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WO2018132998A1 - Method for preparing red luminescent material excited by blue light - Google Patents

Method for preparing red luminescent material excited by blue light Download PDF

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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
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Prior art keywords
fluoride
acid
luminescent material
mixed solution
present
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French (fr)
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
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Yunnan Minzu University
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Yunnan Minzu University
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Priority to PCT/CN2017/071669 priority Critical patent/WO2018132998A1/en
Priority to KR1020187026580A priority patent/KR102157429B1/en
Publication of WO2018132998A1 publication Critical patent/WO2018132998A1/en
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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
    • C09K11/66—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.

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  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

Disclosed is a method for preparing a red luminescent material excited by blue light without using hydrofluoric acid, wherein the red luminescent material has a chemical composition of A2X1-yF6:yMn4+, wherein A is selected from at least one of the alkaline elements; X is selected from at least one of Ti, Si, Ge and Zr; y represents the mole percent coefficient of Mn4+ ions relative to X4+ ions, where 0<y≤0.10; and the method comprises the following steps: a matrix material containing X is mixed with a reactive solvent to obtain a first mixed solution, wherein the reactive solvent comprises a mixture of at least one of formic acid, acetic acid and fluoroacetic acid with anhydrous ethanol or at least one of formic acid, acetic acid and fluoroacetic acid; a fluoride of Mn4+ is added into the first mixed solution to obtain a second mixed solution; and a fluoride of A is added into the second mixed solution to obtain a precipitate, thus obtaining the red luminescent material. The method will not affect the environment by polluting same.

Description

制备蓝光激发的红色发光材料的方法Method for preparing blue-excited red luminescent material 技术领域Technical field

本发明涉及一种蓝光激发的红色发光材料的制备方法，具体地，涉及一种蓝光半导体发光二极管(LED)用的Mn4+离子掺杂的氟化物红色发光材料的制备方法。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).

背景技术Background technique

Mn4+掺杂的氟化物红色发光材料由于其在蓝光区具有很强很宽的激发带以及很强的红光窄带，可被应用于GaN基白光LED照明上。通常，会使用大量的氢氟酸来制备Mn4+掺杂的氟化物红色发光材料。例如，公开号为US2006169998A1的专利文件公开了制备A2MF6(A为Na、K、Rb等；M为Ti、Si、Sn、Ge等)的方法。该方法包括将各种原料溶于高浓度的氢氟酸中，然后结晶，从而得到样品；然而，该方法具有操作时间长、氢氟酸用量过大、产品形貌不均一等缺点。另外，公开号为CN103980896A的专利文件也公开了制备A2MF6(A为Li、Na、K、Rb、Cs中的一种或几种组合；M为Ti、Si、Sn、Ge、Zr中的一种或几种组合)的方法，该方法以六氟锰酸钾或六氟锰酸钠为Mn4+源，通过与已制备好的A2MF6基质材料在氢氟酸溶液中进行交换来得到样品。然而，在制备A2MF6时均使用氢氟酸，而氢氟酸是一种腐蚀性强、毒性大的化学试剂，过量使用会造成严重的环境污染问题。因此如何降低氢氟酸的使用量，获得高效的氟化物红色发光材料具有重要的研究意义和应用前景。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. Typically, a large amount of hydrofluoric acid is used to prepare the Mn 4+ doped fluoride red luminescent material. For example, 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. In addition, 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. However, 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.

发明内容Summary of the invention

【技术问题】【technical problem】

本发明的目的在于提供一种在不使用氢氟酸的情况下制备蓝光激发的红色发光材料的方法。It is an object of the present invention to provide a method of preparing a blue-excited red luminescent material without the use of hydrofluoric acid.

【技术方案】【Technical solutions】

本发明的示例性实施例公开了一种制备蓝光激发的红色发光材料的方 法，所述红色发光材料的化学组成为A2X1-yF6:yMn4+，其中，A选自于碱金属元素中的至少一种；X选自于Ti、Si、Ge和Zr中的至少一种；y表示Mn4+离子相对于X4+离子所占的摩尔百分比系数，0<y≤0.10；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;

所述方法包括：将含有X的基质材料与反应溶剂混合,以得到第一混合溶液，其中，反应溶剂包括甲酸、乙酸和氟乙酸中的至少一种与无水乙醇的混合物或者甲酸、乙酸和氟乙酸中的至少一种；将Mn4+的氟化物加入到第一混合溶液，以得到第二混合溶液；将A的氟化物加入到第二混合溶液以得到沉淀物，从而得到红色发光材料。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 .

根据本发明的示例性实施例，含有X的基质材料可以包括六氟硅酸水溶液、六氟钛酸水溶液、六氟锆酸水溶液和六氟锗酸铵中的至少一种。According to an exemplary embodiment of the present invention, 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.

根据本发明的示例性实施例，六氟硅酸水溶液、六氟钛酸水溶液或六氟锆酸水溶液的质量百分比可以为30％-50％。According to an exemplary embodiment of the present invention, 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%.

根据本发明的示例性实施例，甲酸、乙酸和氟乙酸中的至少一种与无水乙醇的体积比可以为1-100:1。According to an exemplary embodiment of the present invention, 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.

根据本发明的示例性实施例，Mn4+的氟化物可以包括六氟锰酸钾和六氟锰酸钠中的一种。According to an exemplary embodiment of the present invention, the fluoride of Mn 4+ may include one of potassium hexafluoromanganate and sodium hexafluoromanganate.

