CN106566545B - A kind of Mn4+The seven hafnifluoride red illuminating materials and preparation method of activation - Google Patents
A kind of Mn4+The seven hafnifluoride red illuminating materials and preparation method of activation Download PDFInfo
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- CN106566545B CN106566545B CN201610988266.0A CN201610988266A CN106566545B CN 106566545 B CN106566545 B CN 106566545B CN 201610988266 A CN201610988266 A CN 201610988266A CN 106566545 B CN106566545 B CN 106566545B
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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
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Abstract
The present invention relates to inorganic functional material fields, disclose a kind of blue-light LED chip Mn4+The preparation method of seven hafnifluoride red illuminating materials of activation.Blue-light LED chip Mn of the present invention4+The chemical composition of seven hafnifluoride red illuminating materials of activation is K3Hf1‑xF7:xMn4+；X is corresponding doping Mn4+Ion is with respect to Hf4+Molar percentage coefficient shared by ion, 0<x≤0.10.Red illuminating material according to the present invention is under blue light excitation, and based on the red emission of 628 nm or so, luminous efficiency is high.Blue-light LED chip Mn according to the present invention4+The preparation method of seven hafnifluoride red illuminating materials of activation is liquid phase method, and synthesis technology is simple, is suitble to large-scale industrial production.
Description
Technical field
The present invention relates to a kind of blue-light LED chip Mn4+The preparation method of seven hafnifluoride red illuminating materials of activation,
Belong to inorganic functional material preparation field.
Background technology
Based on blue-ray LED solid-state lighting due to its energy-saving and environmental protection, service life is long the advantages that, be widely used in people
In daily life.Due to the commercial yellow luminous material of blue-ray LED（Also known as fluorescence YAG:Ce3+Lack red component transmitting, causes
Such white light LED color temperature is high, and colour rendering index is low.In order to obtain the warm white LED of low color temperature, high color rendering index (CRI), it is desirable to provide one
The fixed red fluorescence powder that can be effectively excited by blue light.
In recent years, Mn4+The fluoride red illuminating material of activation, since their excitation wavelengths can well and blue light
LED chip launch wavelength matches, and its red emission is efficient, so as to cause the concern of people.Such as A2MF6(A is
Na, K, Rb etc.；M is Ti, Si, Sn, Ge etc.) luminescent properties of red fluorescence powder are by wide coverage.
In this invention, we successfully develop the Mn that novel blue light effectively excites in a solution of hydrofluoric acid4+Activation
Seven hafnifluoride red illuminating material K3Hf1-xF7:xMn4+（X is corresponding doping Mn4+Ion is with respect to Hf4+Mole shared by ion
Percent coefficient, 0< x ≤ 0.10）Preparation method.
Invention content
The object of the present invention is to provide a kind of blue-light LED chip Mn4+Seven hafnifluoride red illuminating materials of activation
Preparation method.
To achieve the goals above, blue-light LED chip Mn according to the present invention4+The seven hafnifluoride red hair of activation
Luminescent material, chemical composition are：K3Hf1-xF7:xMn4+；X is corresponding doping Mn4+Ion is with respect to Hf4+Mole percent shared by ion
Than coefficient, 0< x ≤ 0.10.The mass percentage of raw material type used in the present invention and each raw material is respectively：Fluorination
Potassium：38.0 ~ 65.0 % or potassium carbonate：60.0~ 65.0 %；Potassium hexafluoromanganate：0.2~ 10.0 %；Hafnium oxide：20.0 ~
45 %；Hydrofluoric acid：1.0 ~ 20.0 %.
Blue light wavelength of the present invention is 440~480nm.
