CN105950143A - Red phosphor, preparation method thereof and light emitting device using red phosphor - Google Patents
Red phosphor, preparation method thereof and light emitting device using red phosphor Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 46
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract 10
- 239000000463 material Substances 0.000 claims abstract description 59
- DSFLPAXQDSLSKU-UHFFFAOYSA-L [Mn](=O)(=O)(O)O.[F] Chemical compound [Mn](=O)(=O)(O)O.[F] DSFLPAXQDSLSKU-UHFFFAOYSA-L 0.000 claims abstract description 14
- 238000005253 cladding Methods 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 5
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 3
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 3
- 229910052709 silver Inorganic materials 0.000 claims abstract description 3
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims description 50
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 46
- 238000003756 stirring Methods 0.000 claims description 45
- 238000004448 titration Methods 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 33
- 239000007788 liquid Substances 0.000 claims description 32
- 238000000926 separation method Methods 0.000 claims description 31
- 238000005406 washing Methods 0.000 claims description 27
- 239000000843 powder Substances 0.000 claims description 26
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 17
- 238000001556 precipitation Methods 0.000 claims description 14
- 238000012216 screening Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 239000012286 potassium permanganate Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- 150000007513 acids Chemical class 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000000428 dust Substances 0.000 claims description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical class [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 6
- 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 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims 1
- 150000004767 nitrides Chemical class 0.000 abstract description 5
- XPIIDKFHGDPTIY-UHFFFAOYSA-N F.F.F.P Chemical compound F.F.F.P XPIIDKFHGDPTIY-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 63
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 40
- -1 polytetrafluoroethylene Polymers 0.000 description 20
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 20
- 239000004810 polytetrafluoroethylene Substances 0.000 description 20
- 229960002050 hydrofluoric acid Drugs 0.000 description 18
- 239000007789 gas Substances 0.000 description 13
- 229910000590 K2MnF6 Inorganic materials 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 229910004074 SiF6 Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910004595 Na2MnF6 Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 241001025261 Neoraja caerulea Species 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910003638 H2SiF6 Inorganic materials 0.000 description 1
- 229910003708 H2TiF6 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910019990 cerium-doped yttrium aluminum garnet Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229950000845 politef Drugs 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- ZEFWRWWINDLIIV-UHFFFAOYSA-N tetrafluorosilane;dihydrofluoride Chemical compound F.F.F[Si](F)(F)F ZEFWRWWINDLIIV-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
- C09K11/664—Halogenides
- C09K11/665—Halogenides with alkali or alkaline earth metals
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/67—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
-
- 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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- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention discloses red phosphor, a preparation method thereof and a light emitting device using the red phosphor. The chemical formula of the red phosphor is as follows: A2B1-xF6: Mnx, wherein A is one or more elements of Li, Na, K, Ag and Cu; B comprises a C element and one or more elements of Si, Ti and Ge; and x is greater than or equal to 0.001 and smaller than or equal to 0.5. The preparation method comprises the following steps: preparing fluorine manganate which has an A2MnF6 structure and contains Mn4+; preparing fluoride phosphor with an A2B1-xF6: Mnx structure; and carrying out cladding treatment on the phosphor. The red phosphor has high light emitting performance in a high band, half-peak breadth of the red phosphor is only about 7.2 nm, the red phosphor is applied to the field of display, the color gamut NTSC (1931) can be increased to be above 85%, and therefore, shortcomings of nitride red luminescent materials are overcome.
Description
Technical field
The present invention relates to LED technology field, and particularly to one can by ultraviolet, near ultraviolet, purple light and
Fluoride red fluorescence powder that blue light effectively excites and preparation method thereof and the luminous organ of this fluorescent material of employing
Part.
Background technology
Light emitting diode (LED) has low-voltage, specular removal, low energy consumption, the long-life, pollution-free etc.
At semiconductor lighting and liquid crystal flat-panel, advantage, shows that field is successfully applied.White light LEDs at present
Implementation be broadly divided into two kinds: the first is the combination of three primary colours (red, blue, green) LED chip；
Another kind is to excite fluorescence to be mixed to form white light with LED, i.e. coordinates Yellow light-emitting low temperature with blue-light LED chip
Fluorescent material, or coordinate glow green and two kinds of fluorescent material of red light with blue-ray LED, or use ultraviolet
Or purple LED three kinds of fluorescent material of deexcitation red, green, blue etc..In these implementations, blue-ray LED
Chip coordinate YAG:Ce yellow fluorescent powder mode is simple, easy and relative low price, become white
The mainstream scheme of light LED.But making the white-light spectrum formed in this way more single, spectrum is main
Concentrating on yellow region, the white light LEDs color rendering properties causing preparation is relatively low.By adding in encapsulation process
Red fluorescence powder can compensate the red color components of disappearance in white LED spectrum, improves white light LEDs product
Color developing.
