WO2018132998A1 - Procédé de préparation d'un matériau luminescent rouge excité par la lumière bleue - Google Patents

Procédé de préparation d'un matériau luminescent rouge excité par la lumière bleue Download PDF

Info

Publication number
WO2018132998A1
WO2018132998A1 PCT/CN2017/071669 CN2017071669W WO2018132998A1 WO 2018132998 A1 WO2018132998 A1 WO 2018132998A1 CN 2017071669 W CN2017071669 W CN 2017071669W WO 2018132998 A1 WO2018132998 A1 WO 2018132998A1
Authority
WO
WIPO (PCT)
Prior art keywords
fluoride
acid
luminescent material
mixed solution
present
Prior art date
Application number
PCT/CN2017/071669
Other languages
English (en)
Chinese (zh)
Inventor
汪正良
谭慧英
杨至雨
周亚运
周强
罗利军
张秋函
苏长伟
Original Assignee
云南民族大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 云南民族大学 filed Critical 云南民族大学
Priority to PCT/CN2017/071669 priority Critical patent/WO2018132998A1/fr
Priority to KR1020187026580A priority patent/KR102157429B1/ko
Publication of WO2018132998A1 publication Critical patent/WO2018132998A1/fr

Links

Images

Classifications

    • 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
    • C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
    • C09K11/664—Halogenides
    • C09K11/665—Halogenides with alkali 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
    • 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
    • C09K11/61—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing fluorine, chlorine, bromine, iodine or unspecified halogen elements
    • C09K11/611—Chalcogenides
    • C09K11/613—Chalcogenides with alkali or alkakine earth metals

