CN106085428B - A kind of fluorescent material suitable for LED illumination - Google Patents

A kind of fluorescent material suitable for LED illumination Download PDF

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CN106085428B
CN106085428B CN201610468090.6A CN201610468090A CN106085428B CN 106085428 B CN106085428 B CN 106085428B CN 201610468090 A CN201610468090 A CN 201610468090A CN 106085428 B CN106085428 B CN 106085428B
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fluorescent powder
mnf
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CN106085428A (en
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韩涛
王俊
彭玲玲
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Chongqing Benle Science and Technology Co., Ltd.
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Chongqing University of Arts and Sciences
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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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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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
    • C09K11/615—Halogenides
    • C09K11/616—Halogenides with alkali or alkaline earth metals

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  • Engineering & Computer Science (AREA)
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  • Luminescent Compositions (AREA)

Abstract

The present invention relates to a kind of preparation method of manganese base fluorescent powder.It is with MeXTiF6For matrix, KMnO4For raw material, HF is solvent, and reacted under conditions of agent and reducing agent are provided added with part；Wherein, Me can be K, Na, Li plasma or be Ca, Mg plasma, and X phases should be 2~1.This preparation method has the advantages that quick, easy, cost is cheap, and the manganese base fluorescent powder that emission spectrum is red broad peak has been made in it under normal temperature and pressure conditionses.

