CN116970394A - Solid solution fluoride red fluorescent powder and preparation method and application thereof - Google Patents
Solid solution fluoride red fluorescent powder and preparation method and application thereof Download PDFInfo
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- 239000006104 solid solution Substances 0.000 title claims abstract description 71
- 239000000843 powder Substances 0.000 title claims abstract description 64
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 239000000243 solution Substances 0.000 claims abstract description 36
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002244 precipitate Substances 0.000 claims abstract description 14
- 238000006862 quantum yield reaction Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 7
- 230000002596 correlated effect Effects 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000009877 rendering Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 21
- 239000011248 coating agent Substances 0.000 abstract description 8
- 238000000576 coating method Methods 0.000 abstract description 8
- 238000004020 luminiscence type Methods 0.000 abstract description 8
- 239000011159 matrix material Substances 0.000 abstract description 8
- 230000003287 optical effect Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 2
- 239000011572 manganese Substances 0.000 description 90
- 238000003756 stirring Methods 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000875 corresponding effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- XPIIDKFHGDPTIY-UHFFFAOYSA-N F.F.F.P Chemical compound F.F.F.P XPIIDKFHGDPTIY-UHFFFAOYSA-N 0.000 description 1
- 229910001618 alkaline earth metal fluoride Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001194 electroluminescence spectrum Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/67—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals
- C09K11/674—Halogenides
- C09K11/675—Halogenides with alkali or alkaline earth metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
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Abstract
A solid solution fluoride red fluorescent powder and a preparation method thereof, wherein the chemical general formula of the solid solution fluorescent powder is A 2 Nb (1‑x) Ta x F 7 :Mn 4+ Wherein A is Li, na, K, rb or Cs, x is more than or equal to 0.1 and less than or equal to 0.9. The preparation method comprises the following steps: nb is set to 2 O 5 、Ta 2 O 5 Mixing with hydrofluoric acid solution, and reacting at high temperature to obtain a first solution; the first solution is mixed with K 2 MnF 6 After a period of reaction, KHF is added 2 Continuing the reaction until the reaction is finished; and collecting the precipitate, washing and drying to obtain the solid solution fluoride red fluorescent powder. The application adopts A 2 NbF 7 By adding Ta as a light-emitting matrix 5+ The solid solution doped with two same charges is formed, so that the moisture resistance of the fluorescent powder can be effectively improved, and the fluorescent powder is fundamentally prevented from being subjected to fluorescence after the coating modified material is failedThe powder has negative effects on chemical stability and luminescence property, can effectively enhance the optical properties of red emission peak intensity, fluorescence lifetime, quantum yield and the like of the fluorescent powder, and has wide application prospect.
Description
Technical Field
The application relates to the technical field of fluorescent powder materials for LEDs, in particular to a solid solution fluoride red fluorescent powder, a preparation method and application thereof.
Background
White Light Emitting Diodes (WLEDs), which are a fourth generation solid state lighting source gradually replace conventional incandescent and fluorescent lamps, become an indispensable part of life of people, and are widely used in various display fields such as lighting, liquid crystal display, and signage.
Non-rare earth element Mn 4+ Activated fluoride red phosphors have received high attention in recent years due to their strong absorption in the blue region, low phonon energy, high color purity, mild synthesis conditions, low cost, narrow band emission, and are considered one of the best red phosphor candidates for application in warm WLED devices.
Mn 4+ The weak moisture resistance of activated fluoride phosphors is one of the main reasons to inhibit their application to WLED. For example, in K 2 SiF 6 :Mn 4+ And K 2 TiF 6 :Mn 4+ The typical fluoride fluorescent material has the characteristic of poor moisture resistance, and [ MnF ] on the surface of fluorescent powder 6 ] 2- Can be easily hydrolyzed in water to generate MnO 2 ，MnO 2 Absorption of the generated excitation light and suppression of fluorescence lead to a decrease in fluorescence intensity. To reduce [ MnF ] 6 ] 2- The common strategy is mainly to coat the surface of the phosphor particles with an organic or inorganic coating. Patent CN112251219A discloses a wet-resistant fluoride red phosphor, which coats an alkaline earth metal fluoride waterproof layer on Mn 4+ Doping the surface of fluoride red fluorescent powder to improve Mn 4+ And the stability of the fluoride-doped red fluorescent powder in a high-humidity environment. Patent CN109423276A discloses an efficient and stable Mn 4+ Doped fluoride luminescent material, which utilizes A 2 MF 6 Compound coated A 2 MF 6 :Mn 4+ Fluoride phosphor avoiding Mn 4+ Degradation occurs when the material is directly contacted with the external environment.
