CN104357050A - High-color-purity red luminescent material for blue light excitation and preparation method of red luminescent material - Google Patents
High-color-purity red luminescent material for blue light excitation and preparation method of red luminescent material Download PDFInfo
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- CN104357050A CN104357050A CN201410574320.8A CN201410574320A CN104357050A CN 104357050 A CN104357050 A CN 104357050A CN 201410574320 A CN201410574320 A CN 201410574320A CN 104357050 A CN104357050 A CN 104357050A
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Abstract
The invention relates to the field of white light emitting diode, and discloses a preparation method of a high-color-purity red luminescent material for blue light excitation. The high-color-purity red luminescent material for blue light excitation comprises the following chemical constitutions: M<II>Ge(1-x)F6:xMn<4+>, wherein M<II> is selected from one or more of alkaline earth metal ions Ba<2+>, Sr<2+>, Ca<2+> and Mg<2+>; x is a molar percentage coefficient of the correspondingly doped Mn<4+> to Ge<4+> ions; x is larger than or equal to 0 and smaller than or equal to 0.10. The high-color-purity red luminescent material for blue light excitation is prepared with a hydrothermal method. The red florescent powder can be excited by blue light to irradiate 634 nm of red light with the high luminous efficiency and the good color purity.
Description
Technical field
The present invention relates to and be a kind ofly applicable to blue-light excited high color purity red illuminating material and preparation method thereof, specifically, is red illuminating material of a kind of blue-light semiconductor chip (LED) and preparation method thereof.Belong to inorganic functional material preparation field.
Background technology
White light emitting diode (W-LED, white-light-emitting diode) solid state lighting relative to traditional lighting engineering (as incandescent light, luminescent lamp etc.) have energy-conservation, light efficiency is high, suitability is wide, good stability, the plurality of advantages such as environmentally friendly, has become the study hotspot of people.Current business-like white light LEDs still by use GaN base LED chip the blue light (about 460 nm) sent out excite yellow rare-earth fluorescent powder YAG:Ce
3+compound obtains white light, but this kind of white light LEDs lacks the spectrum of red light region due to it, causes that its colour temperature is higher, colour rendering index is poor, and its luminous efficiency is low.Two kinds of methods are addressed this problem.The first, to YAG:Ce
3+bloom is optimized, such as, by introducing the rare earth ion Eu glowed
3+, Sm
3+, Pr
3+etc. improving YAG:Ce
3+red emission.But this type of rare earth ion mixes Eu altogether in blue light region (~ 460 nm) launching efficiency low causing
3+, Sm
3+, Pr
3+yAG:Ce
3+fluorescent material red emission efficiency is low, to YAG:Ce
3+spectrum improvement result not obvious [X. S. Yan, W. W. Li, X. B. Wang, K. Sun, " Facile Synthesis of Ce
3+, Eu
3+co-Doped YAG Nanophosphor for White Light-Emitting Diodes ", J Electrochem Soc.159 (2012) H195; Y. X. Pan, M. M. Wu, Q. Su, " Tailored photoluminescence of YAG:Cephosphor through various methods ", J. Phys. Chem. Solid. 65 (2004) 845].The second, mix appropriate red fluorescence material to improve the transmitting of white light LEDs in red light district.Such as, investigators are by YAG bloom and Ca (La
1-xeu
x)
4si
3o
13rouge and powder mixes mutually, on blue-light LED chip, obtain white light, improves colour rendering index [C. Shen, Y. Yang, S. Jin, J. Ming, H. Feng, Z. Xu, the " Ca (La of white light LEDs
1-xeu
x)
4si
3o
13red emitting phosphor for white light emitting diodes " Physica B 404 (2009) 1481].The vertical Asia of state's inner circumferential waits people also by YAG:Ce
3+bloom mixes with CdTeSe/ZnS quantum dot to be coated on blue-light LED chip and obtains efficient white light [X. M. Xu, Y. L. Wang, W. X. Xia, L. Y. Zhou, F. Z. Gong, L. Wu, " Novel quantum dots:Water-based CdTeSe/ZnS and YAG hybrid phosphor for white light-emitting diodes ", Mater. Chem. Phys. 139 (2013) 210].But the current red light emitting phosphor efficiency being applicable to blue LED die is low, this is because it is low in blue light region assimilated efficiency.Such as, Eu is mixed
3+series red fluorescence powder, due to Eu
3+excite and belong to
f-
fenergy level transition (parity forbidden transition jing), it is weak in blue light region excitation intensity, causes its luminous efficiency low.Therefore study novel blue light LED chip red fluorescence powder and there is important Research Significance and application prospect.