Description

A kind of fluorescent material suitable for LED illumination
The present invention is Application No. 201510103741.7, the division Shen of the patent of invention on the applying date 2015 year 03 month 10 Please.
Technical field
The present invention relates to a kind of light-emitting phosphor material, more particularly to a kind of light-emitting phosphor material applied to LED illumination The preparation method of material.
Background technology
The technical scheme of White-light LED illumination main flow is by blue chip and yellow fluorescent powder encapsulation, chip excitated fluorescent powder The blue light of caused gold-tinted and chip emission combines, and forms recombined white light.But existing yellow fluorescent powder, lack in its emission spectrum Few red light portion, it is difficult to prepare high-color rendering, the white light LEDs lamp bead of warm colour temperature, it is impossible to meet the modern lighting requirement of high quality. New non-rare earth luminous manganese base fluorescent powder, such as：K2TiF6:Mn4+、K2SiF6:Mn4+、K2GeF6:Mn4+、Cs2GeF6:Mn4+、 Cs2SnF6:Mn4+Deng fluorescent material, have the advantages that quantum efficiency is high, simple without self-absorption, preparation method, is widely studied.So And the preparation method of existing manganese base fluorescent powder exist two it is obvious the problem of：First, it is necessary to synthesize presoma in preparation process K2MnF6, and K2MnF6Preparation process it is more complicated；Second, the emission spectrum of its product is red spike, to improving white light LEDs Display it is unfavorable.
The content of the invention
It is an object of the invention to provide a kind of preparation method of the manganese base fluorescent powder suitable for LED illumination.
The purpose of the present invention is achieved through the following technical solutions：
A kind of preparation method of manganese base fluorescent powder suitable for LED illumination, it is specifically what is followed the steps below：
（1）Under normal temperature and pressure conditionses, by KMnO4, KF first add in HF solution, be stirring evenly and then adding into H2O2Carry out anti- Should, after question response, then through filtering, cleaned, dried so that presoma K is made with methanol2MnF5·H2O；The step（1）In, respectively The dosage of material is KMnO according to mol ratio4：KF：H2O2：HF =1：2：4：200 are configured；
（2）By presoma K2MnF5·H2O、K2TiF6、KMnO4, KF add HF solution in, stir reaction 40 h, most Cleaned, dried with methanol through filtering again afterwards；The step（2）In, the dosage of each material is K according to mol ratio2MnF5· H2O：K2TiF6：KMnO4：KF：HF=1：20：5：5:500 are configured.
Obtain after testing：Using the manganese base fluorescent powder obtained by the preparation method, the agent structure of its crystal is matrix K2TiF6, Mn elements substitution matrix K2TiF6The content ratio of middle Ti elements is 5.75 at.%, its excitation peak be 463.4 nm and 363 nm, emission spectrum broadband emission between 580~660 nm：Have five intersection emission peaks, respectively 590.0 nm, 603.6 nm, 616.2 nm, 634.6 nm and 650.4 nm, wherein highest peak are 634.6 nm, and the half-peak of highest peak is a width of 10 nm。
The invention has the advantages that：
The present invention discloses a kind of preparation method of manganese base fluorescent powder, and the preparation method has quick, easy, cost is cheap etc. Advantage, the manganese base fluorescent powder that emission spectrum is red broad peak has been made in it under normal temperature and pressure conditionses；Products therefrom has width Outstanding advantages of band transmitting, specular removal, high colour developing, beneficial to the display for improving white light LEDs, it can be widely applied to high-quality illumination Technology, such as：High colour developing, the coating of warm colour temperature white-light LED encapsulation, fluorescent tube etc..
Brief description of the drawings
Fig. 1 is the XRD spectrums using the product obtained by the preparation method of manganese base fluorescent powder described in the embodiment of the present invention 1 Figure.
Fig. 2 is the EDS spectrums using the product obtained by the preparation method of manganese base fluorescent powder described in the embodiment of the present invention 1 Figure.
Fig. 3 is the exciting light using the product obtained by the preparation method of manganese base fluorescent powder described in the embodiment of the present invention 1 Spectrogram.
Fig. 4 is the transmitting light using the product obtained by the preparation method of manganese base fluorescent powder described in the embodiment of the present invention 1 Spectrogram.
Fig. 5 is the EDS spectrums using the product obtained by the preparation method of manganese base fluorescent powder described in the embodiment of the present invention 2 Figure.
Fig. 6 is the exciting light using the product obtained by the preparation method of manganese base fluorescent powder described in the embodiment of the present invention 2 Spectrogram.
Fig. 7 is the transmitting light using the product obtained by the preparation method of manganese base fluorescent powder described in the embodiment of the present invention 2 Spectrogram.
Embodiment
The present invention is specifically described below by embodiment, it is necessary to it is pointed out here that, following examples are only used It is further detailed in the present invention, it is impossible to be interpreted as limiting the scope of the invention, the field is skilled in technique Personnel can make some nonessential modifications and adaptations according to foregoing invention content to the present invention.
Embodiment 1
A kind of preparation method of manganese base fluorescent powder, it is specifically what is followed the steps below：
（1）Under normal temperature and pressure conditionses, by KMnO4, KF first add in HF solution, be stirring evenly and then adding into H2O2Carry out anti- Should, after question response, then through filtering, cleaned, dried so that presoma K is made with methanol2MnF5·H2O；The step（1）In, respectively The dosage of material is KMnO according to mol ratio4：KF：H2O2：HF =1：2：4：200 are configured；
（2）By presoma K2MnF5·H2O、K2TiF6、KMnO4, KF add HF solution in, stir reaction 40 h, most Cleaned, dried with methanol through filtering again afterwards；The step（2）In, the dosage of each material is K according to mol ratio2MnF5· H2O：K2TiF6：KMnO4：KF：HF=1：20：5：5:500 are configured.
Its in this example prepares the principle reacted：
KMnO4 + KF + 4HF + 2H2O2 → K2MnF5·H2O + 3H2O + 2O2 (1)
2K2MnF5·H2O→ K2MnF6 + MnF2 +2KF + H2O (2)
Wherein, KMnO4While promoting the progress of reaction (2), and react (2) progress, the Mn of generation4+With matrix K2TiF6Also reacted so that Mn4+It is micro to instead of K2TiF6In Ti4+；React (2) and micro Mn4+Substitution reaction it is same Shi Fasheng, mutually promote, finally realize in K2TiF6Middle introducing Mn4+And K is made2TiF6:Mn4+。
Understood with reference to the testing result shown in accompanying drawing 1,2,3 and 4：Using the manganese base fluorescence obtained by the preparation method Powder, the agent structure of its crystal is matrix K2TiF6, Mn elements substitution matrix K2TiF6The content ratio of middle Ti elements is 5.75 At.%, its excitation peak are 463.4 nm and 363 nm, emission spectrum broadband emission between 580~660 nm：There are five intersections Emission peak, respectively 590.0 nm, 603.6 nm, 616.2 nm, 634.6 nm and 650.4 nm, wherein highest peak is 634.6 nm, and a width of 10 nm of half-peak of highest peak.
Embodiment 2
A kind of preparation method of manganese base fluorescent powder, it is specifically what is followed the steps below：
（1）Under normal temperature and pressure conditionses, by KMnO4, KF first add in HF solution, be stirring evenly and then adding into H2O2Carry out anti- Should, after question response, then through filtering, cleaned, dried so that presoma K is made with ethanol2MnF5·H2O；The step（1）In, respectively The dosage of material is KMnO according to mol ratio4：KF：H2O2：HF =1：0.2：2：100 are configured；
（2）By presoma K2MnF5·H2O、K2TiF6、KMnO4, KF add HF solution in, stir reaction 10 h, most Cleaned, dried with ethanol through filtering again afterwards；The step（2）In, the dosage of each material is K according to mol ratio2MnF5· H2O：K2TiF6：KMnO4：KF：HF=1：0.1：0.5：0.5:100 are configured.
Understood with reference to the testing result shown in accompanying drawing 5,6 and 7：Using the manganese base fluorescent powder obtained by the preparation method, The agent structure of its crystal is matrix K2TiF6, Mn elements substitution matrix K2TiF6The content ratio of middle Ti elements is 4.80 At.%, its excitation peak are 462.8 nm and 363 nm, can light and match with LED blue chips and mercury vapour, its emission spectrum exists Broadband emission between 580~660 nm：Have five intersection emission peaks, respectively 590.2 nm, 603.2 nm, 616.2 nm, 634.8 nm and 650.4 nm, wherein highest peak are 634.8 nm, and a width of 10 nm of half-peak of highest peak.
Embodiment 3
A kind of preparation method of manganese base fluorescent powder, it is specifically what is followed the steps below：
（1）Under normal temperature and pressure conditionses, by KMnO4、CaF2First add in HF solution, be stirring evenly and then adding into ethanol progress React, after question response, then through filtering, cleaned, dried so that presoma CaMnF is made with methanol5·H2O；The step（1）In, The dosage of each material is KMnO according to mol ratio4：CaF2：Ethanol：HF =1：5：4：400 are configured；
（2）By presoma CaMnF5·H2O、CaTiF6、KMnO4、CaF2Add in HF solution, stir 10 h of reaction, Finally cleaned again through filtering with methanol, prepared by drying；The step（2）In, the dosage of each material is according to mol ratio CaMnF5·H2O：CaTiF6：KMnO4：CaF2：HF=1：100：5：5:1000 are configured.
After testing：Using the manganese base fluorescent powder obtained by the preparation method, the agent structure of its crystal is matrix CaTiF6, Mn elements substitution matrix CaTiF6The content ratio of middle Ti elements is 8.50 at.%, and its excitation peak is 463.3 nm and 363.0 Nm, it can light and match with LED blue chips and mercury vapour, its emission spectrum broadband emission between 580~660 nm：There are five The emission peak of intersection, respectively 590.5 nm, 603.3 nm, 616.5 nm, 634.0 nm and 650.4 nm, wherein highest peak are 634.0 nm, and a width of 10 nm of half-peak of highest peak.
Embodiment 4
A kind of preparation method of manganese base fluorescent powder, it is specifically what is followed the steps below：
（1）Under normal temperature and pressure conditionses, by KMnO4, NaF first add in HF solution, be stirring evenly and then adding into ethanol progress React, after question response, then through filtering, cleaned, dried so that presoma Na is made with acetone2MnF5·H2O；The step（1） In, the dosage of each material is KMnO according to mol ratio4：NaF：Ethanol：HF =1：1.5：3.5：400 are configured；
（2）By presoma Na2MnF5·H2O、Na2TiF6、KMnO4, NaF add HF solution in, stir reaction 30 h, Finally cleaned again through filtering with acetone, prepared by drying；The step（2）In, the dosage of each material is according to mol ratio Na2MnF5·H2O：Na2TiF6：KMnO4：NaF：HF=1：500：5：5:1000 are configured.
After testing：Using the manganese base fluorescent powder obtained by the preparation method, the agent structure of its crystal is matrix Na2TiF6, Mn elements substitution matrix Na2TiF6The content ratio of middle Ti elements is 10.05 at.%, and its excitation peak is 465.5 nm and 366 Nm, emission spectrum broadband emission between 580~660 nm：There are the emission peak of five intersections, respectively 591.0 nm, 604.2 Nm, 616.4 nm, 635.8 nm and 650.4 nm, wherein highest peak are 635.8 nm, and a width of 10 nm of half-peak of highest peak.