根据本发明的示例性实施例，A的氟化物可以包括氟化钠、氟化钾、氟化铷和氟化铯中的至少一种。According to an exemplary embodiment of the present invention, the fluoride of A may include at least one of sodium fluoride, potassium fluoride, cesium fluoride, and cesium fluoride.

根据本发明的示例性实施例，将含有X的基质材料与反应溶剂混合的步骤可以包括：在室温条件下将含有X的基质材料与反应溶剂混合并搅拌均匀，以得到第一混合溶液。According to an exemplary embodiment of the present invention, 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.

根据本发明的示例性实施例，将Mn4+的氟化物加入到第一混合溶液的步骤可以包括：在将Mn4+的氟化物加入到第一混合物后搅拌20min～60min，以得到第二混合溶液。According to an exemplary embodiment of the present invention, 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.

根据本发明的示例性实施例，将A的氟化物加入到第二混合溶液的步骤可以包括：将A的氟化物加入到第二混合溶液后搅拌1小时-12小时，以得到沉淀物。According to an exemplary embodiment of the present invention, 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.

根据本发明的示例性实施例，所述方法还可以包括：对沉淀物清洗并干燥，从而得到红色发光材料。According to an exemplary embodiment of the present invention, the method may further include: washing the precipitate and drying to obtain a red luminescent material.

【技术效果】[Technical effect]

根据本发明的方法，在不使用氢氟酸的情况下能够制备蓝光激发的红 色发光材料，因此本发明的方法不会对环境污染造成影响。According to the method of the present invention, blue-excited red can be prepared without using hydrofluoric acid A luminescent material, so the method of the invention does not affect environmental pollution.

此外，根据本发明的方法，利用甲酸、乙酸和氟乙酸中的至少一种与无水乙醇的混合物或者甲酸、乙酸和氟乙酸中的至少一种作为反应溶剂制备得到的红色发光材料的形貌均一。Further, according to the method of the present invention, 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.

此外，根据本发明的方法制备过程简单、操作方便、适用于工业化大规模生产。In addition, the preparation method according to the invention is simple in preparation, convenient in operation, and suitable for industrialized mass production.

此外，根据本发明的方法制备得到的红色发光材料在蓝光激发下具有很强的红光发射峰(例如，发射峰位于627nm左右或632nm左右)、发光效率高、色纯度好；而且所得到的红色发光材料的发射光谱色坐标值接近于理想红光的色坐标值：x＝0.67，y＝0.33。In addition, 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 around 627 nm or about 632 nm), has high luminous efficiency, and good color purity; and the obtained The emission spectral color coordinate value of the red luminescent material is close to the color coordinate value of the ideal red light: x=0.67, y=0.33.

附图说明DRAWINGS

图1是根据本发明的示例性实施例的制备红色发光材料的方法的流程图；1 is a flow chart of a method of preparing a red luminescent material, in accordance with an exemplary embodiment of the present invention;

图2为本发明的实施例1得到的Na2TiF6:Mn4+的XRD衍射图；2 is an XRD diffraction pattern of Na 2 TiF 6 :Mn 4+ obtained in Example 1 of the present invention;

图3为本发明的实施例1得到的Na2TiF6:Mn4+的室温激发光谱(监测波长为627nm)和发射光谱(激发波长为460nm)的图；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;

图4为本发明的实施例1得到的Na2TiF6:Mn4+与蓝光LED芯片所制作成的LED器件在20mA电流激发下的电致发光光谱图；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;

图5为本发明的实施例2得到的Na2SiF6:Mn4+的XRD衍射图；Figure 5 is an XRD diffraction pattern of Na 2 SiF 6 :Mn 4+ obtained in Example 2 of the present invention;

图6为本发明的实施例2得到的Na2SiF6:Mn4+的室温激发光谱(监测波长为627nm)和发射光谱(激发波长为460nm)的图；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;

图7为本发明的实施例2得到的Na2SiF6:Mn4+与蓝光LED芯片所制作成的LED器件在20mA电流激发下的电致发光光谱图；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;

图8为本发明的实施例3得到的K2TiF6:Mn4+的XRD衍射图；Figure 8 is an XRD diffraction pattern of K 2 TiF 6 :Mn 4+ obtained in Example 3 of the present invention;

图9为本发明的实施例3得到的K2TiF6:Mn4+的室温激发光谱(监测波长为632nm)和发射光谱(激发波长为460nm)的图；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;

图10为本发明的实施例3得到的K2TiF6:Mn4+与蓝光LED芯片所制作成的LED器件在20mA电流激发下的电致发光光谱图；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;

图11为本发明的实施例4得到的K2GeF6:Mn4+的XRD衍射图；Figure 11 is an XRD diffraction pattern of K 2 GeF 6 :Mn 4+ obtained in Example 4 of the present invention;

图12为本发明的实施例4得到的K2GeF6:Mn4+的室温激发光谱(监测波 长为631nm)和发射光谱(激发波长为460nm)的图；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;

图13为本发明的实施例4得到的K2GeF6:Mn4+与蓝光LED芯片所制作成的LED器件在20mA电流激发下的电致发光光谱图；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;

图14为本发明的实施例5得到的Rb2TiF6:Mn4+的XRD衍射图；Figure 14 is an XRD diffraction pattern of Rb 2 TiF 6 :Mn 4+ obtained in Example 5 of the present invention;

图15为本发明的实施例5得到的Rb2TiF6:Mn4+的室温激发光谱(监测波长为631nm)和发射光谱(激发波长为465nm)的图；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;

图16为本发明的实施例5得到的Rb2TiF6:Mn4+与蓝光LED芯片所制作成的LED器件在20mA电流激发下的电致发光光谱图；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;

图17为本发明的实施例6得到的Cs2ZrF6:Mn4+的XRD衍射图；Figure 17 is an XRD diffraction pattern of Cs 2 ZrF 6 :Mn 4+ obtained in Example 6 of the present invention;

图18为本发明的实施例6得到的Cs2ZrF6:Mn4+的室温激发光谱(监测波长为630nm)和发射光谱(激发波长为480nm)的图；以及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;

图19为本发明的实施例6得到的Cs2ZrF6:Mn4+与蓝光LED芯片所制作成的LED器件在20mA电流激发下的电致发光光谱图。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.