However, although the strategy of coating the surface of the phosphor particles with an organic or inorganic coating can effectively improve the moisture resistance of the phosphor, such coating treatment method not only requires complicated experimental steps, but also the modified materials are easily decomposed at high temperature, resulting in unsatisfactory chemical stability of the phosphor. Furthermore, the surface passivation treatment may induce the matrix ions to participate in oxidation, thereby causing a color reaction, which negatively affects the luminous efficiency.
Disclosure of Invention
An object of the present application is to provide a solid solution fluoride red phosphor prepared by mixing a 2 NbF 7 :Mn 4+ Incorporating Ta therein 5+ Forming a solid solution of Nb 5+ And Ta 5+ The fluorescent powder has rigidity and structural diversity when doped in a certain proportion, thereby aiming at a luminous center Mn 4+ Protecting and effectively reducing [ MnF ] 6 ] 2- Is hydrolyzed to improve the moisture resistance of the fluorescent powder; in addition, compared with A 2 NbF 7 :Mn 4+ Or A 2 TaF 7 :Mn 4+ The mode of forming solid solution can also effectively improve the quantum yield, the variable-temperature luminescence performance and other luminescence performances of the fluorescent powder.
The above object of the present application is achieved by the following technical scheme:
a solid solution fluoride red fluorescent powder has a chemical formula of A 2 Nb (1-x) Ta x F 7 :Mn 4+ Wherein A is Li, na, K, rb or Cs, x is more than or equal to 0.1 and less than or equal to 0.9.
In the technical proposal, the fluoride red fluorescent powder is Nb 5+ And Ta 5+ The two ions with the same charge are doped together to form a solid solution. After the solid solution is formed, the local structure is modulated, has better rigidity and structural diversity, stabilizes Mn 4+ The existence form in the matrix further enhances the stability of the fluorescent powder in the aspect of moisture resistance, and reaches the moisture resistance water of the fluorescent powder coated by the organic or inorganic coatingAnd the problems of decomposition of the modified material at high temperature and the like are eliminated from the root.
At the same time Nb 5+ And Ta 5+ Is effective to increase Mn 4+ The degree of asymmetry of the local environment of the fluorescent powder is greatly improved, so that the quantum yield, the variable-temperature luminescence property and other luminescence properties of the fluorescent powder are enhanced. In the technical scheme, when x is more than or equal to 0.1 and less than or equal to 0.9, A is found through experiments 2 Nb (1-x) Ta x F 7 :Mn 4+ The sharp red emission peak intensity of (2) is higher than that of A 2 NbF 7 :Mn 4+ Or A 2 TaF 7 :Mn 4+ Obviously improves, when x is more than or equal to 0.5 and less than or equal to 0.7, A 2 Nb (1-x) Ta x F 7 :Mn 4+ The sharp red emission peak intensity of (A) is A 2 NbF 7 :Mn 4+ Or A 2 TaF 7 :Mn 4+ More than 1.5 times of the total number of the components. Meanwhile, when x is more than or equal to 0.1 and less than or equal to 0.9, A is 2 Nb (1-x) Ta x F 7 :Mn 4+ The fluorescence lifetime of (a) increases and decreases, and reaches a maximum at x=0.7, a 2 NbF 7 :Mn 4+ 1.35 times, A 2 TaF 7 :Mn 4+ 1.17 times of (2). Furthermore, when 0.1.ltoreq.x.ltoreq.0.9, A 2 Nb (1-x) Ta x F 7 :Mn 4+ The quantum yield of the product can reach 74.91 percent at most, which is obviously higher than that of A 2 NbF 7 :Mn 4+ Or A 2 TaF 7 :Mn 4+ 。
In one or more embodiments, a is Li, na, K, rb or Cs, preferably a is K.
It can be seen that at A 2 NbF 7 By adding Ta as a light-emitting matrix 5+ The method forms a solid solution doped with two same charges, can not only effectively improve the moisture resistance of the fluorescent powder and radically avoid negative effects of the coating modified material on the fluorescence powder chemical stability and the luminescence property after failure, but also effectively enhance the optical properties of the fluorescent powder such as red emission peak intensity, fluorescence lifetime, quantum yield and the like, and has wide application prospect.
In part, bestIn an alternative embodiment, A 2 Nb (1-x) Ta x F 7 :Mn 4+ X is more than or equal to 0.3 and less than or equal to 0.7. Experiments show that when x is more than or equal to 0.1 and less than or equal to 0.9, A 2 Nb (1-x) Ta x F 7 :Mn 4+ The red emission peak intensity, fluorescence lifetime and quantum yield of the fluorescent material show a change trend of increasing and then decreasing, so that x is preferably more than or equal to 0.3 and less than or equal to 0.7 to achieve better luminescence performance.
In some further preferred embodiments, A 2 Nb (1-x) Ta x F 7 :Mn 4+ X is more than or equal to 0.5 and less than or equal to 0.7.