Claims (1)

1. the preparation method of a kind of fluorescent material suitable for LED illumination, it is characterised in that it is specifically to follow the steps below 's：
（1）Under normal temperature and pressure conditionses, by KMnO4, KF first add in HF solution, be stirring evenly and then adding into H2O2Reacted, treated After completion of the reaction, then through filtering, cleaned, dried so that presoma K is made with methanol2MnF5·H2O；The step（1）In, each material Dosage according to mol ratio be KMnO4：KF：H2O2：HF =1：2：4：200 are configured；
（2）By presoma K2MnF5·H2O、K2TiF6、KMnO4, KF add HF solution in, stir reaction 40 h, finally again Through filtering, cleaned, dried with methanol；The step（2）In, the dosage of each material is K according to mol ratio2MnF5·H2O： K2TiF6：KMnO4：KF：HF=1：20：5：5：500 are configured.
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CN105505384B (en) * 2015-12-03 2017-12-19 河北利福光电技术有限公司 A kind of narrow band red light fluorescent powder and preparation method thereof
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CN110257065B (en) * 2019-06-28 2022-05-17 重庆文理学院 Red fluorescent powder with waterproof performance and preparation method thereof

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CN102732249A (en) * 2011-04-08 2012-10-17 信越化学工业株式会社 Preparation of complex fluoride and complex fluoride phosphor
CN103980896A (en) * 2014-04-29 2014-08-13 中国科学院福建物质结构研究所 Preparation method of fluoride fluorescent powder material

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JP5783302B2 (en) * 2013-07-03 2015-09-24 日亜化学工業株式会社 Fluoride phosphor, light emitting device using the same, and method for producing phosphor
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CN102732249A (en) * 2011-04-08 2012-10-17 信越化学工业株式会社 Preparation of complex fluoride and complex fluoride phosphor
CN103980896A (en) * 2014-04-29 2014-08-13 中国科学院福建物质结构研究所 Preparation method of fluoride fluorescent powder material

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