But the most traditional red fluorescence powder such as sulfide and oxide etc., also exist light decay big, chemical
The defects such as poor stability, it is impossible to reach Perfect Matchings with LED chip.The most novel nitride is red
Sulfide and oxide that color fluorescent material is more traditional have had the biggest improvements, such as CaAlSiN3:Eu and
Ba2Si5N8:Eu, but owing to nitride red luminescent material is that wide range is launched and high band luminous efficiency is low
Shortcoming, be applied to display field colour gamut NTSC (1931) and can only achieve about 70%, and can not obtain
To efficient dark red coloured light.
Summary of the invention
The technical problem to be solved is to provide a kind of red fluorescence powder and preparation method thereof and uses
The luminescent device of this fluorescent material, which overcomes the disadvantages mentioned above of prior art.
The technical problem to be solved is achieved through the following technical solutions:
A kind of red fluorescence powder, the chemical formula of described fluorescent material consists of: A2B1-xF6:Mnx, wherein,
A is one or more elements of Li, Na, K, Ag and Cu；
B is one or more elements of C element and Si, Ti and Ge；
0.001≤x≤0.5。
The preparation method of a kind of red fluorescence powder, comprises the following steps:
1) preparation has A2MnF6Structure contains Mn4+Fluorine manganate:
Fluoride containing A or bifluoride are dissolved in Fluohydric acid., add KMnO4, the most molten
Xie Hou, instills H2O2, when solution is become yellow from brown purple, stopping titration, titration is formed after terminating
Golden yellow precipitate thing, solid-liquid separation, washing, it is dried to obtain A2MnF6；
2) there is A2B1-xF6:MnxThe preparation of structure fluoride fluorescent material:
The preparation of No. 1 solution: take hydrofluoric acid solution, is added thereto to the fluoride containing element A or fluorine
Hydride, to be dissolved after, add step 1 prepare A2MnF6, after being completely dissolved, obtain No. 1 solution；
The preparation of No. 2 solution: separately take after hydrofluoric acid solution is heated to uniform temperature, be added thereto to carbon dust,
After to be dissolved, add a certain amount of fluorine-containing salt, acids or oxide, until completely dissolved, obtain 2
Number solution；
Titration: keep No. 2 solution temperatures invariable, No. 2 solution limits of stirring, limit instill No. 1 solution,
Titration process forms precipitation, solid-liquid separation, obtains fluorescent material.
Preferably, in technique scheme, further comprising the steps of:
3) cladding of fluorescent material processes:
In ethanol add Fluohydric acid., regulation pH to 2-6 after, be added thereto to step 2) prepare glimmering
Light powder, heats mixed liquor after mix homogeneously so that it is temperature is maintained between 50 DEG C-80 DEG C；While stir
Mix limit and instill appropriate tetraethyl orthosilicate, solid-liquid separation, after washing is to pH to 7, dry, screening, obtain glimmering
Fluorescent material after light powder powder surface peplos.
The preparation method of a kind of red fluorescence powder, comprises the following steps:
1) preparation has A2MnF6Structure contains Mn4+Fluorine manganate:
Fluoride containing A or bifluoride are dissolved in Fluohydric acid., add KMnO4, the most molten
Xie Hou, instills H2O2, when solution is become yellow from brown purple, stopping titration, titration is formed after terminating
Golden yellow precipitate thing, solid-liquid separation, washing, it is dried to obtain A2MnF6；
2) there is A2B1-xF6:MnxThe preparation of structure fluoride fluorescent material:
The preparation of No. 1 solution: take hydrofluoric acid solution, is added thereto to the fluoride containing element A or fluorine
Hydride, to be dissolved after, add step 1 prepare A2MnF6, after being completely dissolved, obtain No. 1 solution；
The preparation of No. 2 solution: separately take after hydrofluoric acid solution is heated to uniform temperature, add a certain amount of containing
Villiaumite class, acids or oxide, until completely dissolved, obtain No. 2 solution；
Titration: keep No. 2 solution temperatures invariable, be passed through CF4Gas, and use CF4Gas shield,
Stirring No. 2 solution and instill No. 1 solution simultaneously, titration process forms precipitation, solid-liquid separation, obtains fluorescent material.
3) cladding of fluorescent material processes:
In ethanol add Fluohydric acid., regulation pH to 2-6 after, be added thereto to step 2) prepare glimmering
Light powder, heats mixed liquor after mix homogeneously so that it is temperature is maintained between 50 DEG C-80 DEG C；While stir
Mix limit and instill appropriate tetraethyl orthosilicate, solid-liquid separation, after washing is to pH to 7, dry, screening, obtain glimmering
Fluorescent material after light powder powder surface peplos.
