  • Step 1 weighing and physically mixing a raw material consisting of A precursor, M precursor and manganese (Mn) precursor;
  • Step 2 drying the raw material mixture in an 80 ⁇ 150 °C oven
  • Step 3 heat-treating the dried mixture at 100 ⁇ 500 °C in a hydrogen gas, nitrogen gas or a mixed gas atmosphere, to prepare a metal fluoride red phosphor in the composition ratio of the formula (1); It includes.
  • a fluorescent parent material of a metal fluoride or a metal fluoride phosphor containing manganese (Mn) lubricant known in Patent Document 3 or the like can be used as a raw material, and these raw materials are physically used. After mixing, heat treatment is performed under hydrogen gas, nitrogen gas, or a mixed gas atmosphere thereof.
  • the raw material used in the phosphor manufacturing method according to the solid phase method are as follows.
  • the A precursor one or more selected from AF, AHF 2 , A 2 O, A 2 CO 3 , CH 3 COO-A, A 2 MnF 6 , A 2 MF 6 and A 2 MF 6 : Mn 4 + can be used.
  • M precursor one or more selected from AF, AHF 2 , A 2 O, A 2 CO 3 , CH 3 COO-A, A 2 MnF 6 , A 2 MF 6 and A 2 MF 6 : Mn 4 + can be used.
  • M precursor A 2 and A 6 MF 2 MF 6: can be used at least one member selected from Mn 4 +.
  • manganese (Mn) precursor is A 2 MnF 6 And A 2 MF 6: can be used one or more selected from Mn 4 +.
  • a and M are as defined in the formula (1).
  • a 2 MF 6 or A 2 MF 6 : Mn 4 + used as an A precursor, M precursor or manganese (Mn) precursor in the solid phase method of the present invention is a phosphor disclosed in Patent Document 3.
  • a 2 MF 6 or A 2 MF 6 : Mn 4 + used in the solid-phase method of the present invention is specifically K 2 SiF 6 , K 2 GeF 6 , K 2 TiF 6 , K 2 MnF 6 , K 2 SiF 6 : Mn 4 + , K 2 GeF 6 : Mn 4 + , K 2 TiF 6 : Mn 4 + , Rb 2 SiF 6 , Rb 2 GeF 6 , Rb 2 TiF 6 , Rb 2 MnF 6 , Rb 2 SiF 6 : Mn 4+ , Rb 2 GeF 6 : Mn 4 + , Rb 2 TiF 6 : Mn 4 + , (NH 4 ) 2 SiF 6 , (NH 4 ) 2 GeF 6 , (NH 4
  • the above-mentioned raw materials are physically mixed, and the mixing method is a method commonly used in the art, but may be carried out by using a free-flow mortar, a wet ball mill, a dry ball mill, or the like.
  • the physical mixing method There is no particular limitation on the physical mixing method.
  • the physical mixing process of the raw material may be mixed in a powder state by applying a physical force without using a separate solvent, or may be mixed by applying a physical force in a slurry state using a small amount of solvent.
  • Solvents that can be used for mixing the raw materials are also commonly used in the art, and specifically, one or more selected from acetone and alcohols having 1 to 4 carbon atoms can be used.
  • the drying temperature is preferably 80 ⁇ 150 °C, if the drying temperature is too low, the drying time may be long, on the contrary, if the drying temperature is too high, moisture or solvent may react with the raw material to produce unwanted by-products.
  • the mixture of the above-described raw materials is heat-treated at 200 to 1,000 ° C. in a reducing atmosphere to prepare phosphors by stably maintaining the oxidation water of manganese.
  • the reducing atmosphere may be maintained by forming a hydrogen gas, a nitrogen gas or a mixed gas atmosphere thereof.