The preparation method of above-mentioned red illuminating material is to use liquid phase method, and various raw materials are by above-mentioned stoichiometric ratio.Tool
Body includes the following steps：First hafnium oxide is added in hydrofluoric acid solution and is reacted 30~60 minutes, straight dissolving is complete.Then it is added
Potassium hexafluoromanganate reacts 10~30 minutes under 20 ~ 80 DEG C of water bath conditions, adds potassium fluoride or potash solid continues to stir
30~60 minutes.Gained sediment anhydrous acetic acid and absolute methanol are respectively washed 3 times, and finally drying 24 is small in vacuum drying chamber
When, obtained orange red powder is final products.
The red fluorescence powder of the present invention has very strong red emission under blue light excitation（Emission peak is located at the left sides 628 nm
It is right）, luminous efficiency height.The emission spectrum CIE value of sample is close to feux rouges NTSC (National Television Standard
Committee) standard value (x = 0.67, y = 0.33)。
Description of the drawings
Fig. 1 is K in example 13HfF7:Mn4+XRD diffraction patterns；
Fig. 2 is K in example 13HfF7:Mn4+Room temperature excitation spectrum（Monitoring wavelength is 628 nm）And emission spectrum（Excitation
Wavelength is 465 nm）；
Specific implementation mode
Embodiment 1：
Weigh 0.202 g and HfO2It is dissolved in 10ml hydrofluoric acid（40wt%）In, it stirs and is extremely dissolved within 30 minutes completely under room temperature,
0.062g potassium hexafluoromanganates are added into this solution to react 30 minutes；Then 0.406g potassium fluoride solids are added and continue stirring 60
min.Gained sediment anhydrous acetic acid and absolute methanol are respectively washed 3 times, finally 24 hours dry in vacuum drying chamber, are obtained
Orange red powder is final products K3HfF7:Mn4+。
The XRD diffraction patterns of this fluorescent powder are as shown in Fig. 1, diffraction maximum and the standard card JCPDS 78-1827 of sample
（K3HfF7）It is completely the same, the diffraction maximum of any dephasign is not observed, this shows that the sample synthesized by us has single crystalline substance
Phase.
Attached drawing 2 show the room temperature excitation spectrum of sample（Monitoring wavelength is 628 nm）And emission spectrum（Excitation wavelength is
465nm）.Sample is in ultraviolet region（320 nm ~ 390 nm）With blue light area（400 nm ~ 500 nm）With very strong width
Band excitation.Under the excitation of 478 nm light, the transmitting of sample is based on the red emission of 628 nm or so, and excitation purity is high.
Embodiment 2：
Weigh 0.202 g and HfO2It is dissolved in 5ml hydrofluoric acid（40wt%）In, 20 minutes are stirred under 60 DEG C of water bath conditions extremely
Dissolving is complete, and 0.062g potassium hexafluoromanganates are added into this solution and react 30 minutes；Then be added 0.174g potassium fluorides solid after
30 min of continuous stirring.Gained sediment anhydrous acetic acid and absolute methanol are respectively washed 3 times, and finally drying 24 is small in vacuum drying chamber
When, obtained orange red powder is final products K3HfF7:Mn4+。
Embodiment 3：
Weigh 0.202 g and HfO2It is dissolved in 20ml hydrofluoric acid（40wt%）In, 20 minutes are stirred under 40 DEG C of water bath conditions extremely
Dissolving is complete, and 0.062g potassium hexafluoromanganates are added into this solution and react 30 minutes；Then be added 0.590g potash solids after
60 min of continuous stirring.Gained sediment anhydrous acetic acid and absolute methanol are respectively washed 3 times, and finally drying 24 is small in vacuum drying chamber
When, obtained orange red powder is final products K3HfF7:Mn4+。
Embodiment 4：
Weigh 0.197 g and HfO2It is dissolved in 10 ml hydrofluoric acid（40wt%）In, 30 minutes are stirred under normal temperature condition to dissolving