In technique scheme, preferably:
Preferably, described step 1) in, hydrofluoric acid concentration is 40-60wt%, preferably 55wt%；H2O2
Concentration is 30-40wt%, preferably 40wt%.
Preferably, described step 1) in, described fluoride or bifluoride and KMnO4Mol ratio be:
40:1-20:1。
Preferably, described step 2) in, in the preparation of No. 1 solution: hydrofluoric acid concentration is 40-60wt%,
It is preferably 50wt%；In the preparation of No. 2 solution: hydrofluoric acid concentration is 60-80wt%, preferably 65wt%,
Hydrofluoric acid temperature controls at 50-80 DEG C, preferably 70 DEG C；Titration: rate of titration is 0.5-5 drop/sec, preferably
Being 1 drop/sec, be passed through CF4 gas flow and control at 0.1-5L/ minute, container pressure controls at 0.15-1MPa,
Preferably 0.5MPa, it is 10-100 minute that titration terminates rear mixing time, preferably 50 minutes.
Preferably, described step 2) in fluorine-containing salt, acids or oxide refer to comprise Si, Ti and
Fluorine-containing salt, acids or the oxide of the one or more of which of Ge element.
Preferably, described step 3) in, the concentration of Fluohydric acid. is 10-15wt%, preferably 10wt%,
PH is 2-6, preferably 4, and before dropping tetraethyl orthosilicate, solution temperature is maintained at 70-90 DEG C, preferably 80 DEG C,
Titration terminate after stir 5-20 hour, preferably 10 hours.
Preferably, described step 3) in, described fluorescent material is 100 with the weight ratio of described tetraethyl orthosilicate:
(15-55), preferably 100:35.
A kind of white light LED luminescent device comprising above-mentioned red fluorescence powder.
Technique scheme of the present invention, has the advantages that
Compared with prior art, the fluoride red illuminating material of the present invention has stronger sending out at high band
Optical property, and half-peak breadth only has about 7.2nm, is applied to display field, colour gamut NTSC (1931)
Can bring up to more than 85%, thus the shortcoming of the nitride red luminescent material of quasi-complement.Add a certain amount of
The fluorescent material of carbon dust, its brightness is higher, and the most existing fluorescent material of stability is more preferable.
Accompanying drawing explanation
Fig. 1 is the excitation spectrum of the embodiment of the present invention 9.
Fig. 2 is the emission spectrum of the embodiment of the present invention 9.
Fig. 3 is the granule-morphology of the embodiment of the present invention 9.
Detailed description of the invention
Below the specific embodiment of the present invention is described in detail, in order to be further appreciated by the present invention.
Embodiment 1 K2C0.02Si0.93F6:Mn0.05
(1) synthesis has K2MnF6Structure contains Mn4+Fluorine manganate:
Weigh the KHF of 93g2, it is dissolved in the Fluohydric acid. that 800ml concentration is 55wt%, adds 7g
KMnO4, wait to be completely dissolved, instilling 5ml concentration while stirring is the H of 40%2O2, after titration terminates
Stir 40 minutes, precipitation, solid-liquid separation；With washing with acetone 5 times, use 100ml every time；100 DEG C of drying
3 hours, obtain K2MnF6。
(2)K2C0.02Si0.93F6:Mn0.05Preparation:
According to stoichiometric proportion, in polytetrafluoroethylene beaker, add the hydrogen that concentration is 50wt% of 600ml
Fluoric acid, stirring adds 12.4g K2MnF6Until completely dissolved, 187g KHF is added2It is completely dissolved system
Obtain No. 1 solution；
65wt% Fluohydric acid. 2000ml pours in polytetrafluoroethylene beaker, then is put into by beaker in heating bath,
When temperature reaches 70 DEG C, stirring adds 0.24g carbon dust, and adding 350ml concentration after being completely dissolved is 45wt%
Hexafluosilicic acid (H2SiF6) mix homogeneously prepares No. 2 solution；
Keeping No. 2 solution temperature No. 1 solution of dropping, rate of titration is 1 drop/sec, within about 200 minutes, drips
Add, stirred 50 minutes after completion of dropwise addition, solid-liquid separation；With washing with acetone 3 times, use 350ml every time；
Dry 4 hours for 70 DEG C, screening, obtain fluorescent material sample.
(3) cladding of fluorescent material processes:
Adding 1000ml ethanol in the beaker of 2L politef, adding 2ml concentration is 10wt% hydrogen
Fluoric acid, the pH of regulation solution is 4, adds fluorescent material 100g, mixed solution is heated to 50 DEG C, protects
Holding temperature, instill tetraethyl orthosilicate 35ml while stirring, titration time is 120 minutes, after titration terminates
Stir 10 minutes, precipitation, solid-liquid separation, washing with acetone 3 times, 70 DEG C of drying, screening, obtain
K2C0.02Si0.93F6:Mn0.05Sample.
