CN105462582B - A kind of white light LEDs Mn4+Adulterate red fluorescence material and preparation method thereof - Google Patents

A kind of white light LEDs Mn4+Adulterate red fluorescence material and preparation method thereof Download PDF

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CN105462582B
CN105462582B CN201510945658.4A CN201510945658A CN105462582B CN 105462582 B CN105462582 B CN 105462582B CN 201510945658 A CN201510945658 A CN 201510945658A CN 105462582 B CN105462582 B CN 105462582B
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red fluorescence
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CN105462582A (en
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张勤远
宋恩海
叶柿
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South China University of Technology SCUT
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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
    • C09K11/64—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing aluminium
    • C09K11/644—Halogenides
    • C09K11/645—Halogenides with alkali or alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/57—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing manganese or rhenium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps

Abstract

The invention belongs to the technical field of luminescent material, discloses a kind of white light LEDs Mn4+Adulterate red fluorescence material and preparation method thereof.Methods described is：(1) K is prepared2MnF6Powder；(2) by K2MnF6Powder and silicon source powder are added in the HF aqueous solution, and stirring is to being completely dissolved；Then sodium source powder is added, continues to stir, quick cooling, stands, centrifuges, wash, dry, obtain red fluorescence material, its chemical composition is Na3AlF6:xMn4+, x=0.5~30%.The raw material of the present invention is cheap and easy to get, and cost is cheap；Preparation method is simple, and temperature is low, and few using the amount of hydrofluoric acid, condition is controllable, is mass produced suitable for industrialization；The red fluorescence powder of the present invention has good fluorescence heat endurance simultaneously.

Description

A kind of white light LEDs Mn4+Adulterate red fluorescence material and preparation method thereof
Technical field
The invention belongs to the technical field of luminescent material, more particularly to a kind of white light LEDs Mn4+Adulterate red fluorescence material Material and preparation method thereof.
Background technology
White light LEDs due to its long lifespan (>100000 hours), environmental protection, efficiently and energy-conservation etc. relative to conventional light source uniqueness Advantage obtains application in the fields such as automobile, traffic, military affairs and daily life.The realization side of commercial white light LEDs The main still yellow fluorescent powder Y of formula3Al5O12:Ce3+(YAG)+blue chip is combined.Some blue light excites YAG caused by chip Gold-tinted is produced, and the yellow light combine of the remaining blue light of chip and fluorescent material obtains white light.This mode is simple, easily realizes and sends out Light efficiency is high.However, the white light obtained in this way make it that its colour temperature is higher because red color light component is insufficient in YAG fluorescent powder (CCT>6000K) and the relatively low (Ra of colour rendering index<80), be also difficult to illuminate indoors and the medium field of lighting for medical use in obtain extensively Application.Solve this problem, a kind of feasible thinking be further added on original YAG and blue chip combination foundation it is red Color fluorescent material, so as to improve colour rendering index and reduce colour temperature, finally realizes high color rendering index (CRI) and low color to increase red color light component The warm white transmitting of temperature.In past 10 years, rare earth is as composed (Pr3+), samarium (Sm3+), europium (Eu3+/Eu2+) and transition metal Manganese (Mn2+/Mn4+) and chromium (Cr3+) doping various red fluorescence materials be developed.Wherein, the white light LEDs of better performances There is CaAlSiN with red fluorescence material3:Eu2+、M2Si5N8:Eu2+(M=Ca, Sr, Ba) etc..It is however, nitride red using this Fluorescent material also causes the luminous efficiency of white light LEDs significantly to decline while colour rendering reduction colour temperature is improved.This is mainly Because the emission band of such red light flourescent material is wider, quite a few emission spectrum be in it is dark red (>650nm) scope, and Human eye is luminous and its insensitive to the part, causes energy loss more, and luminous efficiency reduces.Furthermore nitride fluorescent material Synthesis condition it is very harsh (high temperature, high pressure), prepare cost it is higher.CaS:Eu2+Although red light flourescent material is with good The characteristics of luminescence, synthesis temperature is relatively mild, but the physics and poor chemical stability of sulfide, it is difficult to is applied in practice. Therefore, exploitation halfwidth is narrower and launch wavelength is less than 650nm, and the high efficiency that preparation method is simple, cost is cheap is red Fluorescent material has great significance.