具体实施方式detailed description

以下结合示例性实施例，进一步详细描述本发明的原理，以使本发明的技术解决方案更加清晰。The principles of the present invention are described in further detail below in conjunction with the exemplary embodiments in order to provide a

在现有技术中，通过会使用氢氟酸作为反应溶剂来制备红色发光材料，而大量使用氢氟酸会对环境造成污染。基于此，本发明提出一种在不使用氢氟酸的情况下制备红色发光材料的方法。In the prior art, 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.

根据本发明的示例性实施例提供制备红色发光材料的方法，其中，红色发光材料的化学组成可以由式1表示：A method of preparing a red luminescent material according to an exemplary embodiment of the present invention, wherein a chemical composition of the red luminescent material may be represented by Formula 1:

A2X1-yF6:yMn4+             式1A 2 X 1-y F 6 : yMn 4+ formula 1

其中，在式1中，A选自于碱金属元素中的至少一种；X选自于Ti、Si、Ge和Zr中的至少一种；y表示Mn4+离子相对于X4+离子所占的摩尔百分比系数，0<y≤0.10。Wherein, in Formula 1, 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. The molar percentage factor, 0 < y ≤ 0.10.

在本发明的示例性实施例中，A可以选自于Na、K、Rb和Cs中的至少一种。可选择地，A可以是Na和/或K。In an exemplary embodiment of the invention, A may be selected from at least one of Na, K, Rb, and Cs. Alternatively, A may be Na and/or K.

在本发明的示例性实施例中，X可以选自于Ti、Si、Ge和Zr中的至少一种的四价元素。可选择地，X可以是Si或Ti。In an exemplary embodiment of the invention, X may be selected from a tetravalent element of at least one of Ti, Si, Ge, and Zr. Alternatively, X may be Si or Ti.

在本发明中，红色发光材料具有A2X1-yF6中的X组分部分地被Mn4+所 代替的结构，所以这样的红色发光材料可以被称为Mn-活化的氟化物红色发光材料。根据本发明的红色发光材料在蓝光激发下具有很强的红光发射峰(例如，发射峰位于627nm左右或632nm左右)、发光效率高；而且所得到的红色发光材料的发射光谱色坐标值接近于理想红光的色坐标值：x＝0.67，y＝0.33。In the present invention, 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. The color coordinate values of the ideal red light: x=0.67, y=0.33.

现在，将在下文中参照图1详细描述制备蓝光激发的红色发光材料的方法。Now, a method of preparing a blue-excited red luminescent material will be described in detail below with reference to FIG.

图1是根据本发明的示例性实施例的制备蓝光激发的红色发光材料的方法的流程图。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.

参照图1，根据本发明的示例性实施例的制备蓝光激发的红色发光材料的方法包括：将含有X的基质材料与反应溶剂混合,以得到第一混合溶液(S100)；将Mn4+的氟化物加入到第一混合溶液，以得到第二混合溶液(S200)；将A的氟化物加入到第二混合溶液，以得到沉淀物(S300)；对沉淀物清洗并干燥，以得到红色发光材料(S400)。Referring to FIG. 1, a method of preparing a blue-excited red luminescent material according to an exemplary embodiment of the present invention 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).

在将含有X的基质材料与反应溶剂混合(S100)中，在室温条件下将含有X的基质材料与反应溶剂混合并搅拌均匀，以得到第一混合溶液。这里，X可以与上述描述的X相同，将不在此进行赘述。In the case where 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. Here, X may be the same as X described above, and will not be described herein.

在本发明的示例性实施例中，含有X的基质材料可以包括六氟硅酸水溶液、六氟钛酸水溶液、六氟锆酸水溶液和六氟锗酸铵中的至少一种。此外，在本发明的示例性实施例中，六氟硅酸水溶液、六氟钛酸水溶液或六氟锆酸水溶液的质量百分比可以为30％-50％。在本发明的非限制性实施例中，在使用六氟锗酸铵时，可以将六氟锗酸铵直接与反应溶剂混合。In an exemplary embodiment of the present invention, 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. Further, in an exemplary embodiment of the present invention, 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%. In a non-limiting embodiment of the invention, ammonium hexafluoroantimonate may be directly mixed with the reaction solvent when ammonium hexafluoroantimonate is used.

在本发明的非限制性实施例中，含有X的基质材料与的比例关系不受具体限制，反应溶剂可以包括能够完全溶解含有X的基质材料的任何适合的量。In a non-limiting embodiment of the invention, 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.

在本发明的示例性实施例中，反应溶剂可以包括甲酸、乙酸和氟乙酸中的至少一种与无水乙醇的混合物或者甲酸、乙酸和氟乙酸中的至少一种。可选择地，反应溶剂可以包括甲酸与无水乙醇的混合物、乙酸与无水乙醇的混合物、氟乙酸与无水乙醇的混合物、甲酸和乙酸与无水乙醇的混合物、乙酸和氟乙酸与无水乙醇的混合物，或者甲酸和氟乙酸与无水乙醇的混合物。In an exemplary embodiment of the present invention, 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. Alternatively, 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.

