CN116376540A - Moisture-resistant fluoride red fluorescent powder and preparation method and application thereof - Google Patents
Moisture-resistant fluoride red fluorescent powder and preparation method and application thereof Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 117
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
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- 229910001506 inorganic fluoride Inorganic materials 0.000 claims abstract description 62
- 150000001412 amines Chemical class 0.000 claims abstract description 49
- 239000011247 coating layer Substances 0.000 claims abstract description 39
- 230000003213 activating effect Effects 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 17
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- 238000006243 chemical reaction Methods 0.000 claims description 32
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- 238000000576 coating method Methods 0.000 claims description 24
- 230000005284 excitation Effects 0.000 claims description 19
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- 125000003277 amino group Chemical group 0.000 claims description 13
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
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- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
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- 239000005642 Oleic acid Substances 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
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- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
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- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000011160 research Methods 0.000 description 2
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- 238000003917 TEM image Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
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- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
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- 230000003628 erosive effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
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- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
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- 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
- C09K11/615—Halogenides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
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- B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
- B42D25/30—Identification or security features, e.g. for preventing forgery
- B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/22—Luminous paints
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/61—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing fluorine, chlorine, bromine, iodine or unspecified halogen elements
- C09K11/617—Silicates
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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 with at least one potential-jump barrier or surface barrier 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 with at least one potential-jump barrier or surface barrier 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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- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Abstract
A wet-proof fluoride red fluorescent powder and a preparation method and application thereof belong to the field of luminescent materials. The moisture-resistant fluoride red phosphor comprises Mn 4+ Activating the full inorganic fluoride red fluorescent powder and an amine coating layer, wherein the amine coating layer is coated on Mn 4+ Activating the surface of the inorganic fluoride red fluorescent powder, wherein the thickness of the amine coating layer is nano-scale, which can effectively relieve Mn 4+ The activated inorganic fluoride red fluorescent powder is easy to hydrolyze and lose efficacy,short service life, high preparation difficulty and complex process.
Description
Technical Field
The application relates to the field of luminescent materials, in particular to a moisture-resistant fluoride red fluorescent powder, and a preparation method and application thereof.
Background
Mn 4+ Activated fluoride A 2 XF 6 (A=Na, K, rb, cs; X=Si, ge, sn, ti, zr) is the current research focus in the field of red phosphors, benefiting from Mn 4+ The unique 3d3 outer layer electronic structure has the characteristics of broadband absorption (300-500 nm) and narrowband emission (610-650 nm), and the excitation peak is matched with the emission peak of a blue light chip, and the emission peak is positioned in a high-energy red light area sensitive to human eyes, so that the fluorescent powder has practical application requirements in the fields of white light LEDs, plant illumination, high-color-gamut display and the like (Nat.Comm.5, 2014,4312; J.Am.Ceram.Soc.103,2020, 1018). However, because of the nature of the ionic crystal, the presence of polar water molecules in the air can cause Mn in the phosphor 4+ Hydrolysis failure, resulting in reduced luminous efficiency and shortened lamp life (ACS appl. Mate. Interfaces 10,2018,18082; angel. Chem. Int. Ed.19,2021, 3986.). At present, common methods for improving the water erosion resistance of the ceramic material comprise organic coating, inorganic homogeneous coating, inorganic heterogeneous coating, surface deactivation and the like. However, these methods have the following problems:
1. in the case of inorganic heterogeneous coating, al 2 O 3 ,TiO 2 ,CaF 2 And SrF 2 (ECS Journal of Solid State Science and Technology,2019,8 (6): R88; chemistry of Materials,2019,31 (18): 7192-202;Materials Research Bulletin,2019,115:98-104;International Journal of Applied Ceramic Technology,2021,18 (4): 1106-13; patent CN 1122512129) and the like were successfully coated on the outside of the phosphor. However, inorganic heterogeneous coating or process flow is complex (e.g. coating Al 2 O 3 ,TiO 2 An atomic layer deposition technology is needed), and the preparation efficiency is low; or a high concentration hydrofluoric acid environment (CaF) 2 And SrF 2 Etc.), which can cause hidden hazards to equipment, operators and the environment. At the same time, the inorganic coating layer and the fluorescent powder matrix have different crystal latticesStructure, refractive index, which typically results in defects at the interface, reduces the probability of radiative transitions, and increases light scattering at the interface, thereby reducing fluorescence intensity.
2. Inorganic homogeneous coating, i.e. using fluorescent powder matrix material as coating layer, forming a matrix protective layer without activator ion on the surface of original fluorescent powder, which can be expressed as A 2 XF 6 :Mn 4+ @A 2 XF 6 . Compared with inorganic heterogeneous coating, the homogeneous coating has the same lattice constant, refractive index and the like as those of the internal fluorescent powder, so that the luminous intensity is not generally reduced, but the fluoride matrix is dissolved in water, so that the matrix protective layer is continuously dissolved in use, the service life is lower, and the fluorescent powder cannot be recycled (patent CN201910630976; journal of Materials Chemistry C,2019,7 (20): 6077-84;Angewandte Chemie,2019,131 (12): 3883-7;Journal of Luminescence,2021,234:117968). And the preparation process of the high-concentration hydrofluoric acid is generally required, so that higher requirements on equipment safety are put forward, and the cost is increased.