  • the reducing atmosphere may be 0 to 40% by volume of hydrogen gas (H 2 ) and 60 to 100% by volume of nitrogen gas (N 2 ). It is good to achieve. More preferably, a mixed gas atmosphere consisting of 20 to 30% by volume of hydrogen gas (H 2 ) and 70 to 80% by volume of nitrogen gas (N 2 ) is maintained. If the content of hydrogen gas is too small, the oxidation state of manganese is maintained. The lower limb may be difficult, and on the contrary, if the content of hydrogen gas is too high, there is a safety problem such as a risk of explosion, so it is better to select the above range.
  • the heat treatment may be performed using an alumina crucible, platinum or tungsten crucible, boron nitride crucible, or the like.
  • the heat treatment temperature is preferably 200 to 1000 ° C. If the heat treatment temperature is too low, the phosphor crystal may not be formed completely, and thus the luminous efficiency may be reduced. If the heat treatment temperature is too high, the luminance of the phosphor crystal may change and the luminance may decrease. .
  • the phosphor produced by the solid phase method described above can be pulverized using a ball mill or a jet mill. If necessary, the above heat treatment and grinding may be repeated two or more times.
  • the cleaning process may be further performed to control the content of the halogen element included in the manufactured phosphor. Even if washing causes variation in the content of the halogen element, the content of the halogen element in the finally prepared phosphor should satisfy the composition ratio of Chemical Formula 1.
  • the cleaning of the prepared phosphor may be performed using one or more solvents selected from acetone and alcohols having 1 to 4 carbon atoms. The cleaned phosphors may bring desirable results in further improving the luminescence brightness.
  • the manufacturing method of the metal fluoride red phosphor by the liquid phase method As a second manufacturing method according to the present invention, the manufacturing method of the metal fluoride red phosphor by the liquid phase method
  • the raw material is dissolved in an acid to prepare a solution, and then the solvent is distilled off under reduced pressure, and then prepared by heat treatment in an atmosphere of hydrogen gas, nitrogen gas or a mixed gas thereof.
  • the raw material used in the phosphor manufacturing method according to the liquid phase method it may be more advantageous to use a material that is well dissolved by an acid.
  • a material that is well dissolved by an acid at least one selected from AF, AHF 2 , A 2 O, A 2 CO 3 , CH 3 COO-A, A 2 MF 6 and A 2 MnF 6 may be used as the A precursor.
  • M precursors include metal oxides containing M metal, H 2 MF 6 And one or more selected from A 2 MF 6 .
  • a 2 MnF 6 may be used as the manganese (Mn) precursor.
  • a and M are as defined in the formula (1).
  • a 2 MF 6 or A 2 MF 6 : Mn 4 + used as an A precursor, an M precursor, or a manganese (Mn) precursor is a phosphor disclosed in Patent Document 3.
  • a 2 MF 6 or A 2 MF 6 : Mn 4 + used in the liquid phase method of the present invention is specifically K 2 SiF 6 , K 2 GeF 6 , K 2 TiF 6 , K 2 MnF 6 , K 2 SiF 6 : Mn 4 + , K 2 GeF 6 : Mn 4 + , K 2 TiF 6 : Mn 4 + , Rb 2 SiF 6 , Rb 2 GeF 6 , Rb 2 TiF 6 , Rb 2 MnF 6 , Rb 2 SiF 6 : Mn 4+ , Rb 2 GeF 6 : Mn 4 + , Rb 2 TiF 6 : Mn 4 + , (NH 4 ) 2 SiF 6 , (NH 4 ) 2 GeF 6 , (NH).
  • an acid is used to dissolve a raw material
  • the acid may be used without any distinction between an organic acid and an inorganic acid as long as the acid can dissolve the raw material.
  • the acid may be used at least one selected from hydrofluoric acid (HF), hydrochloric acid (HCl) and sulfuric acid (H 2 SO 4 ).
  • the acid solution in which the raw material is dissolved is removed by distilling off the solvent using a vacuum distillation apparatus to obtain a solid.
  • the solid obtained is dried in an oven at 80-150 ° C. to completely remove residual moisture and solvent.
  • the drying temperature is preferably 80 ⁇ 150 °C, if the drying temperature is too low, the drying time can be long, on the contrary, if the drying temperature is too high, moisture or solvent can react with the raw material to produce unwanted by-products. .