在本发明的示例性实施例中，甲酸、乙酸和氟乙酸中的至少一种与无水乙醇的体积比可以为1-100:1。可选择地，可以为5-90:1、10-80:1、20-70:1、 30-60:1或40-50:1，或上述给出的数值限定的任意范围内，例如，可以为1-10:1。In an exemplary embodiment of the present invention, 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.

在本发明中，通过利用甲酸、乙酸和氟乙酸中的至少一种与无水乙醇的混合物或者甲酸、乙酸和氟乙酸中的至少一种代替氢氟酸作为反应溶剂，能够降低对环境的污染。In the present invention, 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. .

在将Mn4+的氟化物加入到第一混合溶液(S200)中，在将Mn4+的氟化物加入到第一混合物后搅拌20min～60min，以得到第二混合溶液。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.

在本发明的示例性实施例中，Mn4+的氟化物可以包括六氟锰酸钾和六氟锰酸钠中的一种。In an exemplary embodiment of the invention, the fluoride of Mn 4+ may include one of potassium hexafluoromanganate and sodium hexafluoromanganate.

在本发明中，在六氟锰酸钾和六氟锰酸钠中的一种加入到第一混合溶液中后，Mn4+与第一混合溶液中X4+进行离子交换。在本发明的示例性实施例中，Mn4+是作为发光中心，它的含量直接影响样品的发光效率，含量过低，发光效率过低；含量过高，也会导致浓度猝灭现象发生，从而也会降低样品的发光效率，因此需要调控发光材料中Mn4+的含量。在本发明中，Mn4+与X4+摩尔比为0.01-0.1:1。In the present invention, one of manganese and potassium hexafluorophosphate, sodium hexafluorophosphate manganese added to the first mixed solution, Mn 4+ first mixed solution X 4+ ion exchange. In an exemplary embodiment of the present invention, 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. In the present invention, the molar ratio of Mn 4+ to X 4+ is from 0.01 to 0.1:1.

将A的氟化物加入到第二混合溶液(S300)中，将A的氟化物加入到第二混合溶液后搅拌1小时-12小时，以得到沉淀物。这里，A可以与上述描述的A相同，将不在此进行赘述。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. Here, A may be the same as A described above, and will not be described herein.

在本发明的示例性实施例中，A的氟化物可以包括氟化钠、氟化钾、氟化铷和氟化铯中的至少一种。In an exemplary embodiment of the present invention, the fluoride of A may include at least one of sodium fluoride, potassium fluoride, cesium fluoride, and cesium fluoride.

在本发明中，向第二混合溶液中加入A的氟化物能够使第二混合溶液沉淀，从而得到红色发光材料。In the present invention, 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.

在本发明的示例性实施例中，A的氟化物与含有X的基质材料的摩尔比可以为0.5-10:1，可选择地，可以为1-9:1、2-8:1、3-6:1或4-5:1，或上述给出的数值限定的任意范围内，例如，可以为2-7:1。如果A的氟化物用量过低，则样品很难沉淀出来；如果A的氟化物用量过高，则会出现其它杂相物质生成，导致样品物相不纯。In an exemplary embodiment of the present invention, 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.

在本发明的示例性实并干燥(S400)中，可以利用无水甲醇或无水乙醇对沉淀物进行清洗，并在真空中干燥10h-30h，从而得到蓝光激发的红色发光材料。In an exemplary solid drying (S400) of the present invention, 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.

在本发明的制备蓝光激发的红色发光材料的方法中，各步骤均在室温 下进行。In the method for preparing a blue-excited red luminescent material of the present invention, each step is at room temperature Go on.

此外，在不使用氢氟酸的情况下采用离子交换-共沉淀法得到了蓝光激发的红色发光材料。Further, a blue light-excited red luminescent material was obtained by ion exchange-coprecipitation without using hydrofluoric acid.

在本发明的非限制性实施例中，蓝光的激发波长可以为420nm-480nm。In a non-limiting embodiment of the invention, the excitation wavelength of blue light may range from 420 nm to 480 nm.

根据本发明的制备蓝光激发的红色发光材料的方法可以获得如下效果中的至少一个：The method of preparing a blue-excited red luminescent material according to the present invention can obtain at least one of the following effects:

1、根据本发明的方法，在不使用氢氟酸的情况下能够制备蓝光激发的红色发光材料，因此本发明的方法不会对环境污染造成影响。1. According to the method of the present invention, 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.

2、根据本发明的方法，利用甲酸、乙酸和氟乙酸中的至少一种与无水乙醇的混合物或者甲酸、乙酸和氟乙酸中的至少一种作为反应溶剂制备得到红色发光材料的形貌均一。2. According to the method of the present invention, 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. .

3、根据本发明的方法制备过程简单、操作方便、适用于工业化大规模生产。3. The method according to the invention has simple preparation process, convenient operation and is suitable for industrial large-scale production.

4、根据本发明的方法制备得到的红色发光材料在蓝光激发下具有很强的红光发射峰(例如，发射峰位于627nm左右或632nm左右)、发光效率高、色纯度好；而且所得到的红色发光材料的发射光谱色坐标值接近于理想红光的色坐标值：x＝0.67，y＝0.33。4. 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 around 627 nm or about 632 nm), has high luminous efficiency, and good color purity; and the obtained The emission spectral color coordinate value of the red luminescent material is close to the color coordinate value of the ideal red light: x=0.67, y=0.33.

下面结合实施例对根据本发明的制备蓝光激发的红色发光材料的方法进行更详细的描述。The method of preparing a blue-excited red luminescent material according to the present invention will now be described in more detail with reference to the examples.