3. Surface deactivation, i.e. Mn doping of phosphor surface layer 4+ Removing to form a matrix protective layer without activator ion, which has the same principle of improving water corrosion resistance as inorganic homogeneous coating, thus having similar defects and being incapable of long-term recycling (Advanced Materials Interfaces,2019,6 (9): 1802006;ACS applied materials)&interfaces,2018,10(21):18082-92；)。
4. The main materials of the existing organic coating are alkyl phosphate, oleic acid, silane coupling agent, polypropylene glycol and the like, and the preparation process is complex, the flow is complicated, the cost is high, for example, the carbon coating needs to use a vapor deposition technology, the cost is high, and the yield is low (Ceramics International,2020,46 (7): 8811-8); the silane coupling agent needs to pretreat the fluorescent powder by using plasma, and then the polycondensation reaction of the silane coupling agent is carried out, so that the preparation period is long (Colloids and Surfaces A: physicochemical and Engineering Aspects,2017, 520:850-4); the oleic acid coating requires a high temperature and high pressure environment and the moisture resistance effect is not significant (ACS appl. Mater. Interfaces,2017,9,7232-7240).
Disclosure of Invention
The application provides a moisture-resistant fluoride red fluorescent powder, and a preparation method and application thereof, which can effectively relieve Mn 4+ The activated inorganic fluoride red fluorescent powder is easy to hydrolyze and lose efficacy, and has the problems of short service life, high preparation difficulty and complex process.
Embodiments of the present application are implemented as follows:
in a first aspect, the present examples provide a moisture-resistant fluoride red phosphor, wherein the moisture-resistant fluoride red phosphor comprises Mn 4+ Activating the full inorganic fluoride red fluorescent powder and an amine coating layer, wherein the amine coating layer is coated on Mn 4+ Activating the surface of the full inorganic fluoride red fluorescent powder, wherein the thickness of the amine coating layer is nano-scale.
The moisture-resistant fluoride red fluorescent powder provided by the application is coated on Mn through an amine coating layer 4+ Activating the surface of the inorganic fluoride red fluorescent powder, effectively isolating water vapor by using an amine coating layer, and avoiding Mn 4+ The full inorganic fluoride red fluorescent powder is activated to hydrolyze, the service life of the full inorganic fluoride red fluorescent powder is effectively prolonged, the amine coating layer can be kept stable for a long time in a humid environment, and the service life of the moisture-proof fluoride red fluorescent powder is further prolonged, so that the full inorganic fluoride red fluorescent powder can be recycled.
In some alternative embodiments, in combination with the first aspect, the composition of the amine coating comprises an unsaturated aliphatic amine having 10 to 20 carbon atoms.
Optionally, the unsaturated fatty amine comprises at least one of undecylenamine, dodecenamine, tridecenylamine, tetradecylenamine, pentadecenylamine, hexadecylenamine, heptadecenylamine, octadecyl enamine.
Alternatively, the amine coating is of the composition octadecylenamine.
With reference to the first aspect, in some alternative embodiments, the amine-based coating layer includes at least one amine group and at least one linear unsaturated organic carbon chain, at least a portion of the amine groups being aligned with Mn 4+ The fluoride ions activating the surface of the inorganic fluoride red fluorescent powder combine and form hydrogen bonds, and a linear unsaturated organic carbon chain points to Mn 4+ External activating of full inorganic fluoride red fluorescent powderA side;
alternatively, the linear unsaturated organic carbon chain has a carbon number of 10 to 20, and contains a carbon-carbon double bond.
Alternatively, the linear unsaturated organic carbon chain has a carbon number of 18.
With reference to the first aspect, in some alternative embodiments, mn 4+ The chemical formula of the activated inorganic fluoride red fluorescent powder is A 2 XF 6 :Mn 4+ Wherein A is selected from at least one of Li, na, K, rb and Cs, and X is selected from at least one of Si, ge, ti and Zr.
In some alternative embodiments, in combination with the first aspect, the excitation wavelength of the wet-resistant fluoride red phosphor is between 300 and 500nm and the wavelength of the strongest emission peak is between 620 and 640nm.
In a second aspect, the present examples provide a method for preparing the moisture-resistant fluoride red phosphor provided in the first aspect, comprising: mn is added to 4+ Activating the inorganic fluoride red fluorescent powder, amine compounds and alcohol, mixing and dispersing to obtain a solid-liquid mixture; reacting the solid-liquid mixture at a temperature of not less than 25 ℃ for at least 1h; wherein the amine compound has a linear unsaturated organic carbon chain and an amine group.
The preparation method provided by the application has the advantages of simple process, simple flow, low cost and low processing difficulty, can realize batch production of the moisture-resistant fluoride red fluorescent powder, has good moisture resistance, and can be stably used in a humid environment for a long time.
With reference to the second aspect, in some alternative embodiments, the temperature of the reaction is 100-200 ℃ and the time of the reaction is 1-9h.
Alternatively, the alcohol comprises a monohydric alcohol having no more than 6 carbon atoms.
With reference to the second aspect, in some alternative embodiments, mn 4+ The molar ratio of the activated inorganic fluoride red fluorescent powder to the amine compound is 1 (0.1-10).
Alternatively, mn 4+ Particle size 0.1 for activating the full inorganic fluoride red phosphor-50μm。
With reference to the second aspect, in some alternative embodiments, the dispersing comprises ultrasonic dispersing.
Alternatively, the ultrasonic power of ultrasonic dispersion is 50-300W and the ultrasonic time is 0.5-1h.