Definitions

  • the invention relates to a method for preparing a blue light-emitting red light-emitting material, in particular to a method for preparing a Mn 4+ ion-doped fluoride red light-emitting material for a blue semiconductor light-emitting diode (LED).
  • a blue light-emitting red light-emitting material in particular to a method for preparing a Mn 4+ ion-doped fluoride red light-emitting material for a blue semiconductor light-emitting diode (LED).
  • the Mn 4+ doped fluoride red luminescent material can be applied to GaN-based white LED illumination because of its strong and wide excitation band in the blue region and a strong red light narrow band.
  • a large amount of hydrofluoric acid is used to prepare the Mn 4+ doped fluoride red luminescent material.
  • the patent document of the publication No. US2006169998A1 discloses a process for preparing A 2 MF 6 (A is Na, K, Rb, etc.; M is Ti, Si, Sn, Ge, etc.).
  • the method comprises dissolving various raw materials in a high concentration of hydrofluoric acid and then crystallizing to obtain a sample; however, the method has the disadvantages of long operation time, excessive use of hydrofluoric acid, and uneven product morphology.
  • the patent document published as CN103980896A also discloses the preparation of A 2 MF 6 (A is one or a combination of Li, Na, K, Rb, Cs; M is Ti, Si, Sn, Ge, Zr a method of one or several combinations), using potassium hexafluoromanganate or sodium hexafluoromanganate as a source of Mn 4+ , by reacting with a prepared A 2 MF 6 matrix material in a hydrofluoric acid solution Exchange to get the sample.
  • hydrofluoric acid is used in the preparation of A 2 MF 6 , and hydrofluoric acid is a highly corrosive and toxic chemical agent, and excessive use can cause serious environmental pollution problems. Therefore, how to reduce the amount of hydrofluoric acid used and obtain high-efficiency fluoride red luminescent materials has important research significance and application prospects.
  • An exemplary embodiment of the present invention discloses a method of preparing a blue-excited red luminescent material having a chemical composition of A 2 X 1-y F 6 : yMn 4+ , wherein A is selected from a base At least one of metal elements; X is selected from at least one of Ti, Si, Ge, and Zr; y represents a molar percentage coefficient of Mn 4+ ions relative to X 4+ ions, 0 ⁇ y ⁇ 0.10;
  • the method comprises: mixing a matrix material containing X with a reaction solvent to obtain a first mixed solution, wherein the reaction solvent comprises a mixture of at least one of formic acid, acetic acid, and fluoroacetic acid and absolute ethanol or formic acid, acetic acid, and At least one of fluoroacetic acid; adding fluoride of Mn 4+ to the first mixed solution to obtain a second mixed solution; adding fluoride of A to the second mixed solution to obtain a precipitate, thereby obtaining a red luminescent material .
  • the matrix material containing X may include at least one of an aqueous solution of hexafluorosilicic acid, an aqueous solution of hexafluorotitanate, an aqueous solution of hexafluorozirconate, and ammonium hexafluoroantimonate.
  • the mass percentage of the aqueous solution of hexafluorosilicic acid, the aqueous solution of hexafluorotitanate or the aqueous solution of hexafluorozirconate may be 30% to 50%.
  • the volume ratio of at least one of formic acid, acetic acid, and fluoroacetic acid to absolute ethanol may be from 1 to 100:1.
  • the fluoride of Mn 4+ may include one of potassium hexafluoromanganate and sodium hexafluoromanganate.
  • the fluoride of A may include at least one of sodium fluoride, potassium fluoride, cesium fluoride, and cesium fluoride.
  • the step of mixing the matrix material containing X with the reaction solvent may include mixing the matrix material containing X with a reaction solvent and stirring uniformly at room temperature to obtain a first mixed solution.
  • the step of adding the fluoride of Mn 4+ to the first mixed solution may include: stirring the Mn 4+ fluoride after adding the first mixture to the first mixture for 20 min to 60 min to obtain a second mixture.
  • the step of adding the fluoride of A to the second mixed solution may include: adding the fluoride of A to the second mixed solution, and stirring for 1 hour to 12 hours to obtain a precipitate.
  • the method may further include: washing the precipitate and drying to obtain a red luminescent material.
  • blue-excited red can be prepared without using hydrofluoric acid A luminescent material, so the method of the invention does not affect environmental pollution.
  • the morphology of the red luminescent material prepared by using at least one of formic acid, acetic acid and fluoroacetic acid and anhydrous ethanol or at least one of formic acid, acetic acid and fluoroacetic acid as a reaction solvent is used. Uniform.
  • the preparation method according to the invention is simple in preparation, convenient in operation, and suitable for industrialized mass production.
  • FIG. 1 is a flow chart of a method of preparing a red luminescent material, in accordance with an exemplary embodiment of the present invention