Transient metal Mn4+The fluoride fluorescent material of doping is considered as a kind of preferable red fluorescence material.It is nineteen sixty-eight, beautiful State's patent (U.S.Patent, 1971,3576756) reports Mn4+The K of activation2SiF6, K2TiF6Deng red light flourescent material；It Afterwards, AM General company has applied for Mn again4+The A of activation2MF5(A=Li, Na, K, Rb, Cs, NH4；M=Al, Ga, In), ZnMF6 And A2NF7(E=Nb, Ta)；EFF6(E=Ge, Si, Ti, Zr；F=Mg, Ca, Sr, Ba, Zn) etc. fluoride red fluorescence powder it is special Profit (U.S.Patent, 2009,7497973；U.S.Patent,2010,7648649；U.S.Patent,2010,7847309). But the preparation method described in patent is by the way that by dissolution of raw material, in high concentration of hydrofluoric acid, then heating volatilization cocrystallization obtains Target product, this method can produce a large amount of toxic gas HF, and preparation process is difficult to control, and is unsuitable for industrialized production.Patent WO2009/119486 discloses another preparation method, i.e., metal Si is dissolved in liquor potassic permanganate, and reaction is produced Thing, but the preparation efficiency of this method is very low, is equally unsuitable for mass producing.
The content of the invention
The shortcomings that it is an object of the invention to overcome prior art, there is provided it is a kind of relatively low to equipment requirement, suitable for extensive The white light LEDs Mn of production4+Adulterate red fluorescence material.
Another object of the present invention is to provide above-mentioned white light LEDs Mn4+Adulterate the preparation method of red fluorescence material.
The purpose of the present invention is achieved by the following scheme：
A kind of white light LEDs Mn4+Red fluorescence material is adulterated, its chemical composition is Na3AlF6:xMn4+, Mn in formula4+Doping The molar concentration of Al positions is x=0.5~30%, preferably 0.5~10%.
A kind of white light LEDs Mn4+The preparation method of red fluorescence material is adulterated, is comprised the following steps：
(1) K is prepared2MnF6Powder；
(2) by K2MnF6Powder and silicon source powder are added in the HF aqueous solution, and stirring is to being completely dissolved；Then sodium source powder is added Body, continue to stir, quick cooling, stand, centrifuge, wash, dry, it is red fluorescence material to obtain yellow mercury oxide.
The concentration of step (2) the HF aqueous solution is 10~49%, preferably 30~49%.
Step (2) temperature quickly cooled down is 0~5 DEG C；The type of cooling is cooled down using frozen water；During the standing Between be 2~5h；The washing refers to be washed using acetone or alcohol；The centrifugal rotational speed is 1000~4000r/min；Institute Dry temperature is stated as 40~80 DEG C, drying time is 2~10h.
Step (2) 10~30min of time for continuing stirring；The temperature for continuing stirring is 0~70 DEG C, and stirring turns Speed is 400~1000r/min.
Step (1) described K2MnF6Raw powder's production technology is：By KMnO4It is dissolved in the HF aqueous solution, stirs, then Add KHF2Continue to stir, quick cooling, 1-5ml H is added dropwise2O2The aqueous solution, when the color of reactant solution is become by purple K is obtained for brown color2MnF6Suspension；Stand, centrifuge washing, dry, obtain K2MnF6Powder.The KMnO4：HF is water-soluble Liquid：KHF2：The amount ratio of hydrogen peroxide solution is 2.25g：150ml：45g：(1-5)ml.The concentration of the HF aqueous solution is 10- 49%, preferably 30-49%.The time for continuing stirring is 20~50min；The chilling temperature is 0~5 DEG C；It is described quiet It is 2~5h to put the time；The washing refers to be washed using acetone；The centrifugal rotational speed is 1000~4000r/min；It is described Dry temperature is 40~80 DEG C, and drying time is 2~10h.The H2O2The concentration of the aqueous solution is 10~49wt%.