  • the dried solid is heat-treated at 200 to 1,000 ° C. in a reducing atmosphere to prepare a phosphor by stably maintaining the oxidation water of manganese.
  • the reducing atmosphere may be maintained by forming a hydrogen gas, a nitrogen gas or a mixed gas atmosphere thereof.
  • the reducing atmosphere may be 0 to 40% by volume of hydrogen gas (H 2 ) and 60 to 100% by volume of nitrogen gas (N 2 ). It is good to achieve. More preferably, a mixed gas atmosphere consisting of 20 to 30% by volume of hydrogen gas (H 2 ) and 70 to 80% by volume of nitrogen gas (N 2 ) is maintained. If the content of hydrogen gas is too small, the oxidation state of manganese is maintained. The lower limb may be difficult, and on the contrary, if the content of hydrogen gas is too high, there is a safety problem such as a risk of explosion, so it is better to select the above range.
  • the heat treatment may be performed using an alumina crucible, platinum or tungsten crucible, boron nitride crucible, or the like.
  • the heat treatment temperature is preferably 200 to 1000 ° C. If the heat treatment temperature is too low, the phosphor crystal may not be formed completely, and thus the luminous efficiency may be reduced. If the heat treatment temperature is too high, the luminance of the phosphor crystal may change and the luminance may decrease. .
  • the phosphor produced by the liquid phase method described above can be pulverized using a ball mill or a jet mill. If necessary, the above heat treatment and grinding may be repeated two or more times.
  • the cleaning process may be further performed to control the content of the halogen element included in the manufactured phosphor. Even if washing causes variation in the content of the halogen element, the content of the halogen element in the finally prepared phosphor should satisfy the composition ratio of Chemical Formula 1.
  • the cleaning of the prepared phosphor may be performed using one or more solvents selected from acetone and alcohols having 1 to 4 carbon atoms. The cleaned phosphors may bring desirable results in further improving the luminescence brightness.
  • the raw materials consisting of A precursor, M precursor, and manganese (Mn) precursor were respectively weighed in the amounts of freely prepared ingredients, 5 mL of ethanol was added, and physical mixing was performed for 10 minutes.
  • the raw material mixture was placed in an oven maintained at 100 ° C. and dried for 1 hour to completely remove ethanol.
  • the dried raw material mixture was placed in a platinum and boron nitride crucible and heat-treated at 400 ° C. for 30 minutes in a reducing atmosphere. At this time, the reducing atmosphere was maintained by supplying a mixed gas of 150 mL / min hydrogen and 450 mL / min nitrogen.
  • the phosphor obtained by the heat treatment was pulverized to have a particle size of 20 ⁇ m or less to obtain a phosphor powder.
  • the raw material consisting of A precursor, M precursor and manganese (Mn) precursor was weighed, dissolved in 100 mL of hydrofluoric acid (HF), and stirred.
  • the raw material-containing solution was sufficiently stirred to dissolve and then distilled under reduced pressure to obtain a solid.
  • the solid obtained was placed in an oven maintained at 100 ° C. and dried for 1 hour to completely remove residual hydrofluoric acid.
  • the dried solid was put into platinum and boron nitride crucible and heat treated at 400 ° C. for 30 minutes in a reducing atmosphere. At this time, the reducing atmosphere was maintained by supplying a mixed gas of 150 mL / min hydrogen and 450 mL / min nitrogen.
  • the phosphor obtained by the heat treatment was pulverized to have a particle size of 20 ⁇ m or less to obtain a phosphor powder.
  • the raw materials consisting of A precursor, M precursor and manganese (Mn) precursor were respectively weighed in the amounts of freely prepared ingredients, and 5 mL of acetone was added thereto for 10 minutes. Was carried out.
  • the raw material mixture was placed in an oven maintained at 60 ° C. and dried for 1 hour to completely remove acetone.