实施例1：Example 1:

将2.5ml 50％六氟钛酸水溶液溶于18ml甲酸和2ml无水乙醇的反应溶剂中；然后加入0.12g六氟锰酸钠，搅拌20分钟；最后加入1.05g氟化钠继续搅拌2小时。所得沉淀物用无水甲醇清洗数次，并于真空干燥箱中干燥24小时，从而得到红色发光材料Na2TiF6:Mn4+；此外，通过原子吸收光谱测得该样品中Mn4+为0.049mol。检测结果示出在图2至图4中。2.5 ml of a 50% aqueous solution of hexafluorotitanate was dissolved in a reaction solvent of 18 ml of formic acid and 2 ml of absolute ethanol; then 0.12 g of sodium hexafluoromanganate was added and stirred for 20 minutes; finally, 1.05 g of sodium fluoride was added and stirring was continued for 2 hours. The resulting precipitate was washed several times with anhydrous methanol, and dried in a vacuum oven for 24 hours to obtain a red luminescent material Na 2 TiF 6: Mn 4+; Further, by atomic absorption spectroscopy to obtain the sample is Mn 4+ 0.049 mol. The results of the detection are shown in Figures 2 to 4.

图2为本发明的实施例1得到的Na2TiF6:Mn4+的XRD衍射图。图3为本发明的实施例1得到的Na2TiF6:Mn4+的室温激发光谱(监测波长为627nm)和发射光谱(激发波长为460nm)的图。图4为本发明的实施例1得到的Na2TiF6:Mn4+与蓝光LED芯片所制作成的LED器件在20mA电流激发下的电致发光光谱图。 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.

如图2所示，该实施例1得到的Na2TiF6:Mn4+与标准卡片JCPDS 15-0581(Na2TiF6)相对照，两者完全一致，没有观察到任何杂相的衍射峰，这表明制备得到的红色发光材料具有单一晶相。As shown in Fig. 2, 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.

如图3所示，得到的红色发光材料在紫外光区和蓝色光区均具有很强的宽带激发。在460nm光激发下，红色发光材料的发射波长以红光发射波长为主，发射波长在627nm左右，这对应于Mn4+的2Eg-4A2g跃迁。As shown in FIG. 3, the obtained red luminescent material has strong broadband excitation in both the ultraviolet region and the blue region. Under the excitation of 460 nm light, 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+ .

图4是在将得到的红色发光材料涂布在蓝光LED芯片上的LED器件后，在20mA的电流下对其进行激发所得到的光谱图。从图4中可以看出，460nm左右的发射峰为LED芯片所发出的蓝光，本发明得到的红色发光材料的发射峰位于红光区域，其最强发射峰位于627nm处。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. As can be seen from FIG. 4, 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.

实施例2：Example 2:

将5ml 30％六氟硅酸水溶液溶于15g氟乙酸和5ml无水乙醇的反应溶剂中；然后加入0.12g六氟锰酸钠，搅拌30分钟；最后加入1.05g氟化钠继续搅拌4小时。所得沉淀物用无水甲醇清洗数次，并于真空干燥箱中干燥24小时，从而得到红色发光材料Na2SiF6:Mn4+；此外，通过原子吸收光谱测得该样品中Mn4+为0.041mol。检测结果示出在图5至图7中。5 ml of a 30% aqueous solution of hexafluorosilicic acid was dissolved in a reaction solvent of 15 g of fluoroacetic acid and 5 ml of absolute ethanol; then 0.12 g of sodium hexafluoromanganate was added and stirred for 30 minutes; finally, 1.05 g of sodium fluoride was added and stirring was continued for 4 hours. The resulting precipitate was washed several times with anhydrous methanol, and dried in a vacuum oven for 24 hours to obtain a red luminescent material Na 2 SiF 6: Mn 4+; Further, by atomic absorption spectroscopy to obtain the sample is Mn 4+ 0.041 mol. The results of the detection are shown in Figs. 5 to 7.

图5为本发明的实施例2得到的Na2SiF6:Mn4+的XRD衍射图。图6为本发明的实施例2得到的Na2SiF6:Mn4+的室温激发光谱(监测波长为627nm)和发射光谱(激发波长为460nm)的图。图7为本发明的实施例2得到的Na2SiF6:Mn4+与蓝光LED芯片所制作成的LED器件在20mA电流激发下的电致发光光谱图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.

如图5所示，该实施例2得到的Na2SiF6:Mn4+与标准卡片JCPDS 33-1280相对照，两者完全一致，没有观察到任何杂相的衍射峰，这表明制备得到的红色发光材料具有单一晶相。As shown in Fig. 5, 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.

如图6所示，得到的红色发光材料在紫外光区和蓝色光区均具有很强的宽带激发。在460nm光激发下，在460nm光激发下，红色发光材料的发射波长以红光发射波长为主，发射波长在627nm左右，这对应于Mn4+的2Eg-4A2g跃迁。As shown in Fig. 6, the obtained red luminescent material has strong broadband excitation in both the ultraviolet region and the blue region. Under the excitation of 460 nm light, under the excitation of 460 nm light, 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+ .

图7是在将得到的红色发光材料涂布在蓝光LED芯片上的LED器件后，在20mA的电流下对其进行激发所得到的光谱图。从图7中可以看出，460nm左右的发射峰为LED芯片所发出的蓝光，本发明得到的红色发光材料的发射 峰位于红光区域，其最强发射峰位于627nm处。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.