Further, the solid solution fluoride red fluorescent powder is long rod-shaped particles, and the length of the solid solution fluoride red fluorescent powder is 20-50 mu m.
Further, the quantum yield of the solid solution fluoride red phosphor is greater than 60%.
The application also aims to provide a preparation method for preparing any solid solution fluoride red fluorescent powder, which has the advantages of simple and easily obtained raw materials, mild reaction conditions and short reaction time, is beneficial to industrial mass production, and the solid solution fluoride red fluorescent powder prepared by the method has long rod-shaped particles with the length of 20-50 mu m and has excellent optical performance.
The above object of the present application is achieved by the following technical scheme:
a preparation method for preparing any one of the solid solution fluoride red fluorescent powder, which specifically comprises the following steps:
nb is set to 2 O 5 、Ta 2 O 5 Mixing with hydrofluoric acid solution, and reacting at high temperature to obtain a first solution;
the first solution is mixed with K 2 MnF 6 After a period of reaction, KHF is added 2 Continuing the reaction until the reaction is finished;
and collecting the precipitate, washing and drying to obtain the solid solution fluoride red fluorescent powder.
In the technical scheme, nb is weighed according to a certain mass ratio, such as 9:1,7:3 and 5:5 2 O 5 、Ta 2 O 5 . Nb is set to 2 O 5 、Ta 2 O 5 Adding the mixture into HF solution to react at high temperature to obtain first solution. In a partially preferred embodiment, nb 2 O 5 、Ta 2 O 5 Mixing with hydrofluoric acid solution and reacting for 20-40 minutes at 100-120 ℃. In one or more embodiments, nb 2 O 5 、Ta 2 O 5 In a liner of a reaction kettle containing HF solution, placing the reaction kettle in an oven at 120 ℃ for 30 minutes, and reacting to obtain colorless transparent first solution. In one embodiment, the volume of hydrofluoric acid solution is 6mL. In one embodiment, the hydrofluoric acid solution has a mass percent concentration of 40%.
In the technical scheme, K is added into the first solution 2 MnF 6 After a period of reaction, KHF is added into the reaction system 2 The reaction was continued until the reaction was completed to obtain a precipitate. In a part of the preferred embodiments, the first solution is mixed with K 2 MnF 6 The reaction time is 10-15 minutes. In one or more embodiments, after the first solution has cooled to room temperature, a stoichiometric ratio of K is added 2 MnF 6 Continuously stirring for 10 min in the lining of the reaction kettle, and adding KHF with corresponding metering ratio 2 Stirring for 30 minutes. In a partially preferred embodiment, KHF is added 2 With the Nb 2 O 5 And Ta 2 O 5 The molar ratio of (2) is 10:1-12:1, namely KHF 2 With Nb 2 O 5 、Ta 2 O 5 The molar ratio of the sum to the KHF is 10:1 to 12:1, and further preferably 2 With the Nb 2 O 5 、Ta 2 O 5 The molar ratio of the sum is 12:1.
In the technical scheme, after the reaction is finished, collecting light pink precipitate, washing the precipitate with absolute ethyl alcohol for a plurality of times, and then drying the precipitate in an oven to obtain A 2 Nb (1-x) Ta x F 7 :Mn 4+ Solid solution fluoride red phosphor.
The preparation method provided by the technical scheme has the advantages of simple and easily obtained raw materials and proper synthesis temperature, can be suitable for practical production and application, and the synthesized solid solution fluorescent powder is long rod-shaped particles with the length of about 20-50 mu m, has excellent optical performance, higher luminous efficiency and has application value in practice.
It is still another object of the present application to provide a White Light Emitting Diode (WLED) having CIE chromaticity coordinates (0.3525,0.3587), correlated color temperature cct=4758K, and color rendering index ra=94.1, using any of the aforementioned solid solution fluoride red phosphors.
Mn synthesized by the application 4+ The activated solid solution fluoride red fluorescent powder has high color purity and low correlated color temperature, can be well matched with a blue light chip, presents the characteristics of broadband absorption and narrowband emission, and accords with the characteristics of warm white light.