Step (2) described K2MnF6The mol ratio of powder and silicon source powder is (0.5~30)：100, be preferably (0.5~2): 100。
Silicon source powder described in step (2) is AlF3Or Al (OH)3One or more of, preferably AlF3；The sodium source powder Body is NaOH, Na2CO3Or one or more of NaF, preferably NaF.
The mol ratio of sodium source powder described in step (2) and silicon source powder is (2~10):1, be preferably (3~5):1.
Relative to prior art, the invention has the advantages that and effect：
(1) host material fluoride Na of the invention3AlF6In without the more valuable metallic element such as rare earth, Ti or Ge, its Preparing raw material is cheap and easy to get, and cost is cheap；
(2) preparation method of the invention is simple, and temperature is low, and few using the amount of hydrofluoric acid, condition is controllable, big suitable for industrializing Large-scale production, operation easy to spread；
(3) red fluorescence powder of the invention has good fluorescence heat endurance, when temperature rises to 200 DEG C, lights strong Degree also has more than the 99% of room temperature, does not have fluorescence thermal quenching substantially, better than all red fluorescence powders reported at present.
Brief description of the drawings
Fig. 1 is Na in embodiment 53AlF6:0.5%Mn4+XRD standard cards and product XRD；
Fig. 2 is Na in embodiment 53AlF6:0.5%Mn4+Excitation and emission spectra；
Fig. 3 is Na in embodiment 53AlF6:0.5%Mn4+The alternating temperature emission spectrum and fluorescence lifetime in the case where 467nm is excited Curve map；Wherein (a) is alternating temperature emission spectrum, and (b) is the fluorescence decay curve under different temperatures, and (c) is luminous intensity and temperature Degree and the graph of relation of fluorescence lifetime and temperature.
Embodiment
With reference to embodiment, the present invention is further illustrated, but those skilled in the art understands, following implementations Example is not the limitation to invention protection domain, and any improvement and change on the basis of the present invention is all in protection scope of the present invention Within.
Embodiment 1
K2MnF6The preparation of powder：
Under conditions of room temperature, by 2.25g KMnO4Powder is dissolved in the 150ml 49wt%HF aqueous solution, is stirred, Add 45g KHF2Powder continues to stir 40min, is then quickly cooled down with frozen water, 4ml 49wt%H is added dropwise2O2It is water-soluble Liquid, K is obtained when the color of reactant solution is changed into brown color from purple2MnF6Suspension；4h is stood, centrifuge washing (wash by acetone Wash), in 70 DEG C of dry 6h, obtain K2MnF6Powder, it is standby.
Embodiment 2
Na3AlF6:0.5%Mn4+The preparation of fluorescent material：
By 0.00617g K2MnF6With 0.419g AlF3It is dissolved in 10ml hydrofluoric acid (49wt.%), stirs 10 minutes (rotating speed of stirring is 4000r/min), obtains clear solution；Then 0.999g NaOH powder is added in clear solution, room Continue stirring 30 minutes under temperature, be quickly cooled to 4 DEG C, centrifugation, washed 3 times with ethanol, dry 7h in 80 DEG C, that is, obtain Na3AlF6:0.5%Mn4+。
Sample excites the lower feux rouges for producing and becoming clear in purple light and blue light.The excitation spectrum of sample is by the two of 357nm and 460nm Individual broadband composition, wherein, the blue light perfect matching that most strong excitation band (460nm) is sent with GaN blue chips, emission spectrum It is made up of six spikes respectively positioned at 606nm, 610nm, 620nm, 628nm, 632nm and 645nm, its chromaticity coordinates is located at：X= 0.687, y=0.312, belong to the feux rouges of pure color.