Embodiment 2 Na2C0.04Si0.91F6:Mn0.05
(1) synthesis has Na2MnF6Structure contains Mn4+Fluorine manganate:
Weigh the NaF of 40g, be dissolved in the Fluohydric acid. that 800ml concentration is 55wt%, add 7g's
KMnO4, wait to be completely dissolved, instilling 5ml concentration while stirring is the H of 40%2O2, titration is stirred after terminating
Mix 40 minutes, precipitation, solid-liquid separation；With washing with acetone 5 times, use 100ml every time；Dry 3 for 100 DEG C
Hour, obtain Na2MnF6。
(2)Na2C0.04Si0.91F6:Mn0.05Preparation:
According to stoichiometric proportion, in polytetrafluoroethylene beaker, add the hydrogen that concentration is 80wt% of 600ml
Fluoric acid, stirring adds 10.7g Na2MnF6Until completely dissolved, add 80g NaF and be completely dissolved prepared
No. 1 solution；
80wt% Fluohydric acid. 2000ml pours in polytetrafluoroethylene beaker, then is put into by beaker in heating bath,
After temperature reaches 70 DEG C, add the hexafluosilicic acid (H that 350ml concentration is 45wt%2SiF6) mix homogeneously
Prepare No. 2 solution；
Keep No. 2 solution temperatures, be passed through CF4Gas, flow 1L/min, and use CF4Gas shield,
Protective atmosphere pressure is 0.5MPa, is simultaneously added dropwise No. 1 solution, and rate of titration is 1 drop/sec, about 200
Minute it is added dropwise to complete, stirs 50 minutes after completion of dropwise addition, solid-liquid separation；With washing with acetone 3 times, every time
Use 350ml；Dry 4 hours for 70 DEG C, screening, fluorescent material sample must be obtained.
(3) cladding of fluorescent material processes:
With the method for embodiment 1, final Na2C0.04Si0.91F6:Mn0.05。
Embodiment 3 K2C0.06Ti0.89F6:Mn0.05
(1) synthesis has K2MnF6Structure contains Mn4+Fluorine manganate:
Weigh the KF of 55.1g, be dissolved in the Fluohydric acid. that 800ml concentration is 55wt%, add 7g
KMnO4, wait to be completely dissolved, instilling 5ml concentration while stirring is the H of 40%2O2, after titration terminates
Stir 40 minutes, precipitation, solid-liquid separation；With washing with acetone 5 times, use 100ml every time；100 DEG C of drying
3 hours, obtain K2MnF6。
(2)K2C0.06Ti0.89F6:Mn0.05Preparation:
According to stoichiometric proportion, in polytetrafluoroethylene beaker, add the hydrogen that concentration is 70wt% of 600ml
Fluoric acid, stirring adds 12.4g K2MnF6Until completely dissolved, add 110g KF and be completely dissolved prepared
No. 1 solution；
70wt% Fluohydric acid. 2000ml pours in polytetrafluoroethylene beaker, then is put into by beaker in heating bath,
When temperature reaches 75 DEG C, stirring adds 0.72g carbon dust, and adding 350ml concentration after being completely dissolved is 45wt%
Fluotitanic acid (H2TiF6) mix homogeneously prepares No. 2 solution；
Keeping No. 2 solution temperature No. 1 solution of dropping, rate of titration is 1 drop/sec, within about 200 minutes, drips
Add, stirred 50 minutes after completion of dropwise addition, solid-liquid separation；With washing with acetone 3 times, use 350ml every time；
Dry 4 hours for 70 DEG C, screening, obtain fluorescent material sample.
(3) cladding of fluorescent material processes:
With the method for embodiment 1, final K2C0.06Ti0.89F6:Mn0.05。
Embodiment 4 Ag2C0.08(Si0.81Ti0.06)F6:Mn0.05
(1) synthesis has Ag2MnF6Structure contains Mn4+Fluorine manganate:
Weigh the AgF of 120.5g, be dissolved in the Fluohydric acid. that 800ml concentration is 55wt%, add 7g
KMnO4, wait to be completely dissolved, instilling 5ml concentration while stirring is the H of 40%2O2, after titration terminates
Stir 40 minutes, precipitation, solid-liquid separation；With washing with acetone 5 times, use 100ml every time；100 DEG C of drying
3 hours, obtain Ag2MnF6。
(2)Ag2C0.08(Si0.81Ti0.06)F6:Mn0.05Preparation:
According to stoichiometric proportion, in polytetrafluoroethylene beaker, add the hydrogen that concentration is 70wt% of 600ml
Fluoric acid, stirring adds 19.2gAg2MnF6Until completely dissolved, add 241g AgF and be completely dissolved system
Obtain No. 1 solution；
70wt% Fluohydric acid. 2000ml pours in polytetrafluoroethylene beaker, then is put into by beaker in heating bath,
After temperature reaches 75 DEG C, add the hexafluosilicic acid (H that 300ml concentration is 45wt%2SiF6) and 40ml
Concentration is the fluotitanic acid (H of 40wt%2TiF6), mix homogeneously prepares No. 2 solution；
No. 2 solution temperatures are kept to be passed through CF4Gas, flow 2L/min, and use CF4Gas shield, protects
Protecting atmosphere pressures is 0.5MPa, is simultaneously added dropwise No. 1 solution, and rate of titration is 1 drop/sec, about 200 points
Clock is added dropwise to complete, and stirs 50 minutes, solid-liquid separation after completion of dropwise addition；With washing with acetone 3 times, use every time
350ml；Dry 4 hours for 70 DEG C, screening, obtain fluorescent material sample.