  • Example 2 is an XRD diffraction pattern of Na 2 TiF 6 :Mn 4+ obtained in Example 1 of the present invention
  • Example 3 is a view showing a room temperature excitation spectrum (monitoring wavelength of 627 nm) and an emission spectrum (excitation wavelength of 460 nm) of Na 2 TiF 6 :Mn 4+ obtained in Example 1 of the present invention;
  • Example 4 is an electroluminescence spectrum diagram of an LED device fabricated by using Na 2 TiF 6 :Mn 4+ and a blue LED chip obtained in Example 1 of the present invention under a current excitation of 20 mA;
  • Figure 5 is an XRD diffraction pattern of Na 2 SiF 6 :Mn 4+ obtained in Example 2 of the present invention
  • Example 6 is a view showing a room temperature excitation spectrum (monitoring wavelength of 627 nm) and an emission spectrum (excitation wavelength of 460 nm) of Na 2 SiF 6 :Mn 4+ obtained in Example 2 of the present invention;
  • Example 7 is an electroluminescence spectrum diagram of an LED device fabricated by using Na 2 SiF 6 :Mn 4+ and a blue LED chip obtained in Example 2 of the present invention under a current excitation of 20 mA;
  • Figure 8 is an XRD diffraction pattern of K 2 TiF 6 :Mn 4+ obtained in Example 3 of the present invention.
  • Example 9 is a view showing a room temperature excitation spectrum (monitoring wavelength of 632 nm) and an emission spectrum (excitation wavelength of 460 nm) of K 2 TiF 6 :Mn 4+ obtained in Example 3 of the present invention;
  • Example 10 is an electroluminescence spectrum diagram of an LED device fabricated by K 2 TiF 6 :Mn 4+ and a blue LED chip obtained in Example 3 of the present invention under a current excitation of 20 mA;
  • Figure 11 is an XRD diffraction pattern of K 2 GeF 6 :Mn 4+ obtained in Example 4 of the present invention.
  • Figure 12 is a view showing a room temperature excitation spectrum (monitoring wavelength of 631 nm) and an emission spectrum (excitation wavelength of 460 nm) of K 2 GeF 6 :Mn 4+ obtained in Example 4 of the present invention;
  • Example 13 is an electroluminescence spectrum diagram of an LED device fabricated by K 2 GeF 6 :Mn 4+ and a blue LED chip obtained in Example 4 of the present invention under a current excitation of 20 mA;
  • Figure 14 is an XRD diffraction pattern of Rb 2 TiF 6 :Mn 4+ obtained in Example 5 of the present invention.
  • Example 15 is a view showing a room temperature excitation spectrum (monitoring wavelength of 631 nm) and an emission spectrum (excitation wavelength of 465 nm) of Rb 2 TiF 6 :Mn 4+ obtained in Example 5 of the present invention;
  • 16 is an electroluminescence spectrum diagram of an LED device fabricated by Rb 2 TiF 6 :Mn 4+ and a blue LED chip obtained in Example 5 of the present invention under a current excitation of 20 mA;
  • Figure 17 is an XRD diffraction pattern of Cs 2 ZrF 6 :Mn 4+ obtained in Example 6 of the present invention.
  • Example 18 is a view showing a room temperature excitation spectrum (monitoring wavelength of 630 nm) and an emission spectrum (excitation wavelength of 480 nm) of Cs 2 ZrF 6 :Mn 4+ obtained in Example 6 of the present invention;
  • Fig. 19 is a graph showing the electroluminescence spectrum of an LED device fabricated by using Cs 2 ZrF 6 : Mn 4+ and a blue LED chip obtained in Example 6 of the present invention under a current of 20 mA.
  • a red luminescent material is prepared by using hydrofluoric acid as a reaction solvent, and a large amount of hydrofluoric acid is used to cause environmental pollution. Based on this, the present invention proposes a method of preparing a red luminescent material without using hydrofluoric acid.
  • A is selected from at least one of alkali metal elements;
  • X is selected from at least one of Ti, Si, Ge, and Zr; and
  • y represents Mn 4+ ions relative to X 4+ ions.
  • A may be selected from at least one of Na, K, Rb, and Cs.
  • A may be Na and/or K.
  • X may be selected from a tetravalent element of at least one of Ti, Si, Ge, and Zr.
  • X may be Si or Ti.
  • the red luminescent material has a structure in which the X component in A 2 X 1-y F 6 is partially replaced by Mn 4+ , so such a red luminescent material may be referred to as Mn-activated fluoride red.
  • Luminescent material The red luminescent material according to the present invention has a strong red light emission peak under blue light excitation (for example, an emission peak is located at about 627 nm or about 632 nm), and has high luminous efficiency; and the obtained red luminescent material has an emission spectral color coordinate value close to that.
  • FIG. 1 is a flow chart of a method of preparing a blue-excited red luminescent material, in accordance with an exemplary embodiment of the present invention.
  • a method of preparing a blue-excited red luminescent material includes: mixing a matrix material containing X with a reaction solvent to obtain a first mixed solution (S100); and Mn 4+ Fluoride is added to the first mixed solution to obtain a second mixed solution (S200); fluoride of A is added to the second mixed solution to obtain a precipitate (S300); the precipitate is washed and dried to obtain red light Material (S400).