Embodiment 3
Na3AlF6:0.5%Mn4+The preparation of fluorescent material：
By 0.00617g K2MnF6With 0.419g AlF3It is dissolved in 10ml hydrofluoric acid (49wt.%), stirring obtains for 10 minutes To clear solution；Then by 2.649g Na2CO3Powder is added in clear solution, continue at room temperature stirring 30 minutes (stirring Rotating speed is 4000r/min), it is quickly cooled to 4 DEG C and obtains light-yellow precipitate, centrifuge, washed 3 times with acetone, in 80 DEG C of drying 8h, that is, obtain Na3AlF6:0.5%Mn4+。
Sample excites the lower feux rouges for producing and becoming clear in purple light and blue light.The excitation spectrum of sample is by the two of 357nm and 460nm Individual broadband composition, wherein, the blue light perfect matching that most strong excitation band (460nm) is sent with GaN blue chips, emission spectrum It is made up of six spikes respectively positioned at 606nm, 610nm, 620nm, 628nm, 632nm and 645nm, its chromaticity coordinates is located at：X= 0.687, y=0.312, belong to the feux rouges of pure color.
Embodiment 4
Na3AlF6:0.5%Mn4+The preparation of fluorescent material
By 0.00617g K2MnF6With 0.419g AlF3It is dissolved in 10ml hydrofluoric acid (49wt.%), stirs 10 minutes, Obtain clear solution；Then 1.049g NaF powder is added in clear solution, continue at room temperature stirring 30 minutes (stirring Rotating speed is 4000r/min), it is quickly cooled to 4 DEG C and obtains light-yellow precipitate, centrifuge, washed 3 times with ethanol, 7h is dried in 80 DEG C, Obtain Na3AlF6:0.5%Mn4+.Sample excites the lower feux rouges for producing and becoming clear in purple light and blue light.
The excitation spectrum of sample is made up of 357nm and 460nm two broadbands, wherein, most strong excitation band (460nm) with The blue light perfect matching that GaN blue chips are sent, emission spectrum by six respectively positioned at 606nm, 610nm, 620nm, 628nm, 632nm and 645nm spike composition, its chromaticity coordinates are located at：X=0.687, y=0.312, belong to the red of pure color Light.
Embodiment 5
Na3AlF6:0.5%Mn4+The preparation of fluorescent material
By 0.00617g K2MnF6With 0.39g Al (OH)3It is dissolved in 10ml hydrofluoric acid (49wt.%), stirs 10 minutes Obtain clear solution；Then 1.049g NaF powder is added in clear solution, continue at room temperature stirring 30 minutes (stirring Rotating speed is 4000r/min), it is quickly cooled to 4 DEG C and obtains light-yellow precipitate, centrifuge, washed 3 times with ethanol, 7h is dried in 80 DEG C, Obtain Na3AlF6:0.5%Mn4+.Its XRD test chart as shown in figure 1, excitation and emission spectra as shown in Fig. 2 fluorescence heat is steady Qualitative test is as shown in Figure 3.
From fig. 1, it can be seen that manufactured in the present embodiment is pure object phase sample Na3AlF6:Mn4+；Fig. 2 understands that sample exists Produce the high feux rouges of bright excitation under blue light or ultraviolet excitation, and the most strong excitation peak of sample is located at 465 nanometers Left and right, matched well with current commercial blue chip；Fig. 3 understands that sample has very excellent fluorescence heat endurance, in temperature Degree does not have fluorescence decay substantially when being up to 200 DEG C, the large power white light LED excited suitable for current blue chip.
Sample excites the lower feux rouges for producing and becoming clear in purple light and blue light.The excitation spectrum of sample is by the two of 357nm and 460nm Individual broadband composition, wherein, the blue light perfect matching that most strong excitation band (460nm) is sent with GaN blue chips, emission spectrum It is made up of six spikes respectively positioned at 606nm, 610nm, 620nm, 628nm, 632nm and 645nm, its chromaticity coordinates is located at：X= 0.687, y=0.312, belong to the feux rouges of pure color.