(3) cladding of fluorescent material processes:
With the method for embodiment 1, final Ag2C0.08(Si0.81Ti0.06)F6:Mn0.05。
Embodiment 5 Li2C0.04(Si0.80Ge0.13)F6:Mn0.03
(1) synthesis has Li2MnF6Structure contains Mn4+Fluorine manganate:
Weigh the LiF of 24.7g, be dissolved in the Fluohydric acid. that 800ml concentration is 55wt%, add 7g
KMnO4, wait to be completely dissolved, instilling 5ml concentration while stirring is the H of 40%2O2, after titration terminates
Stir 40 minutes, precipitation, solid-liquid separation；With washing with acetone 5 times, use 100ml every time；100 DEG C of drying
3 hours, obtain K2MnF6。
(2)Li2C0.04(Si0.80Ge0.13)F6:Mn0.03Preparation:
According to stoichiometric proportion, in polytetrafluoroethylene beaker, add the hydrogen that concentration is 70wt% of 600ml
Fluoric acid, stirring adds 5.5g Li2MnF6Until completely dissolved, add 50.3g LiF and be completely dissolved prepared
No. 1 solution；
70wt% Fluohydric acid. 2000ml pours in polytetrafluoroethylene beaker, then is put into by beaker in heating bath,
When temperature reaches 75 DEG C, stirring adds 0.48g carbon dust, and adding 280ml concentration after being completely dissolved is 45wt%
Hexafluosilicic acid and 60ml concentration be the fluogermanic acid of 45wt%；
Keeping No. 2 solution temperature No. 1 solution of dropping, rate of titration is 1 drop/sec, within about 200 minutes, drips
Add, stirred 50 minutes after completion of dropwise addition, solid-liquid separation；With washing with acetone 3 times, use 350ml every time；
Dry 4 hours for 70 DEG C, screening, obtain fluorescent material sample.
(3) cladding of fluorescent material processes:
With the method for embodiment 1, final Li2C0.04(Si0.80Ge0.11)F6:Mn0.03。
Embodiment 6 (KLi)2C0.04Ti0.89F6:Mn0.07
(1) synthesis has (KLi)2MnF6Structure contains Mn4+Fluorine manganate:
Weigh the KF of 27.6g, 12.4g LiF, be dissolved in the Fluohydric acid. that 800ml concentration is 55wt%,
Add the KMnO of 7g4, wait to be completely dissolved, instilling 5ml concentration while stirring is the H of 40%2O2,
Titration is stirred 40 minutes after terminating, precipitation, solid-liquid separation；With washing with acetone 4 times, use 100ml every time；
Dry 3 hours, obtain (KLi) for 100 DEG C2MnF6。
(2)(KLi)2C0.04Ti0.89F6:Mn0.05Preparation:
According to stoichiometric proportion, in polytetrafluoroethylene beaker, add the hydrogen that concentration is 70wt% of 600ml
Fluoric acid, stirring adds 8.6g (KLi)2MnF6Until completely dissolved, 55g KF, 25g LiF are added complete
CL prepares No. 1 solution；
70wt% Fluohydric acid. 2000ml pours in polytetrafluoroethylene beaker, then is put into by beaker in heating bath,
After temperature reaches 75 DEG C, add the fluotitanic acid (H that 350ml concentration is 45wt%2TiF6) mix homogeneously
Prepare No. 2 solution；
No. 2 solution temperatures are kept to be passed through CF4Gas, flow 1.0L/min, and use CF4Gas shield, protects
Protecting atmosphere pressures is 0.5MPa, is simultaneously added dropwise No. 1 solution, and rate of titration is 1 drop/sec, about 200 points
Clock is added dropwise to complete, and stirs 50 minutes, solid-liquid separation after completion of dropwise addition；With washing with acetone 3 times, use every time
350ml；Dry 4 hours for 70 DEG C, screening, obtain fluorescent material sample.