  • the matrix material containing X is mixed with a reaction solvent (S100)
  • the matrix material containing X is mixed with a reaction solvent at room temperature and stirred uniformly to obtain a first mixed solution.
  • X may be the same as X described above, and will not be described herein.
  • the matrix material containing X may include at least one of an aqueous solution of hexafluorosilicic acid, an aqueous solution of hexafluorotitanate, an aqueous solution of hexafluorozirconate, and ammonium hexafluoroantimonate.
  • the mass percentage of the aqueous solution of hexafluorosilicic acid, the aqueous solution of hexafluorotitanate or the aqueous solution of hexafluorozirconate may be 30% to 50%.
  • ammonium hexafluoroantimonate may be directly mixed with the reaction solvent when ammonium hexafluoroantimonate is used.
  • the ratio of the matrix material containing X to is not specifically limited, and the reaction solvent may include any suitable amount capable of completely dissolving the matrix material containing X.
  • the reaction solvent may include a mixture of at least one of formic acid, acetic acid, and fluoroacetic acid and absolute ethanol or at least one of formic acid, acetic acid, and fluoroacetic acid.
  • the reaction solvent may include a mixture of formic acid and absolute ethanol, a mixture of acetic acid and absolute ethanol, a mixture of fluoroacetic acid and absolute ethanol, a mixture of formic acid and acetic acid and absolute ethanol, acetic acid and fluoroacetic acid, and anhydrous a mixture of ethanol, or a mixture of formic acid and fluoroacetic acid and absolute ethanol.
  • the volume ratio of at least one of formic acid, acetic acid, and fluoroacetic acid to absolute ethanol may be from 1 to 100:1. Alternatively, it may be 5-90:1, 10-80:1, 20-70:1 30-60:1 or 40-50:1, or any range defined by the numerical values given above, for example, may be 1-10:1.
  • environmental pollution can be reduced by using a mixture of at least one of formic acid, acetic acid, and fluoroacetic acid and anhydrous ethanol or at least one of formic acid, acetic acid, and fluoroacetic acid instead of hydrofluoric acid as a reaction solvent. .
  • the Mn 4+ fluoride is added to the first mixed solution (S200), and after the Mn 4+ fluoride is added to the first mixture, the mixture is stirred for 20 minutes to 60 minutes to obtain a second mixed solution.
  • the fluoride of Mn 4+ may include one of potassium hexafluoromanganate and sodium hexafluoromanganate.
  • Mn 4+ is used as a luminescent center, and its content directly affects the luminous efficiency of the sample, and the content is too low, and the luminous efficiency is too low; if the content is too high, the concentration quenching phenomenon may also occur. Thereby, the luminous efficiency of the sample is also lowered, so it is necessary to regulate the content of Mn 4+ in the luminescent material.
  • the molar ratio of Mn 4+ to X 4+ is from 0.01 to 0.1:1.
  • the fluoride of A is added to the second mixed solution (S300), and the fluoride of A is added to the second mixed solution and stirred for 1 hour to 12 hours to obtain a precipitate.
  • A may be the same as A described above, and will not be described herein.
  • the fluoride of A may include at least one of sodium fluoride, potassium fluoride, cesium fluoride, and cesium fluoride.
  • the addition of the fluoride of A to the second mixed solution enables precipitation of the second mixed solution, thereby obtaining a red luminescent material.
  • the molar ratio of the fluoride of A to the matrix material containing X may be from 0.5 to 10:1, alternatively, may be from 1 to 9:1, from 2 to 8:1. -6:1 or 4-5:1, or any range defined by the numerical values given above, for example, may be 2-7:1. If the amount of fluoride in A is too low, the sample is difficult to precipitate; if the amount of fluoride in A is too high, other heterogeneous substances will be formed, resulting in impure phase of the sample.
  • the precipitate may be washed with anhydrous methanol or absolute ethanol and dried in a vacuum for 10 to 30 hours to obtain a blue-excited red luminescent material.
  • each step is at room temperature Go on.
  • a blue light-excited red luminescent material was obtained by ion exchange-coprecipitation without using hydrofluoric acid.
  • the excitation wavelength of blue light may range from 420 nm to 480 nm.
  • a blue light-excited red luminescent material can be prepared without using hydrofluoric acid, so that the method of the present invention does not affect environmental pollution.
  • the morphology of the red luminescent material is uniform by using at least one of formic acid, acetic acid and fluoroacetic acid and anhydrous ethanol or at least one of formic acid, acetic acid and fluoroacetic acid as a reaction solvent. .
  • the method according to the invention has simple preparation process, convenient operation and is suitable for industrial large-scale production.