In a third aspect, the present examples provide the use of the moisture resistant fluoride red phosphor provided in the first aspect for the preparation of a light emitting device, paint or display device.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered limiting the scope, and that other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an XRD contrast pattern of the phosphor powders KSFM, KSFM@OAm-3x and PDF07-0217 standard card provided in example 1;
FIG. 2 is a TEM image of phosphor KSFM@OAm-3x provided in example 1;
FIG. 3 is a graph of the emission spectrum of the phosphor KSFM, KSFM@OAm-3x provided in example 1 under 450nm blue excitation;
FIG. 4 is a graph comparing quantum yields of the phosphors KSFM, KSFM@OAm-3x provided in example 1;
FIG. 5 is a graph showing the change of the luminescence intensity of the phosphors KSFM, KSFM@OAm-3x provided in example 1 with time under the moisture resistance test condition;
FIG. 6 is a graph showing the concentration change of each ion in the solution of the phosphors KSFM, KSFM@OAm-3x provided in example 1 under the moisture resistance test condition;
FIG. 7 is an XRD contrast pattern of the phosphor powder KSFM, KSFM@OAm-RT and PDF07-0217 standard card provided in example 2;
FIG. 8 is a graph of the emission spectrum of the phosphor KSFM, KSFM@OAm-RT provided in example 2 under 450nm blue excitation;
FIG. 9 is a graph showing the change of the luminescence intensity of the phosphors KSFM, KSFM@OAm-3x provided in example 2 with time under the moisture resistance test condition;
FIG. 10 is a graph of the emission spectrum of the fluorescent powders KTFM and KTFM@OAm provided in example 3 under the excitation of 450nm blue light;
FIG. 11 is a graph showing the change of the luminescence intensity of the phosphor KTFM and KTFM@OAm provided in example 3 with time under the moisture resistance test condition;
FIG. 12 is a graph showing emission spectra of the phosphor KSFM+ OAm provided in comparative example 1 and the phosphors KSFM, KSFM@OAm-3x provided in example 1 under 455nm blue excitation;
FIG. 13 is a graph showing the change of the luminescence intensity of the phosphor KSFM+ OAm provided in comparative example 1 with time under the moisture resistance test condition;
FIG. 14 is a graph showing the comparison of the intensity of the emission peaks of the phosphor KSFM+ OAm provided in comparative example 1 and the phosphor KSFM+ OAm-200-3h provided in comparative example 2 after 5 minutes of immersion, and the emission peaks of the phosphors KSFM, KSFM@OAm-3x provided in example 1 at 631nm under excitation of 455 nm.
Detailed Description
Embodiments of the present application will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustration of the present application and should not be construed as limiting the scope of the present application. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The following is a specific description of the moisture-resistant fluoride red phosphor and the preparation method and application thereof:
in a first aspect, the present examples provide a moisture-resistant fluoride red phosphor, wherein the moisture-resistant fluoride red phosphor comprises Mn 4+ Activating the full inorganic fluoride red fluorescent powder and an amine coating layer, wherein the amine coating layer is coated on Mn 4+ Activating the surface of the full inorganic fluoride red fluorescent powder, wherein the thickness of the amine coating layer is nano-scale.
Mn 4+ Activating the red phosphor of the inorganic fluoride to indicate that the red phosphor is activatedInorganic fluoride red fluorescent powder as base material and Mn as main material 4+ Activation, which contains no organic components. Mn (Mn) 4+ The activated perfluorinated inorganic fluoride red phosphor can be prepared by itself or can be purchased from the market without limitation.
The amine coating layer contains amino (-NH) 2 ) Amine compound of (2), amine group of amine compound and Mn 4 + Activating the fluoride ion combination on the surface of the inorganic fluoride red fluorescent powder to form the coating on Mn 4+ Activating the organic coating layer on the surface of the inorganic fluoride red fluorescent powder.
The moisture-resistant fluoride red fluorescent powder provided by the application is coated on Mn through an amine coating layer 4+ Activating the surface of the inorganic fluoride red fluorescent powder, effectively isolating water vapor by using an amine coating layer, and avoiding Mn 4+ The full inorganic fluoride red fluorescent powder is activated to hydrolyze, the service life of the full inorganic fluoride red fluorescent powder is effectively prolonged, the amine coating layer can be kept stable for a long time in a humid environment, and the service life of the moisture-proof fluoride red fluorescent powder is further prolonged, so that the full inorganic fluoride red fluorescent powder can be recycled.
In some alternative examples, the composition of the amine coating includes an unsaturated fatty amine having 10-20 carbon atoms. Alternatively, the unsaturated fatty amine has a carbon number of 11 to 20, further alternatively 11 to 18. Formamide or unsaturated fatty amine with 10-20 carbon atoms can be mixed with Mn 4+ And (3) activating fluorine ions on the surface of the inorganic fluoride red fluorescent powder to combine to form a hydrogen bond to form an amine coating layer.
Optionally, the unsaturated fatty amine comprises at least one of undecylenamine, dodecenamine, tridecenylamine, tetradecylenamine, pentadecenylamine, hexadecylenamine, heptadecenylamine, octadecyl enamine.
The unsaturated fatty amine has a linear unsaturated organic carbon chain and an amine group at the end of the carbon chain, so that the amine group in the unsaturated fatty amine has a molecular weight of Mn 4+ The fluoride ions activating the surface of the inorganic fluoride red fluorescent powder combine and form hydrogen bonds, and a linear unsaturated organic carbon chain points to Mn 4+ Activating the outer side of the inorganic fluoride red fluorescent powder to form an amine coating layer with good hydrophobic effect, and is beneficial toThereby improving the quantum yield.