(3) cladding of fluorescent material processes:
With the method for embodiment 1, final (KLi)2C0.04Ti0.89F6:Mn0.07。
Embodiment 7 Ag2C0.06Ge0.85F6:Mn0.09
(1) synthesis has Ag2MnF6Structure contains Mn4+Fluorine manganate:
Weigh the AgF of 120.5g, be dissolved in the Fluohydric acid. that 800ml concentration is 55wt%, add 7g
KMnO4, wait to be completely dissolved, instilling 5ml concentration while stirring is the H of 40%2O2, after titration terminates
Stir 40 minutes, precipitation, solid-liquid separation；With washing with acetone 4 times, use 100ml every time；100 DEG C of drying
3 hours, obtain Ag2MnF6。
(2)AgC0.06Ge0.85F6:Mn0.09Preparation:
According to stoichiometric proportion, in polytetrafluoroethylene beaker, add the hydrogen that concentration is 70wt% of 600ml
Fluoric acid, stirring adds 34.6gAg2MnF6Until completely dissolved, add 230.9gAgF and be completely dissolved system
Obtain No. 1 solution；
70wt% Fluohydric acid. 2000ml pours in polytetrafluoroethylene beaker, then is put into by beaker in heating bath,
When temperature reaches 75 DEG C, stirring adds 0.72g carbon dust, adds germanium oxide 88.8g after being completely dissolved, mixed
Close and uniformly prepare No. 2 solution；
Keeping No. 2 solution temperature No. 1 solution of dropping, rate of titration is 1 drop/sec, within about 200 minutes, drips
Add, stirred 50 minutes after completion of dropwise addition, solid-liquid separation；With washing with acetone 3 times, use 350ml every time；
Dry 4 hours for 70 DEG C, screening, obtain fluorescent material sample.
(3) cladding of fluorescent material processes:
With the method for embodiment 1, final Ag2C0.06Ge0.85F6:Mn0.09。
Embodiment 8 (NaLi)2C0.02(Si0.69Ti0.09Ge0.09)F6:Mn0.11
(1) synthesis has (NaLi)2MnF6Structure contains Mn4+Fluorine manganate:
Weigh the NaF of 20g, 12.3g LiF, be dissolved in the Fluohydric acid. that 800ml concentration is 55wt%,
Add the KMnO of 7g4, wait to be completely dissolved, instilling 5ml concentration while stirring is the H of 40%2O2,
Titration is stirred 40 minutes after terminating, precipitation, solid-liquid separation；With washing with acetone 5 times, use 100ml every time；
Dry 3 hours, obtain (NaLi) for 100 DEG C2MnF6。
(2)(NaLi)2C0.02(Si0.69Ti0.09Ge0.09)F6:Mn0.11Preparation:
According to stoichiometric proportion, in polytetrafluoroethylene beaker, add the hydrogen that concentration is 70wt% of 600ml
Fluoric acid, stirring adds 7.1g (NaLi)2MnF6Until completely dissolved, 37.5g NaF, 23g LiF are added
It is completely dissolved prepared No. 1 solution；
70wt% Fluohydric acid. 2000ml pours in polytetrafluoroethylene beaker, then is put into by beaker in heating bath,
After temperature reaches 75 DEG C, add the hexafluosilicic acid (H that 200ml concentration is 45wt%2SiF6), 80ml dense
Degree is the fluotitanic acid (H of 40wt%2TiF6) and 60ml concentration be the fluogermanic acid of 45wt%, mix homogeneously
Prepare No. 2 solution；
No. 2 solution temperatures are kept to be passed through CF4Gas, flow 0.5L/min, and use CF4Gas shield, protects
Protecting atmosphere pressures is 0.5MPa, is simultaneously added dropwise No. 1 solution, and rate of titration is 1 drop/sec, about 200 points
Clock is added dropwise to complete, and stirs 50 minutes, solid-liquid separation after completion of dropwise addition；With washing with acetone 3 times, use every time
350ml；Dry 4 hours for 70 DEG C, screening, obtain fluorescent material sample.