  • 2 is an XRD diffraction pattern of Na 2 TiF 6 :Mn 4+ obtained in Example 1 of the present invention.
  • 3 is a graph showing a room temperature excitation spectrum (monitoring wavelength of 627 nm) and an emission spectrum (excitation wavelength of 460 nm) of Na 2 TiF 6 :Mn 4+ obtained in Example 1 of the present invention.
  • 4 is an electroluminescence spectrum of an LED device fabricated by using Na 2 TiF 6 :Mn 4+ and a blue LED chip obtained in Example 1 of the present invention under a current of 20 mA.
  • the Na 2 TiF 6 : Mn 4+ obtained in this Example 1 was compared with the standard card JCPDS 15-0581 (Na 2 TiF 6 ), and the two were completely identical, and no diffraction peak of any impurity phase was observed. This indicates that the prepared red luminescent material has a single crystal phase.
  • the obtained red luminescent material has strong broadband excitation in both the ultraviolet region and the blue region.
  • the emission wavelength of the red luminescent material is mainly red light emission wavelength, and the emission wavelength is about 627 nm, which corresponds to the 2 E g - 4 A 2g transition of Mn 4+ .
  • FIG. 4 is a spectrum diagram obtained by applying the obtained red light-emitting material to an LED device on a blue LED chip, and exciting it at a current of 20 mA.
  • the emission peak of about 460 nm is the blue light emitted by the LED chip, and the emission peak of the red luminescent material obtained by the present invention is located in the red light region, and the strongest emission peak is located at 627 nm.
  • Fig. 5 is an XRD diffraction pattern of Na 2 SiF 6 :Mn 4+ obtained in Example 2 of the present invention.
  • Fig. 6 is a graph showing the room temperature excitation spectrum (monitoring wavelength of 627 nm) and emission spectrum (excitation wavelength of 460 nm) of Na 2 SiF 6 :Mn 4+ obtained in Example 2 of the present invention.
  • 7 is an electroluminescence spectrum of an LED device fabricated by using Na 2 SiF 6 :Mn 4+ and a blue LED chip obtained in Example 2 of the present invention under a current excitation of 20 mA.
  • the Na 2 SiF 6 : Mn 4+ obtained in this Example 2 was compared with the standard card JCPDS 33-1280, and the two were completely identical, and no diffraction peak of any impurity phase was observed, which indicates that the prepared The red luminescent material has a single crystalline phase.
  • the obtained red luminescent material has strong broadband excitation in both the ultraviolet region and the blue region.
  • the emission wavelength of the red luminescent material is mainly red light emission wavelength, and the emission wavelength is about 627 nm, which corresponds to the 2 E g - 4 A 2g transition of Mn 4+ .
  • Fig. 7 is a spectrum diagram obtained by applying the obtained red light-emitting material to an LED device on a blue LED chip, and exciting it at a current of 20 mA. It can be seen from FIG. 7 that the emission peak around 460 nm is the blue light emitted by the LED chip, and the emission of the red luminescent material obtained by the present invention is obtained. The peak is located in the red region and its strongest emission peak is at 627 nm.
  • Fig. 8 is an XRD diffraction pattern of K 2 TiF 6 :Mn 4+ obtained in Example 3 of the present invention.
  • Fig. 9 is a graph showing the room temperature excitation spectrum (monitoring wavelength of 632 nm) and emission spectrum (excitation wavelength of 460 nm) of K 2 TiF 6 :Mn 4+ obtained in Example 3 of the present invention.
  • Fig. 10 is a graph showing the electroluminescence spectrum of an LED device fabricated by K 2 TiF 6 :Mn 4+ and a blue LED chip obtained in Example 3 of the present invention under a current of 20 mA.
  • the K 2 TiF 6 : Mn 4+ obtained in this Example 3 was compared with the standard card JCPDS 08-0488, and the two were completely identical, and no diffraction peak of any impurity phase was observed, indicating that the prepared The red luminescent material has a single crystalline phase.
  • the obtained red luminescent material has strong broadband excitation in both the ultraviolet region and the blue region.
  • the emission wavelength of the red luminescent material is mainly red light emission wavelength, and the emission wavelength is about 632 nm, which corresponds to the 2 E g - 4 A 2g transition of Mn 4+ .
  • Fig. 10 is a spectrum diagram obtained by applying the obtained red light-emitting material to an LED device on a blue LED chip, and exciting it at a current of 20 mA.
  • the emission peak of about 460 nm is the blue light emitted by the LED chip, and the emission peak of the red luminescent material obtained by the present invention is located in the red light region, and the strongest emission peak is located at 632 nm.
  • Figure 11 is an XRD diffraction pattern of K 2 GeF 6 :Mn 4+ obtained in Example 4 of the present invention.
  • Fig. 12 is a graph showing the room temperature excitation spectrum (monitoring wavelength of 631 nm) and emission spectrum (excitation wavelength of 460 nm) of K 2 GeF 6 :Mn 4+ obtained in Example 4 of the present invention.