Alternatively, the amine coating is of the composition octadecylenamine.
When the amine coating layer contains octadecylamine (alias oil amine), the moisture-resistant fluoride red fluorescent powder has excellent moisture resistance, and the quantum yield is improved, compared with Mn 4+ The activation of the full inorganic fluoride red fluorescent powder is improved, and the luminous performance is superior to that of uncoated Mn 4+ Activating the full inorganic fluoride red fluorescent powder.
Wherein the thickness of the amine coating layer is nano-scale. In the present application, the thickness of the nano-scale means that the thickness is not more than 100nm, for example, the thickness of the amine coating layer is any one value or between any two values of 1nm, 5nm, 10nm, 15nm, 20nm, 25nm, 30nm, 40nm, 45nm, 50nm, 70nm, and within the above thickness range, not only the moisture resistance of the red phosphor can be achieved, but also the light emitting performance thereof is not sacrificed.
In some alternative examples, the amine coating comprises at least one amine group and at least one linear unsaturated organic carbon chain, at least a portion of the amine group being aligned with Mn 4+ The fluoride ions activating the surface of the inorganic fluoride red fluorescent powder combine and form hydrogen bonds, and a linear unsaturated organic carbon chain points to Mn 4+ The outside of the fully inorganic fluoride red phosphor is activated.
By using amino groups and Mn 4+ The fluoride ions activating the surface of the inorganic fluoride red fluorescent powder combine and form hydrogen bonds, and the linear unsaturated organic carbon chain is utilized to point to Mn 4+ Activating the outer side of the inorganic fluoride red fluorescent powder to form an amine coating layer with good hydrophobic effect, and the Mn is used for 4+ The activated inorganic fluoride red fluorescent powder and the amine coating layer are combined by utilizing hydrogen bonds, so that the long-term stable coating of the amine coating layer on Mn can be realized 4+ The surface of the inorganic fluoride red phosphor is activated so that the moisture-resistant fluoride red phosphor can exist stably even if it is in a humid environment for a long period of time.
Alternatively, the linear unsaturated organic carbon chain has a carbon number of 10 to 20, and contains a carbon-carbon double bond.
Illustratively, the linear unsaturated organic carbon chain has a carbon number of any one of 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20.
Alternatively, the linear unsaturated organic carbon chain has a carbon number of 18.
In some alternative examples, mn 4+ The chemical formula of the activated inorganic fluoride red fluorescent powder is A 2 XF 6 :Mn 4+ Wherein A is selected from at least one of Li, na, K, rb and Cs, and X is selected from at least one of Si, ge, ti and Zr.
Mn as described above 4+ The activated inorganic fluoride red fluorescent powder can be prepared by itself or can be purchased directly from the market, and is not limited herein.
Wherein Mn is 4+ The excitation wavelength of the activated inorganic fluoride red fluorescent powder is 300-500nm, and the wavelength of the strongest emission peak is 620-640nm.
In some alternative examples, the excitation wavelength of the wet-resistant fluoride red phosphor is between 300-500nm and the wavelength of the strongest emission peak is between 620-640nm.
The excitation wavelength of the wet-resistant fluoride red fluorescent powder is positioned in a blue light area, the wet-resistant fluoride red fluorescent powder can be directly matched with commercial blue light LEDs and the like, and the color rendering index of the wet-resistant fluoride red fluorescent powder can be improved when the wet-resistant fluoride red fluorescent powder is applied to white light LEDs and the like because the wavelength of the strongest emission peak is positioned between 620 and 640nm.
In a second aspect, the present application provides a preparation method of the above-mentioned wet-resistant fluoride red phosphor, which has simple process, simple flow, low cost and low processing difficulty, and can realize mass production of the wet-resistant fluoride red phosphor, and the obtained wet-resistant fluoride red phosphor has good wet resistance and can be used in a humid environment stably for a long time.
The preparation method comprises the following steps:
s1, mn 4+ Activating the inorganic fluoride red fluorescent powder, the amine compound and alcohol, mixing and dispersing to obtain a solid-liquid mixture. Wherein the amine compound has a linear unsaturated organic carbon chain and an amine group。
Alcohol as solvent for dispersing Mn 4+ Activating the full inorganic fluoride red fluorescent powder and the amine compound to make the two fully contacted.
Alternatively, the alcohol is a monohydric alcohol.
Alternatively, the alcohol includes a monohydric alcohol having no more than 6 carbon atoms, that is, the alcohol may be at least one of methanol, ethanol, propanol, butanol, pentanol, hexanol, and the like.
In some alternative examples, mn 4+ The molar ratio of the activated inorganic fluoride red fluorescent powder to the amine compound is 1 (0.1-10).
In the above molar ratio range, an amine coating layer having a thickness of a nanometer scale can be obtained, and the formed amine coating layer hardly affects the luminous intensity of the finally obtained wet-resistant fluoride red phosphor.
Illustratively, mn 4+ The molar ratio of the activated inorganic fluoride red fluorescent powder to the amine compound is any one value or between any two values of 1:0.1, 1:0.5, 1:1, 1:2, 1:3, 1:5, 1:7 and 1:10.