Compared with the prior art, the application has the following advantages and beneficial effects:
1. the application adopts A 2 NbF 7 By adding Ta as a light-emitting matrix 5+ The method has the advantages that two solid solutions doped with the same charge can be formed, so that the moisture resistance of the fluorescent powder can be effectively improved, the negative influence of the coating modified material on the fluorescent powder chemical stability and the luminous performance after failure can be radically avoided, the optical properties such as the red emission peak intensity, the fluorescent life, the quantum yield and the like of the fluorescent powder can be effectively enhanced, and the method has a wide application prospect;
2. the application analyzes Nb in the solid solution fluorescent powder 5+ And Ta 5+ In the content ratio of A 2 Nb (1-x) Ta x F 7 :Mn 4+ X is more than or equal to 0.5 and less than or equal to 0.7, and the sharp red emission peak intensity is A 2 NbF 7 :Mn 4+ Or A 2 TaF 7 :Mn 4+ The quantum yield can reach 74.91% at most, the fluorescence lifetime is A 2 NbF 7 :Mn 4+ 1.35 times, A 2 TaF 7 :Mn 4+ 1.17 times of the total weight of the fluorescent lamp, the luminous performance is obviously improved;
3. the preparation method provided by the application has the advantages of simple and easily obtained raw materials, mild reaction conditions and short reaction time, is beneficial to industrial mass production, and the long rod-shaped particles with the length of 20-50 mu m of the solid solution fluoride red fluorescent powder prepared by the method have excellent optical performance;
4. the solid solution fluorescent powder provided by the application has high color purity and low correlated color temperature, and shows the characteristics of broadband absorption and narrowband emission after being matched with a blue light chip, wherein CIE chromaticity coordinates are (0.3525,0.3587), correlated color temperature CCT=4758K, and color rendering index Ra=94.1.
Drawings
The accompanying drawings, which are included to provide a further understanding of embodiments of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the principles of the application. In the drawings:
FIG. 1 is a block flow diagram of a method of preparation in an embodiment of the application;
FIG. 2 shows K in an embodiment of the application 2 Nb (1-x) Ta x F 7 X-ray diffraction pattern of solid solution material.
FIG. 3 shows K in an embodiment of the application 2 Nb (1-x) Ta x F 7 :Mn 4+ X-ray diffraction pattern of solid solution material.
FIG. 4 shows K in an embodiment of the application 2 Nb 0.3 Ta 0.7 F 7 :Mn 4+ Is a scanning electron microscope image of (1).
FIG. 5 shows K in an embodiment of the application 2 Nb (1-x) Ta x F 7 :Mn 4+ An emission spectrum of the solid solution material.
FIG. 6 shows K in an embodiment of the application 2 Nb 0.3 Ta 0.7 F 7 :Mn 4+ Is a CIE coordinate diagram of (c).
FIG. 7 shows K in an embodiment of the application 2 Nb (1-x) Ta x F 7 :Mn 4+ Fluorescence lifetime diagram of solid solution material.
FIG. 8 shows K in an embodiment of the application 2 Nb (1-x) Ta x F 7 :Mn 4+ Quantum yield plot for solid solution materials.
FIG. 9 shows K in an embodiment of the application 2 Nb (1-x) Ta x F 7 :Mn 4+ (x= 0,0.7,1) moisture stability diagram of solid solution material.
FIG. 10 shows K in an embodiment of the application 2 Nb (1-x) Ta x F 7 :Mn 4+ (x= 0,0.7,1) electroluminescence spectrum and CIE coordinate diagram of solid solution material.
Detailed Description
For the purpose of making apparent the objects, technical solutions and advantages of the present application, the present application will be further described in detail with reference to the following examples and the accompanying drawings, wherein the exemplary embodiments of the present application and the descriptions thereof are for illustrating the present application only and are not to be construed as limiting the present application.
All the raw materials of the present application are not particularly limited in their sources, and can be commercially available or prepared according to conventional methods well known to those skilled in the art. All the raw materials of the present application are not particularly limited in purity, and the present application preferably employs analytical purity or purity requirements conventional in the field of fluorescent powder. All raw materials of the application, the brands and abbreviations of which belong to the conventional brands and abbreviations in the field of the related application are clear and definite, and the person skilled in the art can purchase from the market or prepare by the conventional method according to the brands, abbreviations and the corresponding application.
[ example 1 ] K 2 Nb (1-x) Ta x F 7 Preparation of solid solution materials
Weighing Nb with a certain mass ratio according to x of 0.1, 0.3, 0.5, 0.7 or 0.9 in a target system 2 O 5 And Ta 2 O 5 Or Nb alone 2 O 5 Or Ta 2 O 5 In a reactor liner containing 6mL of HF solution, the reactor was placed in an oven at 120deg.C for 30 minutes to give a colorless transparent solution. After cooling to room temperature, 0.9372g of KHF was added 2 Stirring for 30min. Collecting light pink precipitate after reaction, washing with absolute ethanol for five times, and drying in oven at 80deg.C for 12 hr to obtain K 2 Nb (1-x) Ta x F 7 (0.ltoreq.x.ltoreq.1) solid solution material.
For the solid solution material K of the above mass ratios 2 Nb (1-x) Ta x F 7 The X-ray diffraction analysis was performed, and the spectrum is shown in fig. 2, and it can be seen that all diffraction peaks of the solid solution matrix material prepared in this example are coincident with standard cards, and characteristic peaks are shown to shift to the left, indicating that a continuous solid solution was synthesized.