  • Figure 13 is a graph showing the electroluminescence spectrum of an LED device fabricated by K 2 GeF 6 :Mn 4+ and a blue LED chip obtained in Example 4 of the present invention under a current of 20 mA.
  • the K 2 GeF 6 : Mn 4+ obtained in this Example 4 was compared with the standard card JCPDS 07-0241, and the two were completely identical, and no diffraction peak of any impurity phase was observed, indicating that the prepared The red luminescent material has a single crystalline phase.
  • the obtained red luminescent material has strong broadband excitation in both the ultraviolet region and the blue region.
  • the emission wavelength of the red luminescent material is mainly red light emission wavelength under the excitation of 460 nm light, and the emission wavelength is about 631 nm, which corresponds to the 2 E g - 4 A 2g transition of Mn 4+ .
  • Fig. 13 is a spectrum diagram obtained by applying the obtained red light-emitting material to an LED device on a blue LED chip, and exciting it at a current of 20 mA.
  • the emission peak of about 460 nm is the blue light emitted by the LED chip, and the emission peak of the red luminescent material obtained by the present invention is located in the red light region, and the strongest emission peak is located at 631 nm.
  • Figure 14 is an XRD diffraction pattern of Rb 2 TiF 6 :Mn 4+ obtained in Example 5 of the present invention.
  • Fig. 15 is a graph showing the room temperature excitation spectrum (monitoring wavelength of 631 nm) and emission spectrum (excitation wavelength of 465 nm) of Rb 2 TiF 6 :Mn 4+ obtained in Example 5 of the present invention.
  • Figure 16 is a graph showing the electroluminescence spectrum of an LED device fabricated by Rb 2 TiF 6 :Mn 4+ and a blue LED chip obtained in Example 5 of the present invention under a current of 20 mA.
  • the Rb 2 TiF 6 : Mn 4+ obtained in this Example 5 was compared with the standard card JCPDS 51-0611, and the two were completely identical, and no diffraction peak of any impurity phase was observed, which indicates that the prepared The red luminescent material has a single crystalline phase.
  • the obtained red luminescent material has strong broadband excitation in both the ultraviolet region and the blue region.
  • the emission wavelength of the red luminescent material is mainly red light emission wavelength, and the emission wavelength is about 631 nm, which corresponds to the 2 E g - 4 A 2g transition of Mn 4+ .
  • Fig. 16 is a spectrum chart obtained by applying the obtained red light-emitting material to an LED device on a blue LED chip, and exciting it at a current of 20 mA. It can be seen from FIG. 16 that the emission peak around 465 nm is the blue light emitted by the LED chip, and the emission peak of the red luminescent material obtained by the present invention is located in the red light region, and the strongest emission peak is located at 631 nm.
  • Figure 17 is an XRD diffraction pattern of Cs 2 ZrF 6 :Mn 4+ obtained in Example 6 of the present invention.
  • Fig. 18 is a graph showing the room temperature excitation spectrum (monitoring wavelength of 630 nm) and emission spectrum (excitation wavelength of 480 nm) of Cs 2 ZrF 6 :Mn 4+ obtained in Example 6 of the present invention.
  • Fig. 19 is a graph showing the electroluminescence spectrum of an LED device fabricated by using Cs 2 ZrF 6 : Mn 4+ and a blue LED chip obtained in Example 6 of the present invention under a current of 20 mA.
  • the Cs 2 ZrF 6 : Mn 4+ obtained in this Example 6 was compared with the standard card JCPDS 74-0173, and the two were completely identical, and no diffraction peak of any impurity phase was observed, which indicates that the prepared The red luminescent material has a single crystalline phase.
  • the obtained red luminescent material has a strong broadband excitation in both the ultraviolet region and the blue region.
  • the emission wavelength of the red luminescent material is mainly red light emission wavelength, and the emission wavelength is about 630 nm, which corresponds to the 2 E g - 4 A 2g transition of Mn 4+ .
  • Fig. 19 is a spectrum diagram obtained by applying the obtained red light-emitting material to an LED device on a blue LED chip, and exciting it at a current of 20 mA.
  • the emission peak of about 460 nm is the blue light emitted by the LED chip, and the emission peak of the red luminescent material obtained by the present invention is located in the red light region, and the strongest emission peak is located at 630 nm.
  • a red luminescent material is prepared by using at least one of formic acid, acetic acid and fluoroacetic acid and anhydrous ethanol or at least one of formic acid, acetic acid and fluoroacetic acid as a reaction solvent.
  • the appearance is uniform.
  • the red luminescent material prepared according to the method of the present invention has a strong red light emission peak under blue light excitation (for example, an emission peak is located at about 627 nm or about 632 nm), and the luminous efficiency is high.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Luminescent Compositions (AREA)