Alternatively, mn 4+ The particle size of the activated inorganic fluoride red phosphor is 0.1-50 μm.
It can be understood that the thickness of the amine coating layer is nano-scale, so that the effect on the size is small, and the particle size and Mn of the moisture-resistant fluoride red fluorescent powder 4+ The particle size of the activated perfluorinated inorganic fluoride red phosphor does not differ much, and is therefore based on Mn in the above particle size range 4+ The moisture-resistant fluoride red fluorescent powder prepared by activating the full inorganic fluoride red fluorescent powder can be directly applied to the preparation of a light-emitting device, a coating or a display device.
Illustratively, mn 4+ The particle size of the activated perfluorinated red phosphor is any one of or between any two of 0.1 μm, 0.5 μm, 1 μm, 3 μm, 5 μm, 7 μm, 10 μm, 13 μm, 15 μm, 18 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm.
The dispersion means include, but are not limited to, stirring.
In some alternative examples, dispersing includes ultrasonic dispersing.
Is beneficial to Mn by using ultrasonic dispersion mode 4+ The activated full inorganic fluoride red fluorescent powder and amine compound are uniformly dispersed and fully contacted, which is favorable for forming uniform coating on Mn in the later period 4+ Activating amine coating layer on the surface of the inorganic fluoride red fluorescent powder, optimizing the moisture resistance and improving the stability of the moisture resistance.
Alternatively, the ultrasonic power of ultrasonic dispersion is 50-300W and the ultrasonic time is 0.5-1h.
Within the above parameters, mn is favored 4+ Activating the full inorganic fluoride red fluorescent powder and the amine compound to be uniformly dispersed in the solid-liquid mixture, so as to realize the full contact of the full inorganic fluoride red fluorescent powder and the amine compound.
Illustratively, the ultrasonic power is any one value or between any two values of 50W, 70W, 100W, 150W, 200W, 250W, 300W, and the ultrasonic time is any one value or between any two values of 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, 1h.
S2, reacting the solid-liquid mixture for at least 1h at the temperature of not lower than 25 ℃.
In some alternative examples, the temperature of the reaction is 100-200 ℃ and the time of the reaction is 1-9 hours.
Under the above reaction conditions, mn can be obtained 4+ Activating full inorganic fluoride red fluorescent powder and amine compound to fully react, thereby being beneficial to amino and Mn 4+ And the fluoride ions on the surface of the activated inorganic fluoride red fluorescent powder are combined and form hydrogen bonds, the reaction time is reasonable, and the energy consumption waste is avoided.
Illustratively, the temperature of the reaction is any one value or between any two values of 100 ℃, 110 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃,180 ℃, 190 ℃, 200 ℃, and the time of the reaction is any one value or between any two values of 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h.
In a third aspect, the present examples provide the use of the above moisture resistant fluoride red phosphor for the preparation of a light emitting device, paint or display device.
Light emitting devices include, but are not limited to, white LEDs, white LDs, and also plant illumination.
The moisture-resistant fluoride red phosphor of the present application, and its preparation method and application are described in further detail below with reference to examples.
Example 1
(1) The chemical formula is K 2 SiF 6 :Mn 4+ Mn of (2) 4+ Activating fluoride red fluorescent powder
K 2 SiF 6 :Mn 4+ The preparation method comprises the following specific processes: 3.556g NH 4 F. 1.394g KF was placed in a 100mL polytetrafluoroethylene liner, 8mL deionized water was added dropwise to the vessel and stirred for 5 minutes, followed by 0.296g K 2 MnF 6 And stirred for 10 minutes. Subsequently, 32mL of hydrochloric acid solution (3 mol/L) was dropped into the reaction solution, and stirred for 10 minutes. 2.5g of tetraethyl silicate (TEOS) was dropped into the solution and vigorously stirred for 3 hours. Centrifuging the reaction solution to remove supernatant, repeatedly washing the lower precipitate with absolute ethanol, centrifuging for 3 times, and vacuum drying the precipitate at 50deg.C for 3 hr to obtain product K 2 SiF 6 :Mn 4+ (labeled KSFM).
(2) Moisture-resistant fluoride red fluorescent powder
The preparation method of the wet-resistant fluoride red fluorescent powder comprises the following steps: will be 1g K 2 SiF 6 :Mn 4+ Fluorescent powder, 4.44mL of oleylamine and 25mL of absolute ethyl alcohol are simultaneously added into a 100mL polytetrafluoroethylene reaction kettle, and the reaction kettle is sealed and dispersed for 1 hour by ultrasonic so that reactants are fully mixed. Subsequently, the reaction vessel was put into an oven at 200℃for 3 hours. Centrifuging the reacted mixture after cooling and vacuum drying at 50deg.C for 3 hr to obtain moisture-resistant fluoride red phosphor, which can be expressed as K 2 SiF 6 :Mn 4+ @ OAm-3x (labeled KSFM @ OAm-3 x).
As shown in FIG. 1, X-ray diffraction analysis was performed on the phosphors KSFM, KSFM@OAm-3X obtained in example 1, wherein the diffraction pattern was matched with the PDF07-0217 standard card, demonstrating that oleylamine was coatedThe phosphor after that (i.e., the moisture-resistant fluoride red phosphor prepared in example 1) had K alone 2 SiF 6 A crystalline phase.
The transmission electron microscope of the phosphor KSFM@OAm-3x obtained in example 1 is shown in FIG. 2, and has a core-shell structure, which shows that oleylamine forms a coating layer on the surface of the phosphor KSFM.