For the solid solution matrix material K of the above mass ratios 2 Nb (1-x) Ta x F 7 EDS measurements were performed and the results are shown in Table 1, showing that the actual proportions of Nb and Ta elements are the same as the theoretical proportions.
Table 1:
[ example 2 ] in Mn 4+ K as luminescence center 2 MnF 6 Preparation of manganese source
Weighing 1.5g KMnO with certain mass 4 、30g KHF 2 In a beaker containing a volume of 6mL HF solution, stirring was continued for 30 minutes at room temperature. Then slowly dripping 1.5mL of hydrogen peroxide into the beaker containing the mixed solution, and reacting for a certain time to obtain golden yellow sediment at the bottom of the beaker. Transferring the precipitate into a centrifuge tube with a suction tube, repeatedly washing with absolute ethanol for three times, and finally drying the prepared sample in an oven at 80deg.C for 8 hr to obtain K 2 MnF 6 A manganese source.
[ example 3 ] K 2 Nb 0.9 Ta 0.1 F 7 :Mn 4+ Preparation of solid solution fluoride red fluorescent powder
0.2273g Nb 2 O 5 And 0.0420g Ta 2 O 5 Adding the mixture into a liner of a reaction kettle containing 6mL of HF solution, and placing the reaction kettle in an oven at 120 ℃ for 30 minutes to obtain colorless transparent solution. After cooling to room temperature, 0.0247 and g K are added 2 MnF 6 Stirring for 10 min in the lining of the reaction kettle,further adding 0.9372g KHF 2 Stirring for 30min. Collecting pale pink precipitate after reaction, washing with absolute ethanol for five times, and drying in oven at 80deg.C for 12 hr to obtain K 2 Nb 0.9 Ta 0.1 F 7 :Mn 4+ Solid solution fluoride red phosphor.
[ example 4 ] K 2 Nb 0.7 Ta 0.3 F 7 :Mn 4+ Preparation of solid solution fluoride red fluorescent powder
0.1768g Nb 2 O 5 And 0.1259g Ta 2 O 5 Adding the mixture into a liner of a reaction kettle containing 6mL of HF solution, and placing the reaction kettle in an oven at 120 ℃ for 30 minutes to obtain colorless transparent solution. After cooling to room temperature, 0.0247g of K was added 2 MnF 6 Into the lining of the reaction vessel, stirring was continued for 10 minutes, and 0.9372g KHF was further added 2 Stirring for 30min. Collecting pale pink precipitate after reaction, washing with absolute ethanol for five times, and drying in oven at 80deg.C for 12 hr to obtain K 2 Nb 0.7 Ta 0.3 F 7 :Mn 4+ Solid solution fluoride red phosphor.
[ example 5 ] K 2 Nb 0.5 Ta 0.5 F 7 :Mn 4+ Preparation of solid solution fluoride red fluorescent powder
0.1263g Nb 2 O 5 And 0.2099g Ta 2 O 5 Adding the mixture into a liner of a reaction kettle containing 6mL of HF solution, and placing the reaction kettle in an oven at 120 ℃ for 30 minutes to obtain colorless transparent solution. After cooling to room temperature, 0.0247 and g K are added 2 MnF 6 Into the lining of the reaction vessel, stirring was continued for 10 minutes, and 0.9372g KHF was further added 2 Stirring for 30min. Collecting pale pink precipitate after reaction, washing with absolute ethanol for five times, and drying in oven at 80deg.C for 12 hr to obtain K 2 Nb 0.5 Ta 0.5 F 7 :Mn 4+ Solid solution fluoride red phosphor.
[ example 6 ] K 2 Nb 0.3 Ta 0.7 F 7 :Mn 4+ Preparation of solid solution fluoride red fluorescent powder
0.0758g Nb 2 O 5 And 0.2939g Ta 2 O 5 Adding the mixture into a liner of a reaction kettle containing 6mL of HF solution, and placing the reaction kettle in an oven at 120 ℃ for 30 minutes to obtain colorless transparent solution. After cooling to room temperature, 0.0247 and g K are added 2 MnF 6 Into the lining of the reaction vessel, stirring was continued for 10 minutes, and 0.9372g KHF was further added 2 Stirring for 30min. Collecting pale pink precipitate after reaction, washing with absolute ethanol for five times, and drying in oven at 80deg.C for 12 hr to obtain K 2 Nb 0.3 Ta 0.7 F 7 :Mn 4+ Solid solution fluoride red phosphor.