Abstract

L'invention concerne un procédé de préparation d'un matériau luminescent rouge excité par la lumière bleue sans utiliser d'acide fluorhydrique, le matériau luminescent rouge ayant une composition chimique de A2X1-yF6:yMn4+, A étant sélectionné parmi au moins l'un des éléments alcalins; X étant sélectionné parmi Ti, Si, Ge et Zr; y représente le coefficient de pourcentage en moles des ions Mn4+ par rapport aux ions X4+, avec 0 < y ≤ 0,10; et le procédé comprend les étapes suivantes : un matériau matriciel contenant X est mélangé avec un solvant réactif pour obtenir une première solution mixte, le solvant réactif comprenant un mélange d'au moins l'un de l'acide formique, de l'acide acétique et de l'acide fluoroacétique avec de l'éthanol anhydre ou au moins l'un de l'acide formique, de l'acide acétique et de l'acide fluoroacétique; un fluorure de Mn4+ est ajouté dans la première solution mixte pour obtenir une seconde solution mélangée; et un fluorure d'A est ajouté dans la seconde solution mélangée pour obtenir un précipité, permettant ainsi d'obtenir le matériau luminescent rouge. Le procédé ne pollue pas l'environnement.
PCT/CN2017/071669 2017-01-19 2017-01-19 Procédé de préparation d'un matériau luminescent rouge excité par la lumière bleue WO2018132998A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/CN2017/071669 WO2018132998A1 (fr) 2017-01-19 2017-01-19 Procédé de préparation d'un matériau luminescent rouge excité par la lumière bleue
KR1020187026580A KR102157429B1 (ko) 2017-01-19 2017-01-19 청색광에 의해 여기된 적색 발광 재료의 제조 방법

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2017/071669 WO2018132998A1 (fr) 2017-01-19 2017-01-19 Procédé de préparation d'un matériau luminescent rouge excité par la lumière bleue

Publications (1)

Publication Number Publication Date
WO2018132998A1 true WO2018132998A1 (fr) 2018-07-26

Family

ID=62907626

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2017/071669 WO2018132998A1 (fr) 2017-01-19 2017-01-19 Procédé de préparation d'un matériau luminescent rouge excité par la lumière bleue

Country Status (2)

Country Link
KR (1) KR102157429B1 (fr)
WO (1) WO2018132998A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113416533A (zh) * 2021-06-09 2021-09-21 浦江县富盛塑胶新材料有限公司 一种彩色水固化玩具中硼砂含量检测的材料
CN114381260A (zh) * 2022-01-20 2022-04-22 广东省科学院资源利用与稀土开发研究所 一种四价锰离子激活氟化物红色发光材料的绿色合成方法
CN114790216A (zh) * 2022-03-09 2022-07-26 山西大学 红色荧光银纳米团簇及其制备方法和应用
CN115197702A (zh) * 2021-04-08 2022-10-18 中国科学院宁波材料技术与工程研究所 一种氟化物盐近红外荧光粉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
CN102732249A (zh) * 2011-04-08 2012-10-17 信越化学工业株式会社 复合氟化物与复合氟化物荧光体的制备
CN102827601A (zh) * 2012-09-17 2012-12-19 中国科学院福建物质结构研究所 氟化物荧光粉体材料及其半导体发光器件
WO2013158929A1 (fr) * 2012-04-18 2013-10-24 Nitto Denko Corporation Céramiques phosphoreuses et leur procédé de fabrication
CN104357050A (zh) * 2014-10-25 2015-02-18 云南民族大学 用于蓝光激发的高色纯度红色发光材料及其制备方法
CN105980523A (zh) * 2014-01-30 2016-09-28 信越化学工业株式会社 复合氟化物荧光体的制造方法和处理方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI438262B (zh) * 2008-02-07 2014-05-21 Mitsubishi Chem Corp A semiconductor light emitting device, a backlight, a color image display device, and a phosphor

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102732249A (zh) * 2011-04-08 2012-10-17 信越化学工业株式会社 复合氟化物与复合氟化物荧光体的制备
WO2013158929A1 (fr) * 2012-04-18 2013-10-24 Nitto Denko Corporation Céramiques phosphoreuses et leur procédé de fabrication
CN102827601A (zh) * 2012-09-17 2012-12-19 中国科学院福建物质结构研究所 氟化物荧光粉体材料及其半导体发光器件
CN105980523A (zh) * 2014-01-30 2016-09-28 信越化学工业株式会社 复合氟化物荧光体的制造方法和处理方法
CN104357050A (zh) * 2014-10-25 2015-02-18 云南民族大学 用于蓝光激发的高色纯度红色发光材料及其制备方法