The emission spectra of the fluorescent powders KSFM and KSFM@OAm-3x obtained in the example 1 under the excitation of 450nm blue light are shown in FIG. 3, and according to FIG. 3, the fluorescent powders KSFM and KSFM@OAm-3x can emit red light under the excitation of 450nm blue light.
As can be seen from FIG. 4, the quantum yields of the phosphors KSFM, KSFM@OAm-3x obtained in example 1 are superior to those of the phosphor KSFM, that is, the phosphor KSFM@OAm-3x has a luminescence property superior to that of the uncoated phosphor KSFM, indicating that the luminescence property of the phosphor (that is, the moisture-resistant fluoride red phosphor prepared in example 1) after the oleylamine coating is improved.
The change of the luminescence intensity of the fluorescent powder KSFM and KSFM@OAm-3x obtained in the example 1 with time under the moisture resistance test condition of 0.3g/5mL of deionized water is shown in FIG. 5, and according to FIG. 5, the KSFM@OAm-3x still maintains 85.2% of the original intensity after being soaked in 0.3g/5mL of deionized water for 6 hours, and no obvious decrease trend exists, which indicates that the moisture resistance of the fluorescent powder coated by the oleylamine (namely the moisture resistance fluoride red fluorescent powder prepared in the example 1) is obviously improved.
Under the moisture resistance test condition of 0.3g/20mL deionized water, the concentration of each ion in the solution of the fluorescent powder KSFM and KSFM@OAm-3x obtained in the example 1 is changed with time as shown in FIG. 6, and according to FIG. 6, the oleylamine coating layer can effectively prevent the fluorescent powder KSFM from contacting with external water, so that the moisture resistance is improved.
Example 2
(1) The chemical formula obtained in example 1 is K 2 SiF 6 :Mn 4+ Mn of (2) 4+ Activating fluoride red fluorescent powder
(2) Moisture-resistant fluoride red fluorescent powder
Preparation method of wet-proof fluoride red fluorescent powderThe method comprises the following steps: will be 1g K 2 SiF 6 :Mn 4+ Fluorescent powder, 7.4mL of oleylamine and 25mL of absolute ethyl alcohol are simultaneously added into a 100mL polytetrafluoroethylene reaction kettle, and the reaction kettle is sealed and sonicated for 1 hour. Subsequently, the reacted mixture was centrifuged and dried in vacuo at 50℃for 3 hours to obtain a wet-resistant fluoride red phosphor. The chemical formula of the moisture-resistant fluoride red fluorescent powder can be expressed as K 2 SiF 6 :Mn 4+ @ OAm-RT (labeled KSFM @ OAm-RT).
As shown in FIG. 7, X-ray diffraction analysis was performed on the phosphors KSFM and KSFM@OAm-RT obtained in example 2, and the diffraction pattern was matched with the PDF07-0217 standard card, indicating that the oleylamine-coated phosphor (i.e., the moisture-resistant fluoride red phosphor prepared in example 2) had K only 2 SiF 6 A crystalline phase.
The emission spectra of the fluorescent powders KSFM and KSFM@OAm-RT obtained in example 2 under the excitation of 450nm blue light are shown in FIG. 8, and both products can emit red light under the excitation of 450nm blue light.
The change of the luminescence intensity of the fluorescent powder KSFM and KSFM@OAm-3x obtained in the example 2 with time under the humidity resistance test condition of 0.3g/5mL deionized water is shown in FIG. 9, and the fluorescent powder KSFM@OAm-3x still maintains 79.6% of the original intensity after being soaked in water for 6 hours, and has no obvious descending trend, which indicates that the humidity resistance of the fluorescent powder (namely the humidity resistance fluoride red fluorescent powder prepared in the example 2) after being coated by the oleylamine under the normal temperature preparation condition is obviously improved.
Example 3
(1) The chemical formula is K 2 TiF 6 :Mn 4+ Mn of (2) 4+ Activating fluoride red fluorescent powder
K 2 TiF 6 :Mn 4+ The preparation method comprises the following specific processes: 2.222g NH 4 F. 0.697g KF was placed in a 100mL polytetrafluoroethylene liner, 4mL deionized water was added dropwise to the vessel and stirred for 5 minutes, followed by 0.089g K 2 MnF 6 And stirred for 10 minutes. Subsequently, 20mL of hydrochloric acid solution (3 mol/L) was dropped into the reaction solution, and stirred for 10 minutes. 2.042g of tetrabutyl titanate was dropped into the solution, and vigorously stirred for 7 hours. The reaction solution is then separated fromRemoving supernatant, repeatedly washing the lower precipitate with absolute ethanol, centrifuging for 3 times, and vacuum drying the precipitate at 50deg.C for 3 hr to obtain product K 2 TiF 6 :Mn 4 + (labeled KTFM).
(2) Moisture-resistant fluoride red fluorescent powder
The preparation method of the wet-resistant fluoride red fluorescent powder comprises the following steps: will be 1g K 2 TiF 6 :Mn 4+ Fluorescent powder, 7.4mL of oleylamine and 25mL of absolute ethyl alcohol are simultaneously added into a 100mL polytetrafluoroethylene reaction kettle, and the reaction kettle is sealed and sonicated for 1 hour to fully mix reactants. Subsequently, the reaction vessel was put into an oven at 200℃for reaction for 5 hours. After cooling, the reacted mixture was centrifuged and dried in vacuo at 50℃for 3 hours to obtain a wet-resistant fluoride red phosphor. The chemical formula of the moisture-resistant fluoride red fluorescent powder can be expressed as K 2 TiF 6 :Mn 4+ @ OAm (labeled ktfm @ oam).