(3) cladding of fluorescent material processes:
With the method for embodiment 1, final (NaLi)2C0.02(Si0.75Ti0.09Ge0.09)F6:Mn0.11。
Embodiment 9 K2C0.04Si0.89F6:Mn0.07
(1) synthesis has K2MnF6Structure contains Mn4+Fluorine manganate:
Weigh the KF of 55.1g, be dissolved in the Fluohydric acid. that 800ml concentration is 55wt%, add 7g
KMnO4, wait to be completely dissolved, instilling 5ml concentration while stirring is the H of 40%2O2, after titration terminates
Stir 40 minutes, precipitation, solid-liquid separation；With washing with acetone 5 times, use 100ml every time；100 DEG C of drying
3 hours, obtain K2MnF6。
(2)K2C0.04Ti0.89F6:Mn0.07Preparation:
According to stoichiometric proportion, in polytetrafluoroethylene beaker, add the hydrogen that concentration is 70wt% of 600ml
Fluoric acid, stirring adds 17.3g K2MnF6Until completely dissolved, add 108g KF and be completely dissolved prepared
No. 1 solution；
70wt% Fluohydric acid. 2000ml pours in polytetrafluoroethylene beaker, then is put into by beaker in heating bath,
After temperature reaches 75 DEG C, add the hexafluosilicic acid (H that 350ml concentration is 45wt%2SiF6) mix homogeneously
Prepare No. 2 solution；
No. 2 solution temperatures are kept to be passed through CF4Gas, flow 1L/min, and use CF4Gas shield, protects
Protecting atmosphere pressures is 0.5MPa, is simultaneously added dropwise No. 1 solution, and rate of titration is 1 drop/sec, about 200 points
Clock is added dropwise to complete, and stirs 50 minutes, solid-liquid separation after completion of dropwise addition；With washing with acetone 3 times, use every time
350ml；Dry 4 hours for 70 DEG C, screening, obtain fluorescent material sample.
(3) cladding of fluorescent material processes:
With the method for embodiment 1, final K2C0.04Si0.89F6:Mn0.07。
Comparative example 1
The fluorescent material product of comparative example, its chemical formula K2Si0.93F6:Mn0.07.Its manufacture method is for pressing
According to stoichiometric proportion, in polytetrafluoroethylene beaker, add the Fluohydric acid. that concentration is 50wt% of 600ml,
Stirring adds 17.3g K2MnF6Until completely dissolved, add 108g KF be completely dissolved prepared No. 1 molten
Liquid.65wt% Fluohydric acid. 2000ml pours in polytetrafluoroethylene beaker, and adding 350ml concentration is 45wt%
Hexafluosilicic acid prepare No. 2 solution；In No. 2 solution drip No. 1 solution, rate of titration be 1 second 1,
Within about 200 minutes, it is added dropwise to complete, stirs 50 minutes after completion of dropwise addition, solid-liquid separation；With washing with acetone 3
Secondary, use 350ml every time；Drying 4 hours for 70 DEG C, screening obtains comparative example.
Above-described embodiment 1-9 and relative luminous intensity, particle size distribution and the process of comparative example 1 gained fluorescent material
Humidity 85%, temperature 85 DEG C, the relative luminous intensity data after 200 hours burin-in process are as shown in table 1.
Table 1
Fluorescent material prepared by the present invention can be used for manufacturing white light LED luminescent device, and detailed process is as follows:
After the fluorescent material of the present invention and the mixing of other fluorescent material are sized mixing, it is coated on blue chip, welding
Good circuit, by silica gel or resin-encapsulated, gained solid state device is white light LED luminescent device.Used
The kind of other fluorescent material and added amount according to product requirement depending on.
The fluoride red illuminating material of the present invention has stronger luminescent properties, and half-peak at high band
Wide only about 7.2nm, is applied to display field, and colour gamut NTSC (1931) can bring up to 85%
Above, thus the shortcoming of the nitride red luminescent material of quasi-complement.
Although the present invention is open as above with embodiment, so it is not intended to limit the present invention, any ability
Field technique personnel, without departing from the spirit and scope of the present invention, all can make various different selection and repair
Changing, therefore protection scope of the present invention is limited by claims and equivalents thereof.
Claims (10)
1. a red fluorescence powder, it is characterised in that the chemical formula of described fluorescent material consists of:
A2B1-xF6:Mnx, wherein,
A is one or more elements of Li, Na, K, Ag and Cu；
B is one or more elements of C element and Si, Ti and Ge；
0.001≤x≤0.5。
The preparation method of red fluorescence powder the most according to claim 1, it is characterised in that include with
Lower step:
1) preparation has A2MnF6Structure contains Mn4+Fluorine manganate:
Fluoride containing A or bifluoride are dissolved in Fluohydric acid., add KMnO4, the most molten
Xie Hou, instills H2O2, when solution is become yellow from brown purple, stopping titration, titration is formed after terminating
Golden yellow precipitate thing, solid-liquid separation, washing, it is dried to obtain A2MnF6；
2) there is A2B1-xF6:MnxThe preparation of structure fluoride fluorescent material:
The preparation of No. 1 solution: take hydrofluoric acid solution, is added thereto to the fluoride containing element A or fluorine
Hydride, to be dissolved after, add step 1 prepare A2MnF6, after being completely dissolved, obtain No. 1 solution；
The preparation of No. 2 solution: separately take after hydrofluoric acid solution is heated to uniform temperature, be added thereto to carbon dust,
After to be dissolved, add a certain amount of fluorine-containing salt, acids or oxide, until completely dissolved, obtain 2
Number solution；
Titration: keep No. 2 solution temperatures invariable, No. 2 solution limits of stirring, limit instill No. 1 solution,
Titration process forms precipitation, solid-liquid separation, obtains fluorescent material.