Embodiment 6
Na3AlF6:1.0%Mn4+The preparation of fluorescent material
By 0.0123g K2MnF6With 0.419g AlF3It is dissolved in 10ml hydrofluoric acid (49wt.%), stirring obtains for 10 minutes To clear solution；Then 1.049g NaF powder is added in clear solution, continues (turn of stirring of stirring 30 minutes at room temperature Speed is 4000r/min), it is quickly cooled to 4 DEG C and obtains light-yellow precipitate, centrifuge, washed 3 times with ethanol, dries 5h in 80 DEG C, i.e., Obtain Na3AlF6:1.0%Mn4+。
Sample excites the lower feux rouges for producing and becoming clear in purple light and blue light.The excitation spectrum of sample is by the two of 357nm and 460nm Individual broadband composition, wherein, the blue light perfect matching that most strong excitation band (460nm) is sent with GaN blue chips, emission spectrum It is made up of six spikes respectively positioned at 606nm, 610nm, 620nm, 628nm, 632nm and 645nm, its chromaticity coordinates is located at：X= 0.687, y=0.312, belong to the feux rouges of pure color.
Embodiment 7
Na3AlF6:2%Mn4+The preparation of fluorescent material
By 0.0247g K2MnF6With 0.419g AlF3It is dissolved in 10ml hydrofluoric acid (49wt.%), stirring obtains for 10 minutes To clear solution；Then 1.049g NaF powder is added in clear solution, continues (turn of stirring of stirring 30 minutes at room temperature Speed is 4000r/min), it is quickly cooled to 4 DEG C and obtains light-yellow precipitate, centrifuge, washed 3 times with ethanol, dries 8h in 80 DEG C, i.e., Obtain Na3AlF6:2.0%Mn4+。
Sample excites the lower feux rouges for producing and becoming clear in purple light and blue light.The excitation spectrum of sample is by the two of 357nm and 460nm Individual broadband composition, wherein, the blue light perfect matching that most strong excitation band (460nm) is sent with GaN blue chips, emission spectrum It is made up of six spikes respectively positioned at 606nm, 610nm, 620nm, 628nm, 632nm and 645nm, its chromaticity coordinates is located at：X= 0.687, y=0.312, belong to the feux rouges of pure color.
Embodiment 8
Na3AlF6:5.0%Mn4+The preparation of fluorescent material
By 0.0617g K2MnF6With 0.419g AlF3It is dissolved in 10ml hydrofluoric acid (49wt.%), stirring obtains for 10 minutes To clear solution；Then 1.049g NaF powder is added in clear solution, continues (turn of stirring of stirring 30 minutes at room temperature Speed is 4000r/min), it is quickly cooled to 4 DEG C and obtains light-yellow precipitate, centrifuge, washed 3 times with ethanol, dries 8h in 80 DEG C, i.e., Obtain Na3AlF6:5.0%Mn4+。
Sample excites the lower feux rouges for producing and becoming clear in purple light and blue light.The excitation spectrum of sample is by the two of 357nm and 460nm Individual broadband composition, wherein, the blue light perfect matching that most strong excitation band (460nm) is sent with GaN blue chips, emission spectrum It is made up of six spikes respectively positioned at 606nm, 610nm, 620nm, 628nm, 632nm and 645nm, its chromaticity coordinates is located at：X= 0.687, y=0.312, belong to the feux rouges of pure color.