The emission spectra of the fluorescent powders KTFM and KTFM@OAm obtained in the embodiment 3 under the excitation of 450nm blue light are shown in figure 10, and the two samples can emit red light under the excitation of 450nm blue light.
The change of the luminescence intensity of the fluorescent powder KTFM and KTFM@OAm obtained in the example 3 with time under the humidity resistance test condition of 0.3g/5mL deionized water is shown in FIG. 11, and 73.3% of the original intensity of the fluorescent powder KTFM@OAm is still maintained after the fluorescent powder KTFM@OAm is soaked in water for 6 hours, and no obvious decrease trend exists, which indicates that the humidity resistance of the fluorescent powder coated by the oleylamine (namely the humidity resistance fluoride red fluorescent powder prepared in the example 3) under the normal temperature preparation condition is obviously improved.
Example 4
It differs from example 1 only in that in step (2), the reaction vessel was placed in a 200 ℃ oven for 1 hour.
Example 5
It differs from example 1 only in that in step (2), the reaction vessel was placed in a 100℃oven for 6 hours.
Example 6
It is different from example 1 only in that in the step (2), the preparation method of the moisture-resistant fluoride red phosphor was includedThe method comprises the following steps: will be 1g K 2 SiF 6 :Mn 4+ Fluorescent powder, 1.88mL of undecylenic amine and 25mL of absolute ethyl alcohol are simultaneously added into a 100mL polytetrafluoroethylene reaction kettle, and the reaction kettle is sealed and dispersed for 1 hour by ultrasonic so that reactants are fully mixed. Subsequently, the reaction vessel was put into an oven at 200℃for 3 hours. Centrifuging the reacted mixture after cooling and vacuum drying at 50deg.C for 3 hr to obtain moisture-resistant fluoride red phosphor, which can be expressed as K 2 SiF 6 :Mn 4+ @C 11 H 23 N (which may be labeled KSFM@C 11 H 23 N)。
Comparative example 1
The preparation method of the wet-resistant fluoride red fluorescent powder comprises the following steps:
3.556g NH 4 F. 1.394g KF was placed in a 100mL polytetrafluoroethylene liner, 8mL deionized water was added dropwise to the vessel and stirred for 5 minutes, followed by 0.296g K 2 MnF 6 And stirred for 10 minutes. Subsequently, 32mL of hydrochloric acid solution (3 mol/L) was dropped into the reaction solution, and stirred for 10 minutes. To the solution, 4.44mL of oleylamine was added dropwise, followed by 2.5g of tetraethyl silicate (TEOS), and the reaction was stirred at 25℃for 3 hours. Centrifuging the reaction solution to remove supernatant, repeatedly washing the lower precipitate with absolute ethanol, centrifuging for 3 times, and vacuum drying the precipitate at 50deg.C for 3 hr to obtain product K 2 SiF 6 :Mn 4 + + OAm (labeled ksfm+ OAm).
The emission spectra of the phosphor KSFM+ OAm obtained in comparative example 1 and the phosphors KSFM, KSFM@OAm-3x obtained in example 1 under 455nm excitation are shown in FIG. 12, wherein the peak emission intensity of the phosphor KSFM+ OAm obtained in comparative example 1 at 631nm is only 5.6% of that of the phosphor KSFM@OAm-3x obtained in example 1, 6.6% of that of KSFM, indicating that the phosphor KSFM is excited at K 2 SiF 6 :Mn 4+ The direct addition of oleylamine in the preparation process can cause the great decrease of the luminous intensity of the fluorescent powder, and the practical application is not possible.
The emission spectra of the phosphor KSFM+ OAm prepared in comparative example 1 before and after moisture resistance testing of 0.3g/5mL deionized water is shown in FIG. 13, and the phosphor KSFM+ OAm is immersed for 5 minutesThe luminous intensity at clock time has fallen to 2.8% of the initial value, which is shown in K 2 SiF 6 :Mn 4+ The fluorescent powder obtained by directly adding oleylamine in the preparation process has extremely poor moisture resistance.
Comparative example 2
This differs from comparative example 2 only in that in the preparation method of the wet-resistant fluoride red phosphor of step (2), 4.44mL of oleylamine was dropped into the solution, followed by 2.5g of tetraethyl silicate (TEOS), and the reaction was hydrothermal-reacted at 200 ℃ for 3 hours. Centrifuging the reaction solution to remove supernatant, repeatedly washing the lower precipitate with absolute ethanol, centrifuging for 3 times, and vacuum drying the precipitate at 50deg.C for 3 hr to obtain product K 2 SiF 6 :Mn 4+ + OAm-200-3h (labeled KSFM+ OAm-200-3 h).
The emission peak intensities of the phosphor KSFM+ OAm prepared in comparative example 1 and the phosphor KSFM+ OAm-200-3h prepared in comparative example 2 and the phosphor KSFM, KSFM@OAm-3x prepared in example 1 after 5 minutes of immersion at 631nm under 455nm excitation are shown in FIG. 14, wherein the emission intensity of the phosphor KSFM+ OAm-200-3h prepared in comparative example 2 at 631nm is only 0.16% of that of the phosphor KSFM@OAm-3x prepared in example 1, 0.19% of that of the KSFM, indicating Mn obtained by adding oleylamine directly during the preparation and performing hydrothermal reaction 4+ The fluorescent powder for activating fluoride red has extremely poor luminescence performance and cannot be practically applied.