[ example 7 ] K 2 Nb 0.1 Ta 0.9 F 7 :Mn 4+ Preparation of solid solution fluoride red fluorescent powder
0.0253g Nb 2 O 5 And 0.3778g Ta 2 O 5 Adding the mixture into a liner of a reaction kettle containing 6mL of HF solution, and placing the reaction kettle in an oven at 120 ℃ for 30 minutes to obtain colorless transparent solution. After cooling to room temperature, 0.0247 and g K are added 2 MnF 6 Into the lining of the reaction vessel, stirring was continued for 10 minutes, and 0.9372g KHF was further added 2 Stirring for 30min. Collecting pale pink precipitate after reaction, washing with absolute ethanol for five times, and drying in oven at 80deg.C for 12 hr to obtain K 2 Nb 0.1 Ta 0.9 F 7 :Mn 4+ Solid solution fluoride red phosphor.
Example 8 luminescence Performance test
The X-ray diffraction analysis was performed on each of the solid solution fluoride red phosphors of examples 3 to 7, and the spectra thereof are shown in fig. 3, and it can be seen that all diffraction peaks of the solid solution fluoride red phosphor coincide with standard cards, indicating that the prepared phosphor is a pure phase, and the preparation method does not change the crystalline phase of the phosphor.
FIG. 4 shows K 2 Nb 0.3 Ta 0.7 F 7 :Mn 4+ As shown in the scanning electron microscope spectrogram of the formula (I), the prepared solid solution fluoride red fluorescent powder is mainly a rod-shaped crystal, has clear edges, the average length is 20-50 mu m, and the average width is 2-10 mu m.
FIG. 5 shows the respective solid solution fluoride red phosphors, K 2 NbF 7 :Mn 4+ And K 2 TaF 7 :Mn 4+ As can be seen from the emission spectrum of (a) by Nb having the same charge 5+ And Ta 5+ After the solid solution is formed, the sharp red emission peak intensity of the fluorescent powder is obviously improved, and K 2 Nb 0.3 Ta 0.7 F 7 :Mn 4+ And K 2 Nb 0.5 Ta 0.5 F 7 :Mn 4+ The emission peak intensity of (2) is K 2 NbF 7 :Mn 4+ Or K 2 TaF 7 :Mn 4+ More than 1.5 times of the total number of the components.
FIG. 6 shows K 2 Nb 0.3 Ta 0.7 F 7 :Mn 4+ The CIE graph of (c) reflects that the phosphor has excellent red emission.
FIG. 7 shows each solid solution fluoride red phosphor, K 2 NbF 7 :Mn 4+ And K 2 TaF 7 :Mn 4+ As can be seen from the fluorescence lifetime graph of (2), with the increase of the value of x, the fluorescence lifetime of the solid solution fluorescent powder is increased and then reduced, and K 2 Nb 0.3 Ta 0.7 F 7 :Mn 4+ Has the maximum fluorescence lifetime.
FIG. 8 shows K 2 Nb 0.5 Ta 0.5 F 7 :Mn 4+ ，K 2 Nb 0.3 Ta 0.7 F 7 :Mn 4+ ，K 2 Nb 0.1 Ta 0.9 F 7 :Mn 4+ ，K 2 NbF 7 :Mn 4+ And K 2 TaF 7 :Mn 4+ As can be seen, when x is 0.7, K 2 Nb 0.3 Ta 0.7 F 7 :Mn 4+ The quantum yield of (c) is significantly improved.
As can be seen, the application is described in the following A 2 NbF 7 By adding Ta as a light-emitting matrix 5+ The two solid solutions doped with the same charge can effectively enhance the optical properties of red emission peak intensity, fluorescence lifetime, quantum yield and the like of the fluorescent powder, and has wide application prospect.
Example 9 moisture resistance test
Respectively taking 0.2g of fluorescent powder K 2 Nb 0.3 Ta 0.7 F 7 :Mn 4+ 、K 2 NbF 7 :Mn 4+ 、K 2 TaF 7 :Mn 4+ 1mL of distilled water is measured and added into the three fluorescent powders, the three fluorescent powders are soaked for 1440min, and after centrifugal drying, the luminous intensity of the fluorescent powders soaked in the water is tested.
FIG. 9 shows K 2 NbF 7 :Mn 4+ ，K 2 Nb 0.3 Ta 0.7 F 7 :Mn 4+ And K 2 TaF 7 :Mn 4+ It can be seen that when x is 0.7, K 2 Nb 0.3 Ta 0.7 F 7 :Mn 4+ Is significantly improved. Therefore, the solid solution fluoride prepared by the application can effectively improve the moisture resistance of the fluorescent powder, and further avoid the negative influence of the coating modified material on the chemical stability and luminous performance of the fluorescent powder after failure.