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115197702A (zh) * 2021-04-08 2022-10-18 中国科学院宁波材料技术与工程研究所 一种氟化物盐近红外荧光粉及其制备方法和应用
CN115197702B (zh) * 2021-04-08 2024-03-22 中国科学院宁波材料技术与工程研究所 一种氟化物盐近红外荧光粉及其制备方法和应用
CN113416533A (zh) * 2021-06-09 2021-09-21 浦江县富盛塑胶新材料有限公司 一种彩色水固化玩具中硼砂含量检测的材料
CN113416533B (zh) * 2021-06-09 2022-04-15 浦江县富盛塑胶新材料有限公司 一种彩色水固化玩具中硼砂含量检测的材料
CN114381260A (zh) * 2022-01-20 2022-04-22 广东省科学院资源利用与稀土开发研究所 一种四价锰离子激活氟化物红色发光材料的绿色合成方法
CN114381260B (zh) * 2022-01-20 2024-02-27 广东省科学院资源利用与稀土开发研究所 一种四价锰离子激活氟化物红色发光材料的绿色合成方法
CN114790216A (zh) * 2022-03-09 2022-07-26 山西大学 红色荧光银纳米团簇及其制备方法和应用
CN114790216B (zh) * 2022-03-09 2023-09-22 山西大学 红色荧光银纳米团簇及其制备方法和应用

Also Published As

Publication number Publication date
KR102157429B1 (ko) 2020-09-17
KR20180110126A (ko) 2018-10-08

Similar Documents

Publication Publication Date Title
CN107236543B (zh) 一种提高Mn4+掺杂氟化物红色荧光粉材料耐湿性能的方法
WO2018132998A1 (fr) Procédé de préparation d&#39;un matériau luminescent rouge excité par la lumière bleue
Shang et al. Blue emitting Ca8La2 (PO4) 6O2: Ce3+/Eu2+ phosphors with high color purity and brightness for white LED: soft-chemical synthesis, luminescence, and energy transfer properties
Li et al. Tunable blue-green emission and energy transfer properties in β-Ca 3 (PO 4) 2: Eu 2+, Tb 3+ phosphors with high quantum efficiencies for UV-LEDs
CN112251219B (zh) 一种耐湿型氟化物红色荧光粉及其制备方法
CN108003872B (zh) 蓝光激发白光led用氟化物红色荧光粉及其制备与改性方法
Guo et al. Preparation of phosphors AEu (MoO 4) 2 (A= Li, Na, K and Ag) by sol-gel method
CN110713827B (zh) 一种掺Mn4+的六氟化物红色荧光粉及合成方法
CN115651655B (zh) 一种具有超高荧光热稳定性的近红外发光材料及其制备方法与应用
CN109423276B (zh) 一种高效稳定的Mn4+掺杂氟化物发光材料及其制备方法
CN115710500A (zh) 一种防水型Mn4+掺杂氟化物红色荧光粉及其制备方法
CN114381260B (zh) 一种四价锰离子激活氟化物红色发光材料的绿色合成方法
CN109722092B (zh) 一种蓝光激发led用红色荧光粉的超级增敏发光及制备方法
CN108587627B (zh) Eu3+离子激活的氟氯碲酸铋及其制备方法和应用
CN107603624B (zh) 一种蓝光激发的Mn4+掺杂氟镱酸盐红光材料及其制备方法
CN114989824A (zh) 短寿命类球形Mn4+掺杂氟化物红色荧光粉、结构、制备方法、发光装置
KR101722052B1 (ko) 형광체의 제조방법 및 이에 따라 제조되는 형광체를 포함하는 발광소자
Chen et al. The structure refinement and fluorescent quenching mechanism of Sr 3− x B 2 SiO 8: xEu 3+ phosphor
CN114806564A (zh) 三价铬离子掺杂氟锑酸盐近红外荧光材料、制备方法及其led光源
CN111057543B (zh) 一种Mn4+掺杂的碱金属氟磷酸盐红色发光材料及制备方法
Zhang et al. Luminescence of SrY2O4: Eu3+ associated with defects
CN106433637A (zh) 一种新型Mn4+激活的高色纯度氟化物红色发光材料制备方法
CN111471460B (zh) 一种高色纯度高热稳定性红色荧光材料及其制备方法
TWI628262B (zh) Method for preparing manganese activated zinc aluminum spinel oxynitride fluorescent powder
WO2020024317A1 (fr) Matériau fluorescent à base de phosphate activé par des ions eu3+, sa préparation et utilisation correspondante

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 20187026580

Country of ref document: KR

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 1020187026580

Country of ref document: KR

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17892947

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17892947

Country of ref document: EP

Kind code of ref document: A1