实施例3：Example 3:

将2.5ml 50％六氟钛酸水溶液溶于18ml乙酸和2ml无水乙醇的反应溶剂中；然后加入0.15g六氟锰酸钾，搅拌40分钟；最后加入1.52g氟化钾继续搅拌1小时。所得沉淀物用无水甲醇清洗数次，并于真空干燥箱中干燥24小时，从而得到红色发光材料K2TiF6:Mn4+；此外，通过原子吸收光谱测得该样品中Mn4+为0.045mol。检测结果示出在图8至图10中。2.5 ml of a 50% aqueous solution of hexafluorotitanate was dissolved in a reaction solvent of 18 ml of acetic acid and 2 ml of absolute ethanol; then 0.15 g of potassium hexafluoromanganate was added and stirred for 40 minutes; finally, 1.52 g of potassium fluoride was added and stirring was continued for 1 hour. The resulting precipitate was washed several times with anhydrous methanol, and dried in a vacuum oven for 24 hours to obtain a red light emitting material K 2 TiF 6: Mn 4+; Further, by atomic absorption spectroscopy to obtain the sample is Mn 4+ 0.045 mol. The results of the detection are shown in Figs. 8 to 10.

图8为本发明的实施例3得到的K2TiF6:Mn4+的XRD衍射图。图9为本发明的实施例3得到的K2TiF6:Mn4+的室温激发光谱(监测波长为632nm)和发射光谱(激发波长为460nm)的图。图10为本发明的实施例3得到的K2TiF6:Mn4+与蓝光LED芯片所制作成的LED器件在20mA电流激发下的电致发光光谱图。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.

如图8所示，该实施例3得到的K2TiF6:Mn4+与标准卡片JCPDS 08-0488相对照，两者完全一致，没有观察到任何杂相的衍射峰，这表明制备得到的红色发光材料具有单一晶相，。As shown in Fig. 8, 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.

如图9所示，得到的红色发光材料在紫外光区和蓝色光区均具有很强的宽带激发。在460nm光激发下，红色发光材料的发射波长以红光发射波长为主，发射波长在632nm左右，这对应于Mn4+的2Eg-4A2g跃迁。As shown in FIG. 9, the obtained red luminescent material has strong broadband excitation in both the ultraviolet region and the blue region. Under the excitation of 460 nm light, 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+ .

图10是在将得到的红色发光材料涂布在蓝光LED芯片上的LED器件后，在20mA的电流下对其进行激发所得到的光谱图。从图10中可以看出，460nm左右的发射峰为LED芯片所发出的蓝光，本发明得到的红色发光材料的发射峰位于红光区域，其最强发射峰位于632nm处。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. As can be seen from FIG. 10, 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.

实施例4：Example 4:

将2.2lg六氟锗酸铵溶于10g氟乙酸和10ml无水乙醇的反应溶剂中；然后加入0.15g六氟锰酸钾，搅拌60分钟；最后加入2.52g氟化钾继续搅拌12小时。所得沉淀物用无水甲醇清洗数次，并于真空干燥箱中干燥24小时，从而得到红色发光材料K2GeF6:Mn4+；此外，通过原子吸收光谱测得该样品中Mn4+为0.042mol。检测结果示出在图11至图13中。2.2 g of ammonium hexafluoroantimonate was dissolved in a reaction solvent of 10 g of fluoroacetic acid and 10 ml of absolute ethanol; then 0.15 g of potassium hexafluoromanganate was added and stirred for 60 minutes; finally, 2.52 g of potassium fluoride was added and stirring was continued for 12 hours. The resulting precipitate was washed several times with anhydrous methanol, and dried in a vacuum oven for 24 hours to obtain a red light emitting material K 2 GeF 6: Mn 4+; Further, by atomic absorption spectroscopy to obtain the sample is Mn 4+ 0.042 mol. The detection results are shown in FIGS. 11 to 13.

图11为本发明的实施例4得到的K2GeF6:Mn4+的XRD衍射图。图12为本发明的实施例4得到的K2GeF6:Mn4+的室温激发光谱(监测波长为631nm)和发射光谱(激发波长为460nm)的图。图13为本发明的实施例4得到的 K2GeF6:Mn4+与蓝光LED芯片所制作成的LED器件在20mA电流激发下的电致发光光谱图。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.

如图11所示，该实施例4得到的K2GeF6:Mn4+与标准卡片JCPDS 07-0241相对照，两者完全一致，没有观察到任何杂相的衍射峰，这表明制备得到的红色发光材料具有单一晶相。As shown in Fig. 11, 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.

如图12所示，得到的红色发光材料在紫外光区和蓝色光区均具有很强的宽带激发。在460nm光激发下，在460nm光激发下，红色发光材料的发射波长以红光发射波长为主，发射波长在631nm左右，这对应于Mn4+的2Eg-4A2g跃迁。As shown in FIG. 12, the obtained red luminescent material has strong broadband excitation in both the ultraviolet region and the blue region. Under the excitation of 460 nm light, 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+ .

图13是在将得到的红色发光材料涂布在蓝光LED芯片上的LED器件后，在20mA的电流下对其进行激发所得到的光谱图。从图13中可以看出，460nm左右的发射峰为LED芯片所发出的蓝光，本发明得到的红色发光材料的发射峰位于红光区域，其最强发射峰位于631nm处。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. As can be seen from FIG. 13, 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.