Example 10 device testing
The red fluorescent powder prepared in the embodiment 3 is packaged into an LED device, and the photoelectric property of the LED device is tested. Blue InGaN chip and commercial yellow phosphor YAG to Ce are adopted 3+ 、K 2 Nb 0.3 Ta 0.7 F 7 :Mn 4+ 、K 2 NbF 7 :Mn 4+ 、K 2 TaF 7 :Mn 4+ A WLED device was prepared. WLED devices are a: blue light chip (GaInN) +commercial yellow fluorescent powder (YAG: ce) 3+ ) And B: blue light chip (GaInN) +commercial yellow fluorescent powder (YAG: ce) 3+ )+K 2 NbF 7 :Mn 4+ Red phosphor, C: blue light chip (GaInN) +commercial yellow fluorescent powder (YAG: ce) 3+ )+K 2 Nb 0.3 Ta 0.7 F 7 :Mn 4+ Red phosphor, D: blue light chip (GaInN) +commercial yellow fluorescent powder (YAG: ce) 3+ )+K 2 TaF 7 :Mn 4+ The red fluorescent powder is used for measuring the luminous performance of the prepared LED device by using an integrating sphere spectrum radiometer system.
As shown in FIG. 10, WLED (B) (C) and WLED (D) have distinct red emission peaks, and K 2 Nb 0.3 Ta 0.7 F 7 :Mn 4+ (C) The red emission peaks of (C) are significantly stronger than those of (B) and (D), while the CIE chromaticity coordinates of (C) are (0.3525,0.3587), the correlated color temperature cct=4758K, and the color rendering index ra=94.1.
The use of "first," "second," etc. (e.g., first solution, etc.) herein is merely for clarity of description to distinguish between corresponding components and is not intended to limit any order or emphasize importance, etc.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the application, and is not meant to limit the scope of the application, but to limit the application to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the application are intended to be included within the scope of the application.
Claims (10)
1. A solid solution fluoride red fluorescent powder is characterized in that the chemical general formula is A 2 Nb (1-x) Ta x F 7 :Mn 4+ Wherein A is Li, na, K, rb or Cs, x is more than or equal to 0.1 and less than or equal to 0.9.
2. The solid solution fluoride red phosphor of claim 1, wherein x is 0.3.ltoreq.0.7.
3. The solid solution fluoride red phosphor of claim 2, wherein x is 0.5-0.7.
4. A solid solution fluoride red phosphor according to claim 3, wherein the solid solution fluoride red phosphor is a long rod-like particle having a length of 20 to 50 μm.
5. A solid solution fluoride red phosphor according to claim 3, wherein the quantum yield of the solid solution fluoride red phosphor is greater than 60%.
6. A method for preparing the solid solution fluoride red phosphor according to any one of claims 1 to 5, comprising the steps of:
nb is set to 2 O 5 、Ta 2 O 5 Mixing with hydrofluoric acid solution, and reacting at high temperature to obtain a first solution;
the first solution is mixed with K 2 MnF 6 After a period of reaction, KHF is added 2 Continuing the reaction until the reaction is finished;
and collecting the precipitate, washing and drying to obtain the solid solution fluoride red fluorescent powder.
7. The method of claim 6, wherein Nb 2 O 5 、Ta 2 O 5 Mixing with hydrofluoric acid solution and reacting for 20-40 minutes at 100-120 ℃.
8. The method of claim 6, wherein the first solution is mixed with K 2 MnF 6 The reaction time is 10-15 minutes.
9. The process according to claim 6, wherein KHF is added 2 With the Nb 2 O 5 And Ta 2 O 5 The molar ratio of (2) is 10:1-12:1.
10. A white light emitting diode having CIE chromaticity coordinates (0.3525,0.3587), correlated color temperature cct=4758K, and color rendering index ra=94.1, using the solid solution fluoride red phosphor of any one of claims 1 to 5.