As can be seen from comparative examples 1 and 2, mn was produced 4+ The mode of adding oleylamine simultaneously in the preparation process of activating the inorganic fluoride red fluorescent powder not only ensures that the prepared product has very weak luminous performance, but also can not form a waterproof coating layer, and the prepared product has very poor moisture resistance.
In summary, the preparation method provided by the application has the advantages of simple process, simple flow, low cost and low processing difficulty, can realize batch production of the moisture-resistant fluoride red fluorescent powder, has good moisture resistance, can be stably used in a humid environment for a long time, and can be applied to preparation of a light-emitting device, a paint or a display device.
The foregoing is merely a specific embodiment of the present application and is not intended to limit the application, and various modifications and variations may be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application should be included in the protection scope of the present application.
Claims (10)
1. A moisture-resistant fluoride red phosphor is characterized in that the moisture-resistant fluoride red phosphor comprises Mn 4+ Activating a full inorganic fluoride red fluorescent powder and an amine coating layer, wherein the amine coating layer is coated on the Mn 4+ Activating the surface of the full inorganic fluoride red phosphor.
2. The wet-resistant fluoride red phosphor of claim 1, wherein the amine-based coating layer comprises an unsaturated aliphatic amine having 10 to 20 carbon atoms;
optionally, the unsaturated fatty amine comprises at least one of undecylenamine, dodecenamine, tridecenylamine, tetradecylenamine, pentadecenylamine, hexadecylenamine, heptadecenylamine, octadecyl enamine;
optionally, the amine coating layer comprises octadecylamine.
3. The wet-resistant fluoride red phosphor of claim 1, wherein the amine coating comprises at least one amine group and at least one linear unsaturated organic carbon chain, at least a portion of the amine group and the Mn 4+ The fluoride ions activating the surface of the inorganic fluoride red fluorescent powder combine and form hydrogen bonds, and the linear unsaturated organic carbon chain points to the Mn 4+ Activating the outer side of the inorganic fluoride red fluorescent powder;
optionally, the linear unsaturated organic carbon chain contains 10-20 carbon atoms, and contains carbon-carbon double bonds;
optionally, the linear unsaturated organic carbon chain has a carbon number of 18.
4. The wet-resistant fluoride red phosphor of any one of claims 1-3, wherein the Mn 4+ The chemical formula of the activated inorganic fluoride red fluorescent powder is A 2 XF 6 :Mn 4+ Wherein A is selected from at least one of Li, na, K, rb and Cs, and X is selected from at least one of Si, ge, ti and Zr.
5. The wet-resistant fluoride red phosphor of any one of claims 1 to 3, wherein the excitation wavelength of the wet-resistant fluoride red phosphor is 300 to 500nm and the wavelength of the strongest emission peak is 620 to 640nm.
6. The method for preparing the wet-resistant fluoride red phosphor according to any one of claims 1 to 5, comprising:
mn of the mixture 4+ Activating the inorganic fluoride red fluorescent powder, amine compounds and alcohol, mixing and dispersing to obtain a solid-liquid mixture;
reacting the solid-liquid mixture at a temperature of not less than 25 ℃ for at least 1h;
wherein the amine compound has a linear unsaturated organic carbon chain and an amine group.
7. The method according to claim 6, wherein the temperature of the reaction is 100 to 200 ℃, and the time of the reaction is 1 to 9 hours;
alternatively, the alcohol comprises a monohydric alcohol having no more than 6 carbon atoms.
8. The method according to claim 6, wherein the Mn 4+ The molar ratio of the activated inorganic fluoride red fluorescent powder to the amine compound is 1 (0.1-10);
alternatively, the Mn 4+ The particle size of the activated inorganic fluoride red phosphor is 0.1-50 μm.
9. The method of preparation of claim 6, wherein the dispersing comprises ultrasonic dispersion;
optionally, the ultrasonic power of the ultrasonic dispersion is 50-300W, and the ultrasonic time is 0.5-1h.
10. Use of the moisture resistant fluoride red phosphor of any one of claims 1-5 in the manufacture of a light emitting device, paint or display.
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| US20150329770A1 (en) * | 2012-12-28 | 2015-11-19 | Shin-Etsu Chemical Co., Ltd. | Phosphor surface treatment method |
| 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 |
| KR20200095207A (en) * | 2019-01-31 | 2020-08-10 | 한국화학연구원 | Fabrication Method of Metal Fluoride-based Phosphors |
| CN113583656A (en) * | 2021-08-23 | 2021-11-02 | 中国计量大学 | Oleamidooleic acid modified tetravalent manganese doped fluoride red light material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150329770A1 (en) * | 2012-12-28 | 2015-11-19 | Shin-Etsu Chemical Co., Ltd. | Phosphor surface treatment method |
| 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 |
| KR20200095207A (en) * | 2019-01-31 | 2020-08-10 | 한국화학연구원 | Fabrication Method of Metal Fluoride-based Phosphors |
| CN113583656A (en) * | 2021-08-23 | 2021-11-02 | 中国计量大学 | Oleamidooleic acid modified tetravalent manganese doped fluoride red light material and preparation method thereof |
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