Embodiment 9
Na3AlF6:10%Mn4+The preparation of fluorescent material
By 0.1235g K2MnF6With 0.419g AlF3It is dissolved in 10ml hydrofluoric acid (49wt.%), stirring obtains for 10 minutes To clear solution；Then 1.049g NaF powder is added in clear solution, continues (turn of stirring of stirring 30 minutes at room temperature Speed is 4000r/min), it is quickly cooled to 4 DEG C and obtains light-yellow precipitate, centrifuge, washed 3 times with ethanol, dries 8h in 80 DEG C, i.e., Obtain Na3AlF6:10%Mn4+。
Sample excites the lower feux rouges for producing and becoming clear in purple light and blue light.The excitation spectrum of sample is by the two of 357nm and 460nm Individual broadband composition, wherein, the blue light perfect matching that most strong excitation band (460nm) is sent with GaN blue chips, emission spectrum It is made up of six spikes respectively positioned at 606nm, 610nm, 620nm, 628nm, 632nm and 645nm, its chromaticity coordinates is located at：X= 0.687, y=0.312, belong to the feux rouges of pure color.
Embodiment 10
Na3AlF6:15%Mn4+The preparation of fluorescent material
By 0.1853g K2MnF6With 0.419g AlF3It is dissolved in 10ml hydrofluoric acid (49wt.%), stirring obtains for 10 minutes To clear solution；Then 1.049g NaF powder is added in clear solution, continues (turn of stirring of stirring 30 minutes at room temperature Speed is 4000r/min), it is quickly cooled to 4 DEG C and obtains light-yellow precipitate, centrifuge, washed 3 times with ethanol, dries 8h in 80 DEG C, i.e., Obtain Na3AlF6:15%Mn4+。
Sample excites the lower feux rouges for producing and becoming clear in purple light and blue light.The excitation spectrum of sample is by 357nm's and 460 nm Two broadband compositions, wherein, the blue light perfect matching that most strong excitation band (460nm) is sent with GaN blue chips, launch light Spectrum is made up of six spikes respectively positioned at 606nm, 610nm, 620nm, 628nm, 632nm and 645nm, and its chromaticity coordinates is located at：x =0.687, y=0.312, belong to the feux rouges of pure color.
Embodiment 11
Na3AlF6:20%Mn4+The preparation of fluorescent material
By 0.247g K2MnF6With 0.419g AlF3It is dissolved in 10ml hydrofluoric acid (49wt.%), stirring obtains for 10 minutes Clear solution；Then 1.049g NaF powder is added in clear solution, continues to stir 30 minutes (rotating speeds of stirring at room temperature For 4000r/min), it is quickly cooled to 4 DEG C and obtains light-yellow precipitate, centrifuge, washed 3 times with ethanol, dries 8h in 80 DEG C, produce To Na3AlF6:20%Mn4+。
Sample excites the lower feux rouges for producing and becoming clear in purple light and blue light.The excitation spectrum of sample is by the two of 357nm and 460nm Individual broadband composition, wherein, the blue light perfect matching that most strong excitation band (460nm) is sent with GaN blue chips, emission spectrum It is made up of six spikes respectively positioned at 606nm, 610nm, 620nm, 628nm, 632nm and 645nm, its chromaticity coordinates is located at：X= 0.687, y=0.312, belong to the feux rouges of pure color.
Embodiment 12
Na3AlF6:30%Mn4+The preparation of fluorescent material
By 0.371g K2MnF6With 0.419g AlF3It is dissolved in 10ml hydrofluoric acid (49wt.%), stirring obtains for 10 minutes Clear solution；Then 1.049g NaF powder is added in clear solution, continues to stir 30 minutes (rotating speeds of stirring at room temperature For 4000r/min), it is quickly cooled to 4 DEG C and obtains light-yellow precipitate, centrifuge, washed 3 times with ethanol, dries 8h in 80 DEG C, produce To Na3AlF6:30%Mn4+。
Sample excites the lower feux rouges for producing and becoming clear in purple light and blue light.The excitation spectrum of sample is by the two of 357nm and 460nm Individual broadband composition, wherein, the blue light perfect matching that most strong excitation band (460nm) is sent with GaN blue chips, emission spectrum It is made up of six spikes respectively positioned at 606nm, 610nm, 620nm, 628nm, 632nm and 645nm, its chromaticity coordinates is located at：X= 0.687, y=0.312, belong to the feux rouges of pure color.