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Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105038776A (en) * | 2015-06-18 | 2015-11-11 | 北京宇极科技发展有限公司 | Preparation method of Mn<4+> doped fluoride fluorescent powder material and method for surface modification of Mn<4+> doped fluoride fluorescent powder material |
| US20160090528A1 (en) * | 2014-09-30 | 2016-03-31 | Nichia Corporation | Fluoride fluorescent material, method for producing the same, and light emitting device |
| CN105950137A (en) * | 2016-05-05 | 2016-09-21 | 中国人民大学 | Mn<4+> doped fluoride red fluorescent powder, preparation method and application thereof |
| CN106010514A (en) * | 2016-06-27 | 2016-10-12 | 华南理工大学 | Mn<4+>-doped fluorogallate red fluorescent powder and preparation method thereof |
| CN106554776A (en) * | 2016-10-10 | 2017-04-05 | 云南民族大学 | A kind of effective fluoride red fluorescence powder, preparation method thereof of blue-light semiconductor light-emitting diodes |
| CN106634989A (en) * | 2016-12-09 | 2017-05-10 | 华南理工大学 | Mn<4+> doped fluoride red light fluorescent powder for high color rendering and warm white light LED (Light Emitting Diode) and preparation method of Mn<4+> doped fluoride red light fluorescent powder |
| CN107142102A (en) * | 2017-06-15 | 2017-09-08 | 华南理工大学 | A kind of Mn4+The surface modifying method of doped fluoride red fluorescence powder material |
| CN107236543A (en) * | 2017-06-15 | 2017-10-10 | 华南理工大学 | One kind improves Mn4+The method of doped fluoride red fluorescence powder material moisture resistance properties |
| CN108192617A (en) * | 2018-01-28 | 2018-06-22 | 江西理工大学 | A kind of Mn4+New Fluoride red fluorescence material of doping and preparation method thereof |
| CN110184057A (en) * | 2019-06-12 | 2019-08-30 | 上海应用技术大学 | A kind of oxygen fluoride red fluorescence powder and preparation method thereof |
| CN110240895A (en) * | 2019-07-16 | 2019-09-17 | 江西理工大学 | Mn4+The recovery of performance method of doped fluoride or oxyfluoride fluorescent material |
| CN111748345A (en) * | 2020-05-21 | 2020-10-09 | 南昌大学 | Mn (manganese)4+Activated fluoride red fluorescent powder and preparation method thereof |
| CN112175609A (en) * | 2020-05-29 | 2021-01-05 | 江西理工大学 | Green preparation method of water-resistant fluoride red fluorescent powder |
| CN112251219A (en) * | 2020-10-29 | 2021-01-22 | 桂林理工大学 | Moisture-proof fluoride red fluorescent powder and preparation method thereof |
-
2023
- 2023-07-31 CN CN202310950017.2A patent/CN116970394A/en active Pending
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160090528A1 (en) * | 2014-09-30 | 2016-03-31 | Nichia Corporation | Fluoride fluorescent material, method for producing the same, and light emitting device |
| CN105038776A (en) * | 2015-06-18 | 2015-11-11 | 北京宇极科技发展有限公司 | Preparation method of Mn<4+> doped fluoride fluorescent powder material and method for surface modification of Mn<4+> doped fluoride fluorescent powder material |
| CN105950137A (en) * | 2016-05-05 | 2016-09-21 | 中国人民大学 | Mn<4+> doped fluoride red fluorescent powder, preparation method and application thereof |
| CN106010514A (en) * | 2016-06-27 | 2016-10-12 | 华南理工大学 | Mn<4+>-doped fluorogallate red fluorescent powder and preparation method thereof |
| CN106554776A (en) * | 2016-10-10 | 2017-04-05 | 云南民族大学 | A kind of effective fluoride red fluorescence powder, preparation method thereof of blue-light semiconductor light-emitting diodes |
| CN106634989A (en) * | 2016-12-09 | 2017-05-10 | 华南理工大学 | Mn<4+> doped fluoride red light fluorescent powder for high color rendering and warm white light LED (Light Emitting Diode) and preparation method of Mn<4+> doped fluoride red light fluorescent powder |
| CN107142102A (en) * | 2017-06-15 | 2017-09-08 | 华南理工大学 | A kind of Mn4+The surface modifying method of doped fluoride red fluorescence powder material |
| CN107236543A (en) * | 2017-06-15 | 2017-10-10 | 华南理工大学 | One kind improves Mn4+The method of doped fluoride red fluorescence powder material moisture resistance properties |
| CN108192617A (en) * | 2018-01-28 | 2018-06-22 | 江西理工大学 | A kind of Mn4+New Fluoride red fluorescence material of doping and preparation method thereof |
| CN110184057A (en) * | 2019-06-12 | 2019-08-30 | 上海应用技术大学 | A kind of oxygen fluoride red fluorescence powder and preparation method thereof |
| CN110240895A (en) * | 2019-07-16 | 2019-09-17 | 江西理工大学 | Mn4+The recovery of performance method of doped fluoride or oxyfluoride fluorescent material |
| CN111748345A (en) * | 2020-05-21 | 2020-10-09 | 南昌大学 | Mn (manganese)4+Activated fluoride red fluorescent powder and preparation method thereof |
| CN112175609A (en) * | 2020-05-29 | 2021-01-05 | 江西理工大学 | Green preparation method of water-resistant fluoride red fluorescent powder |
| CN112251219A (en) * | 2020-10-29 | 2021-01-22 | 桂林理工大学 | Moisture-proof fluoride red fluorescent powder and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 董云开: "过渡金属-稀土离子掺杂的发光材料的合成及发光性能", 中国优秀硕士学位论文电子期刊（工程科技I辑）, no. 2023, 15 February 2023 (2023-02-15), pages 016 - 2301 * |
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