实施例5：Example 5:

将2.5ml 50％六氟钛酸水溶液溶于15ml甲酸和5ml无水乙醇的反应溶剂中；然后加入0.12g六氟锰酸钾，搅拌30分钟；最后加入2.58g氟化铷继续搅拌3小时。所得沉淀物用无水甲醇清洗数次，并于真空干燥箱中干燥24小时，从而得到红色发光材料Rb2TiF6:Mn4+；此外，通过原子吸收光谱测得该样品中Mn4+为0.052mol。检测结果示出在图14至图16中。2.5 ml of a 50% aqueous solution of hexafluorotitanate was dissolved in a reaction solvent of 15 ml of formic acid and 5 ml of absolute ethanol; then 0.12 g of potassium hexafluoromanganate was added and stirred for 30 minutes; finally, 2.58 g of cesium fluoride was added and stirring was continued for 3 hours. The resulting precipitate was washed several times with anhydrous methanol, and dried in a vacuum oven for 24 hours to obtain a red luminescent material Rb 2 TiF 6: Mn 4+; Further, by atomic absorption spectroscopy to obtain the sample is Mn 4+ 0.052 mol. The test results are shown in Figs. 14 to 16.

图14为本发明的实施例5得到的Rb2TiF6:Mn4+的XRD衍射图。图15为本发明的实施例5得到的Rb2TiF6:Mn4+的室温激发光谱(监测波长为631nm)和发射光谱(激发波长为465nm)的图。图16为本发明的实施例5得到的Rb2TiF6:Mn4+与蓝光LED芯片所制作成的LED器件在20mA电流激发下的电致发光光谱图。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.

如图14所示，该实施例5得到的Rb2TiF6:Mn4+与标准卡片JCPDS 51-0611相对照，两者完全一致，没有观察到任何杂相的衍射峰，这表明制备得到的红色发光材料具有单一晶相。As shown in Fig. 14, 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.

如图15所示，得到的红色发光材料在紫外光区和蓝色光区均具有很强的宽带激发。在465nm光激发下，在460nm光激发下，红色发光材料的发射波长以红光发射波长为主，发射波长在631nm左右，这对应于Mn4+的2Eg-4A2g跃迁。 As shown in Fig. 15, the obtained red luminescent material has strong broadband excitation in both the ultraviolet region and the blue region. Under the excitation of 465 nm light, under the excitation of 460 nm light, 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+ .

图16是在将得到的红色发光材料涂布在蓝光LED芯片上的LED器件后，在20mA的电流下对其进行激发所得到的光谱图。从图16中可以看出，465nm左右的发射峰为LED芯片所发出的蓝光，本发明得到的红色发光材料的发射峰位于红光区域，其最强发射峰位于631nm处。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.

实施例6：Example 6

将3.9ml 45％六氟锆酸水溶液溶于15ml甲酸和5ml无水乙醇的反应溶剂中；然后加入0.11g六氟锰酸钾，搅拌30分钟；最后加入3.88g氟化铯继续搅拌8小时。所得沉淀物用无水甲醇清洗数次，并于真空干燥箱中干燥24小时，从而得到红色发光材料Cs2ZrF6:Mn4+；此外，通过原子吸收光谱测得该样品中Mn4+为0.056mol。检测结果示出在图17至图19中。3.9 ml of a 45% aqueous solution of hexafluorozirconate was dissolved in a reaction solvent of 15 ml of formic acid and 5 ml of absolute ethanol; then 0.11 g of potassium hexafluoromanganate was added and stirred for 30 minutes; finally, 3.88 g of cesium fluoride was added and stirring was continued for 8 hours. The resulting precipitate was washed several times with anhydrous methanol, and dried in a vacuum oven for 24 hours to obtain a red luminescent material Cs 2 ZrF 6: Mn 4+; Further, by atomic absorption spectroscopy to obtain the sample is Mn 4+ 0.056 mol. The results of the detection are shown in Figs. 17 to 19.

图17为本发明的实施例6得到的Cs2ZrF6:Mn4+的XRD衍射图。图18为本发明的实施例6得到的Cs2ZrF6:Mn4+的室温激发光谱(监测波长为630nm)和发射光谱(激发波长为480nm)的图。图19为本发明的实施例6得到的Cs2ZrF6:Mn4+与蓝光LED芯片所制作成的LED器件在20mA电流激发下的电致发光光谱图。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.

如图17所示，该实施例6得到的Cs2ZrF6:Mn4+与标准卡片JCPDS 74-0173相对照，两者完全一致，没有观察到任何杂相的衍射峰，这表明制备得到的红色发光材料具有单一晶相。As shown in Fig. 17, 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.

如图18所示，得到的红色发光材料在紫外光区和蓝色光区均具有很强的宽带激发。在480nm光激发下，在460nm光激发下，红色发光材料的发射波长以红光发射波长为主，发射波长在630nm左右，这对应于Mn4+的2Eg-4A2g跃迁。As shown in Fig. 18, the obtained red luminescent material has a strong broadband excitation in both the ultraviolet region and the blue region. Under the excitation of 480 nm light, under the excitation of 460 nm light, 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+ .

图19是在将得到的红色发光材料涂布在蓝光LED芯片上的LED器件后，在20mA的电流下对其进行激发所得到的光谱图。从图19中可以看出，460nm左右的发射峰为LED芯片所发出的蓝光，本发明得到的红色发光材料的发射峰位于红光区域，其最强发射峰位于630nm处。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. As can be seen from FIG. 19, 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.

综上所述，根据本发明的方法，利用甲酸、乙酸和氟乙酸中的至少一种与无水乙醇的混合物或者甲酸、乙酸和氟乙酸中的至少一种作为反应溶剂制备得到红色发光材料的形貌均一。此外，根据本发明的方法制备得到的红色发光材料在蓝光激发下具有很强的红光发射峰(例如，发射峰位于627nm左右或632nm左右)，发光效率高。 In summary, according to the method of the present invention, 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. In addition, 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.