  • the dried raw material mixture was put into a platinum and boron nitride crucible and heat treated at 150 ° C. for 3 minutes using a (NH 4 ) HF 2 precursor in a reducing atmosphere, and heat treated at 300 ° C. for 3 hours using a KHF 2 precursor.
  • the reducing atmosphere was maintained by supplying a mixed gas of 150 mL / min hydrogen and 450 mL / min nitrogen.
  • the phosphor obtained by the heat treatment was pulverized to have a particle size of 50 ⁇ m or less to obtain a phosphor powder.
  • the metal fluoride phosphor represented by A 3 MF 7 : Mn 4 + according to the present invention is a metal fluoride phosphor represented by A 2 [MF 6 ]: Mn 4 + used as a raw material in the present invention. It was confirmed that the material has a crystal structure different from that of.
  • K 3 SiF 7 : Mn 4 + phosphors prepared in Examples 5, 14 and 22 and K 3 TiF 7 : Mn 4 + phosphors prepared in Example 46 were selected.
  • the K 2 [SiF 6 ]: Mn 4+ 0.03 phosphor and the K 2 [TiF 6 ]: Mn 4+ 0.03 phosphor used as raw materials in Examples 22 and 46 were selected.
  • 1 and 2 show the results of XRD analysis for each phosphor.
  • 1 is K 3 SiF 7: Mn 4 + the K 2 SiF used as a fluorescent substance and a raw material 6: XRD spectra to compare the crystal structure of the Mn 4 + 0.03 phosphor.
  • 2 is K TiF 3 7: The K 2 TiF used as Mn 4+ phosphor, and the raw material 6: XRD spectra to compare the crystal structure of the Mn 4 + 0.03 phosphor.
  • the metal fluoride phosphor represented by A 3 MF 7 : Mn 4 + according to the present invention may be identified as a phosphor having a crystal structure different from that of the A 2 MF 6 : Mn 4+ raw material. .
  • FIG. 3a and 3b are the results of analyzing the crystal structure by Rietveld refinement (Rietvled refinement) in order to understand the crystal structure of the K 3 SiF 7 : Mn 4 + phosphor.
  • FIG. 3A shows the XRD analysis of the K 3 SiF 7 : Mn 4 + phosphor
  • FIG. 3B shows the Rietveld structure analysis of the K 3 SiF 7 : Mn 4+ phosphor.
  • the basic crystal structure used for the structural analysis of K 3 SiF 7 : Mn 4 + phosphor was referred to in the ICSD (Inorganic Crystal Structure Database).
  • the crystal structure of K 3 SiF 7 : Mn 4 + phosphor was analyzed by referring to the existing data of K 3 SiF 7 as a parent.
  • Table 8 below shows the characteristic peak positions, the dilatation constant values, and the crystal structures of the respective phosphors using their own programs of the XRD apparatus. As the characteristic peaks shown in Table 8 below, five peaks having large 2 ⁇ intensity values were selected in the XRD pattern.
  • K 3 SiF 7 Mn 4 + phosphor (FIG. 4), (NH 4 ) 3 SiF 7 : Mn x 4 + phosphor (FIG. 5), (NH 4 ) 3 GeF 7 : Mn x 4+ phosphor (FIG. 6) ) And Rb 2 KSiF 7 : Mn x 4 + phosphors (FIG. 7), respectively, are attached to the XRD analysis results of FIGS. 4 to 7.
  • Test Example 2 the light emission characteristics of the prepared phosphor were analyzed.
  • the emission wavelength was analyzed by irradiating 450 nm excitation light using a luminescence analyzer (PerKin Elmer Photo-Luminescence).
  • Table 9 shows a brief summary of the central wavelength in the emission spectrum shown in FIGS.
  • the metal fluoride phosphor of the present invention is excited at a wavelength of 450 nm and has a characteristic of emitting a light emission central wavelength of 610 ⁇ 670 nm. Therefore, the metal fluoride phosphor of the present invention can be usefully used in the production of white LED having a high color rendering index.