Completely, 0.124g potassium hexafluoromanganates are added into this solution to react 30 minutes；Then the continuation of 0.290 g potassium fluoride solids is added
Stir 50 min.Gained sediment anhydrous acetic acid and absolute methanol are respectively washed 3 times, and finally drying 24 is small in vacuum drying chamber
When, obtained orange red powder is final products K3HfF7:Mn4+。
Embodiment 5：
Weigh 0.197 g and HfO2It is dissolved in 15 ml hydrofluoric acid（40wt%）In, it is stirred 30 minutes under 80 DEG C of water bath conditions
It is complete to dissolving, 0.124g potassium hexafluoromanganates reaction 30 minutes is added into this solution；Then 0.414g potash solids are added
Continue to stir 60 min.Gained sediment anhydrous acetic acid and absolute methanol are respectively washed 3 times, finally dry 24 in vacuum drying chamber
Hour, obtained orange red powder is final products K3HfF7:Mn4+。
Claims (4)
1. a kind of blue-light LED chip Mn4+The preparation method of seven hafnifluoride red illuminating materials of activation, steps are as follows：First
Hafnium oxide is added in hydrofluoric acid solution and is reacted 30~60 minutes, straight dissolving is complete, and potassium hexafluoromanganate is then added in 20 ~ 80
It is reacted 10~30 minutes under DEG C water bath condition, adds potassium fluoride or potash solid continues stirring 30~60 minutes, gained is heavy
Starch anhydrous acetic acid and absolute methanol are respectively washed 3 times, finally 24 hours dry in vacuum drying chamber, obtained orange red powder
For final products,
Wherein, the blue-light LED chip Mn4+The chemical composition of seven hafnifluoride red illuminating materials of activation is：K3Hf1- xF7:xMn4+；X is corresponding doping Mn4+Ion is with respect to Hf4+Molar percentage coefficient shared by ion, 0< x ≤ 0.10.
2. preparation method as described in claim 1, which is characterized in that the blue light refers to the light that wavelength is 440nm-480nm.
3. preparation method as described in claim 1, which is characterized in that the type of used raw material and the quality of each raw material hundred
Point content is respectively：Potassium fluoride：38.0~ 65.0 %；Potassium hexafluoromanganate：0.2~ 10.0 %；Hafnium oxide：20.0 ~ 45 %；
Hydrofluoric acid：1.0 ~ 20.0 %.
4. preparation method as described in claim 1, which is characterized in that the type of used raw material and the quality of each raw material hundred
Point content is respectively：Potassium carbonate：60.0~ 65.0 %；Potassium hexafluoromanganate：0.2~ 10.0 %；Hafnium oxide：20.0 ~ 45 %；
Hydrofluoric acid：1.0 ~ 20.0 %.
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Citations (4)
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| US5830242A (en) * | 1995-03-15 | 1998-11-03 | Takeshi Yao | Process for producing metal oxide precipitates |
| CN103003388A (en) * | 2010-07-27 | 2013-03-27 | 通用电气公司 | Moisture-resistant phosphor and associated method |
| CN103102880A (en) * | 2012-12-12 | 2013-05-15 | 中国科学院福建物质结构研究所 | Simple spectrum band up-conversion luminescence nanocrystalline and preparation method thereof |
| CN103429701A (en) * | 2011-03-23 | 2013-12-04 | 通用电气公司 | Color stable manganese-doped phosphors |
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| US10563121B2 (en) * | 2014-06-12 | 2020-02-18 | Current Lighting Solutions, Llc | Red-emitting phosphors and associated devices |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5830242A (en) * | 1995-03-15 | 1998-11-03 | Takeshi Yao | Process for producing metal oxide precipitates |
| CN103003388A (en) * | 2010-07-27 | 2013-03-27 | 通用电气公司 | Moisture-resistant phosphor and associated method |
| CN103429701A (en) * | 2011-03-23 | 2013-12-04 | 通用电气公司 | Color stable manganese-doped phosphors |
| CN103102880A (en) * | 2012-12-12 | 2013-05-15 | 中国科学院福建物质结构研究所 | Simple spectrum band up-conversion luminescence nanocrystalline and preparation method thereof |
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