Claims (7)

  1. A kind of 1. white light LEDs Mn4+Adulterate the preparation method of red fluorescence material, it is characterised in that comprise the following steps：
    (1) K is prepared2MnF6Powder；
    (2) by K2MnF6Powder and silicon source powder are added in the HF aqueous solution, and stirring is to being completely dissolved；Then sodium source powder is added, after Continuous stirring, quick cooling, stands, and centrifuges, and washs, and dries, it is red fluorescence material to obtain yellow mercury oxide；
    The concentration of step (2) the HF aqueous solution is 10~49%；Step (2) described K2MnF6Mole of powder and silicon source powder Than for (0.5~30)：100；The mol ratio of sodium source powder described in step (2) and silicon source powder is (2~10):1；
    Silicon source powder described in step (2) is AlF3Or Al (OH)3One or more of；The sodium source powder is NaOH, Na2CO3 Or one or more of NaF；
    Step (2) temperature quickly cooled down is 0~5 DEG C；Step (2) described time of repose is 2~5h；
    Step (2) washing refers to be washed using acetone or alcohol；
    The white light LEDs Mn4+The chemical composition for adulterating red fluorescence material is Na3AlF6:xMn4+, Mn in formula4+Adulterate Al positions Molar concentration be x=0.5~30%.
  2. 2. white light LEDs Mn according to claim 14+Adulterate the preparation method of red fluorescence material, it is characterised in that：It is described Na3AlF6:xMn4+Middle x is 0.5~10%.
  3. 3. white light LEDs Mn according to claim 14+Adulterate the preparation method of red fluorescence material, it is characterised in that：Step (2) concentration of the HF aqueous solution is 30~49%；The K2MnF6The mol ratio of powder and silicon source powder is (0.5~2): 100；The mol ratio of sodium source powder described in step (2) and silicon source powder is (3~5):1.
  4. 4. white light LEDs Mn according to claim 14+Adulterate the preparation method of red fluorescence material, it is characterised in that：It is described Silicon source powder is AlF3, the sodium source powder is NaF.
  5. 5. white light LEDs Mn according to claim 14+Adulterate the preparation method of red fluorescence material, it is characterised in that：Step (2) 10~30min of time for continuing stirring；The temperature for continuing stirring is 0~70 DEG C, the rotating speed of stirring for 400~ 1000r/min；
    Step (2) described centrifugal rotational speed is 1000~4000r/min；The temperature of step (2) described drying is 40~80 DEG C, is dried Time is 2~10h.
  6. 6. white light LEDs Mn according to claim 14+Adulterate the preparation method of red fluorescence material, it is characterised in that：Step (1) K2MnF6Raw powder's production technology is：By KMnO4It is dissolved in the HF aqueous solution, stirs, then adds KHF2Continue Stirring, it is quick to cool down, 1-5ml H is added dropwise2O2The aqueous solution, produced when the color of reactant solution is changed into brown color from purple To K2MnF6Suspension；Stand, centrifuge washing, dry, obtain K2MnF6Powder.
  7. 7. white light LEDs Mn according to claim 64+Adulterate the preparation method of red fluorescence material, it is characterised in that：It is described KMnO4：The HF aqueous solution：KHF2：The amount ratio of hydrogen peroxide solution is 2.25g：150ml：45g：(1-5)ml；
    The concentration of the HF aqueous solution is 10-49%；The H2O2The concentration of the aqueous solution is 10~49wt%；
    The time for continuing stirring is 20~50min；The chilling temperature is 0~5 DEG C；The time of repose is 2~5h；Institute Washing is stated to refer to be washed using acetone；The centrifugal rotational speed is 1000~4000r/min；The temperature of the drying be 40~ 80 DEG C, drying time is 2~10h.
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