虽然已经参照本发明的示例性实施例具体地示出并描述了本发明，但是本领域普通技术人员将理解，在不脱离如所附权利要求和它们的等同物所限定的本发明的精神和范围的情况下，可以在此做出形式和细节上的各种改变。应当仅仅在描述性的意义上而不是出于限制的目的来考虑实施例。因此，本发明的范围不是由本发明的具体实施方式来限定，而是由权利要求书来限定，该范围内的所有差异将被解释为包括在本发明中。 While the invention has been particularly shown and described with reference to the exemplary embodiments of the embodiments of the invention In the case of a range, various changes in form and detail can be made here. Embodiments should be considered only in a descriptive sense and not for purposes of limitation. Therefore, the scope of the invention is not intended to

Claims (10)

一种制备蓝光激发的红色发光材料的方法，所述红色发光材料的化学组成为A2X1-yF6:yMn4+，其中，A选自于碱金属元素中的至少一种；X选自于Ti、Si、Ge和Zr中的至少一种；y表示Mn4+离子相对于X4+离子所占的摩尔百分比系数，0<y≤0.10；A method for preparing a blue light-excited red light-emitting material, wherein the chemical composition of the red light-emitting material is A 2 X 1-y F 6 : yMn 4+ , wherein A is selected from at least one of alkali metal elements; 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; 所述方法包括如下步骤：The method includes the following steps: 将含有X的基质材料与反应溶剂混合,以得到第一混合溶液，其中，反应溶剂包括甲酸、乙酸和氟乙酸中的至少一种与无水乙醇的混合物或者甲酸、乙酸和氟乙酸中的至少一种；The matrix material containing X is mixed with a reaction solvent to obtain a first mixed solution, wherein the reaction solvent includes at least one of formic acid, acetic acid, and fluoroacetic acid and a mixture of absolute ethanol or at least of formic acid, acetic acid, and fluoroacetic acid. One type; 将Mn4+的氟化物加入到第一混合溶液，以得到第二混合溶液；以及Adding Mn 4+ fluoride to the first mixed solution to obtain a second mixed solution; 将A的氟化物加入到第二混合溶液以得到沉淀物，从而得到红色发光材料。Fluoride of A is added to the second mixed solution to obtain a precipitate, thereby obtaining a red luminescent material. 根据权利要求1所述的方法，其中，含有X的基质材料包括六氟硅酸水溶液、六氟钛酸水溶液、六氟锆酸水溶液和六氟锗酸铵中的至少一种。The method according to claim 1, wherein the matrix material containing X comprises at least one of an aqueous solution of hexafluorosilicic acid, an aqueous solution of hexafluorotitanate, an aqueous solution of hexafluorozirconate, and ammonium hexafluoroantimonate. 根据权利要求2所述的方法，其中，六氟硅酸水溶液、六氟钛酸水溶液或六氟锆酸水溶液的质量百分比为30％-50％。The method according to claim 2, wherein the aqueous solution of hexafluorosilicic acid, aqueous hexafluorotitanate or aqueous solution of hexafluorozirconate has a mass percentage of 30% to 50%. 根据权要求1所述的方法，其中，甲酸、乙酸和氟乙酸中的至少一种与无水乙醇的体积比为1-100:1。The method according to claim 1, wherein the volume ratio of at least one of formic acid, acetic acid and fluoroacetic acid to absolute ethanol is from 1 to 100:1. 根据权利要求1所述的方法，其中，Mn4+的氟化物包括六氟锰酸钾和六氟锰酸钠中的一种。The method according to claim 1, wherein the fluoride of Mn 4+ comprises one of potassium hexafluoromanganate and sodium hexafluoromanganate. 根据权利要求1所述的方法，其中，A的氟化物包括氟化钠、氟化钾、氟化铷和氟化铯中的至少一种。The method of claim 1 wherein the fluoride of A comprises at least one of sodium fluoride, potassium fluoride, cesium fluoride and cesium fluoride. 根据权利要求1所述的方法，其中，将含有X的基质材料与反应溶剂混合的步骤包括：在室温条件下将含有X的基质材料与反应溶剂混合并搅拌均匀，以得到第一混合溶液。The method according to claim 1, wherein the step of mixing the matrix material containing X with the reaction solvent comprises: mixing the matrix material containing X with a reaction solvent at room temperature and stirring uniformly to obtain a first mixed solution. 根据权利要求1所述的方法，其中，将Mn4+的氟化物加入到第一混合溶液的步骤包括：在将Mn4+的氟化物加入到第一混合物后搅拌20min～60min，以得到第二混合溶液。The method according to claim 1, wherein the step of adding the fluoride of Mn 4+ to the first mixed solution comprises: stirring the Mn 4+ fluoride after adding the first mixture to the first mixture for 20 minutes to 60 minutes to obtain the first Two mixed solutions. 根据权利要求1所述的方法，其中，将A的氟化物加入到第二混 合溶液的步骤包括：将A的氟化物加入到第二混合溶液后搅拌1小时-12小时，以得到沉淀物。The method of claim 1 wherein the fluoride of A is added to the second mixture The step of combining the solution includes: adding the fluoride of A to the second mixed solution, and stirring for 1 hour to 12 hours to obtain a precipitate. 根据权利要求1所述的方法，所述方法还包括：对沉淀物清洗并干燥，从而得到红色发光材料。 The method of claim 1 further comprising: washing the precipitate and drying to obtain a red luminescent material.
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