  • Test Example 3 the afterglow time of the manufactured phosphor was evaluated. Measurement of luminescence over time was carried out using a YAG laser analyzer, a light source using 355 nm, and analyzed using a charge coupled device sensor that can distinguish up to 10 ns.
  • FIG. 13 shows the results of comparing afterglow time with increasing concentration of manganese (Mn) included as an activator in K 3 SiF 7 : Mn 4 + phosphor. That is, the phosphors prepared in Examples 1, 2, 5, and 8 were prepared by increasing K 2 MnF 6 manganese raw material by 0.005, 0.01, 0.03, 0.1 g as an activator with respect to 1 g of K 2 SiF 6 matrix raw material. 3 SiF 7 : Mn 4+ phosphor.
  • the phosphors of Examples 1, 2, 5, and 8 can be confirmed that the afterglow time is shortened to 13.9, 13.6, 12.9, and 11.7 ms. That is, it can be seen that afterglow time is shortened as the amount of the activator increases in the phosphor having the same composition.
  • the K 2 SiF 6 : Mn 4 + phosphor used as a raw material has an afterglow time of 17.3 ms
  • the K 3 SiF 7 : Mn 4 + phosphor prepared in Example 1 has an afterglow.
  • the short time allows the manufacture of light sources with advantages in the display or lighting industry.
  • Test Example 5 a white light emitting diode manufactured by applying the phosphor of the present invention was evaluated.
  • a mixture of 30 mg of a red phosphor and 0.2 g of a silicone resin was applied to the surface of a blue light emitting diode (light emitting wavelength 450 nm) chip, and cured at 150 ° C. for 30 minutes to produce a white light emitting diode.
  • the performance of the white light emitting diode fabricated in the above manner was evaluated by light emission analysis, and the results are shown in FIG. 19.
  • FIG. 19 shows the results of comparatively analyzing the luminescence properties of the well-known LuAG green yellow phosphor and the metal fluoride phosphor prepared in the present invention.
  • Phosphor of the present invention is prepared in Example 14 K 3 SiF 7 : Mn 4 + 0.03 Phosphor and K 3 TiF 7 : Mn 4+ 0.03 prepared in Example 46. Phosphor.
  • the metal fluoride phosphor prepared in the present invention has a narrow half width (FWHM) compared to the LuAG green yellow phosphor. Since the half width is small, it means that the human sense of color is small, and thus, when the white light emitting diamond is manufactured by mixing with the greenish yellow phosphor, it is possible to compensate for the lack of color reproducibility in the red region.
  • FWHM narrow half width

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Abstract

La présente invention concerne un phosphore rouge fluorure métallique et une application du phosphore comme élément électroluminescent, le phosphore rouge fluorure métallique ayant une structure cristalline tétragonale d'une composition nouvelle, et émettant de la lumière dans la longueur d'onde de couleur rouge en étant excité par les rayons ultraviolets ou une source d'excitation bleue, étant ainsi utilement applicable à un élément électroluminescent tel qu'une diode électroluminescente, une diode laser, une diode laser à émission en surface, un élément électroluminescent inorganique, et un élément électroluminescent organique.
PCT/KR2016/010596 2015-09-23 2016-09-22 Phosphore rouge fluorure métallique et élément électroluminescent l'utilisant WO2017052234A1 (fr)

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US15/762,619 US10961450B2 (en) 2015-09-23 2016-09-22 Metal fluoride red phosphor and light emitting element using same
EP16848959.9A EP3354708B1 (fr) 2015-09-23 2016-09-22 Phosphore rouge fluorure métallique et élément électroluminescent l'utilisant
CN201680060843.8A CN108350356B (zh) 2015-09-23 2016-09-22 金属氟化物红色磷光体和使用其的发光元件
JP2018515570A JP6591054B2 (ja) 2015-09-23 2016-09-22 金属フッ化物赤色蛍光体及びこれを用いた発光素子

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KR1020160119738A KR101854114B1 (ko) 2015-09-23 2016-09-20 금속불화물 적색 형광체 및 이를 이용한 발광소자
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