The preparation method of red fluorescence powder the most according to claim 1, it is characterised in that include with
Lower step:
1) preparation has A2MnF6Structure contains Mn4+Fluorine manganate:
Fluoride containing A or bifluoride are dissolved in Fluohydric acid., add KMnO4, the most molten
Xie Hou, instills H2O2, when solution is become yellow from brown purple, stopping titration, titration is formed after terminating
Golden yellow precipitate thing, solid-liquid separation, washing, it is dried to obtain A2MnF6；
2) there is A2B1-xF6:MnxThe preparation of structure fluoride fluorescent material:
The preparation of No. 1 solution: take hydrofluoric acid solution, is added thereto to the fluoride containing element A or fluorine
Hydride, to be dissolved after, add step 1 prepare A2MnF6, after being completely dissolved, obtain No. 1 solution；
The preparation of No. 2 solution: separately take after hydrofluoric acid solution is heated to uniform temperature, add a certain amount of containing
Villiaumite class, acids or oxide, until completely dissolved, obtain No. 2 solution；
Titration: keep No. 2 solution temperatures invariable, be passed through CF4Gas, and use CF4Gas shield,
CF in reaction vessel4Gas controls certain pressure, stirs No. 2 solution and instills No. 1 solution simultaneously, titration
Process forms precipitation, solid-liquid separation, obtains fluorescent material.
4. according to the preparation method of the red fluorescence powder described in Claims 2 or 3, it is characterised in that also
Comprise the following steps:
3) cladding of fluorescent material processes:
In ethanol, add Fluohydric acid., after regulation pH to 2-6, add step 2 wherein) prepare
Fluorescent material, heats mixed liquor after mix homogeneously so that it is temperature is maintained between 50 DEG C-80 DEG C；Limit
Stirring limit instills appropriate tetraethyl orthosilicate, solid-liquid separation, after washing is to pH to 7, dries, screening,
Fluorescent material after the peplos of phosphor surface.
5. according to the preparation method of the red fluorescence powder described in Claims 2 or 3, it is characterised in that institute
State step 1) in, hydrofluoric acid concentration is 40-60wt%, H2O2Concentration is 30-40wt%；Described fluoride
Or bifluoride and KMnO4Mol ratio be: 40:1-20:1.
6. according to the preparation method of the red fluorescence powder described in Claims 2 or 3, it is characterised in that institute
State step 2) in,
In the preparation of No. 1 solution: hydrofluoric acid concentration is 40-60wt%；
In the preparation of No. 2 solution: hydrofluoric acid concentration is 60-80wt%, hydrofluoric acid temperature controls at 50-80 DEG C；
Titration: rate of titration is 0.5-5 drop/sec, it is 10-100 minute that titration terminates rear mixing time, when
It is passed through CF4During gas, flow-control was at 0.1-5L/ minute, and container pressure controls at 0.15-1MPa.
7. according to the preparation method of the red fluorescence powder described in Claims 2 or 3, it is characterised in that institute
State step 2) in fluorine-containing salt, acids or oxide refer to comprise wherein the one of Si, Ti and Ge element
Kind or multiple fluorine-containing salt, acids or oxide.
The preparation method of red fluorescence powder the most according to claim 3, it is characterised in that described step
Rapid 3) in, the concentration of Fluohydric acid. be 10-15wt%, pH be 2-6, dropping tetraethyl orthosilicate before solution temperature
Degree is maintained at 70-90 DEG C, and titration is stirred 5-20 hour after terminating.
The preparation method of red fluorescence powder the most according to claim 3, it is characterised in that described step
Rapid 3) in, described fluorescent material is 100:(15-55 with the weight ratio of described tetraethyl orthosilicate).
10. the white light LEDs of the red fluorescence powder comprised described in claim 1-9 any claim
Luminescent device.
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| CN107573934A (en) * | 2017-08-08 | 2018-01-12 | 五邑大学 | One kind mixes Mn4+Fluogermanic acid potassium red fluorescence powder preparation method |
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| CN113201329A (en) * | 2021-04-27 | 2021-08-03 | 云南民族大学 | Perovskite type fluoride luminescent material and preparation method thereof |
| CN116144353A (en) * | 2022-08-19 | 2023-05-23 | 廊坊莱悦特电子科技有限公司 | Red fluorescent powder, preparation method thereof and light-emitting device adopting red fluorescent powder |
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