Summary of the invention
The object of the invention is the deficiency for existing blue-light excited red illuminating material, provide that a kind of luminous efficiency is high, good stability, be suitable for the red illuminating material of blue-light LED chip.
Another object of the present invention is to provide the preparation method of above-mentioned red illuminating material.
To achieve these goals, involved in the present invention is applicable to blue-light excited red illuminating material, and its chemical constitution is: M
iIge
1-xf
6: xMn
4+.M
iIfor alkaline-earth metal ions Ba
2+, Sr
2+, Ca
2+, Mg
2+in one or more; X is corresponding doped with Mn
4+ion Phase is to Ge
4+molar percentage coefficient shared by ion, 0 < x≤0.10.The mass percentage of raw material type used in the present invention and each raw material is respectively: barium carbonate (BaCO
3): 23.39 ~ 46.79 %; Strontium carbonate powder (SrCO
3): 0 ~ 17.46 %; Calcium carbonate (CaCO
3): 0 ~ 11.87 %; Magnesium oxide (MgO): 0 ~ 4.79 %; Zinc oxide (ZnO): 0 ~ 9.58 %; Germanium oxide (GeO
2): 22.23 ~ 24.61 %; Hydrofluoric acid (HF): 28.50 ~ 57.10 %; Potassium permanganate (KMnO
4): 0.38 ~ 3.81 %.
Blue light wavelength of the present invention is 450 ~ 470 nm.
The preparation method of above-mentioned red illuminating material, adopt hydrothermal method, comprise the steps: stoichiometrically, each component raw material is dissolved in hydrofluoric acid solution, is mixed with mixing solutions, react 4 ~ 12 hours at then mixing solutions being placed in autoclave 120 ~ 180 DEG C, be chilled to room temperature, with distilled water wash gained solid, then in vacuum drying oven dry 24 hours, the last pink powder that obtains was the finished product.
Red illuminating material of the present invention has very strong red emission (emission peak is positioned at about 634 nm) under blue-light excited, and luminous efficiency is high.The emmission spectrum CIE value of sample close to ruddiness NTSC (National Television Standard Committee) standard value (
x=0.67,
y=0.33).
Accompanying drawing explanation
Fig. 1 is the XRD diffractogram of red illuminating material of the present invention;
Fig. 2 is room temperature excitation spectrum (monitoring wavelength is 634 nm) and the emmission spectrum (excitation wavelength is 460 nm) of red illuminating material of the present invention;
Fig. 3 is red illuminating material of the present invention and the electroluminescent spectrum figure of the single red LED made by blue-light LED chip under 20 mA electric currents excite.
Embodiment
Embodiment 1:
Take barium carbonate (BaCO
3): 0.996 g, germanium oxide (GeO2): 0.523 g, potassium permanganate (KMnO
4): 5 mL (40 %) hydrofluoric acid (HF) are then joined above-mentioned solid mixture stirring and dissolving, then add 45 mL distilled water by 0.063g.Reacted 12 hours at 180 DEG C in autoclave by gained solution subsequently, be chilled to room temperature, with distilled water wash gained solid, then in vacuum drying oven dry 24 hours, the last pink powder that obtains was final BaGeF
6: Mn
4+fluorescent material.
The XRD diffractogram of this fluorescent material as shown in Figure 1, with standard card JCPDS 74-0924(BaGeF
6) contrast, both are completely the same, do not observe the diffraction peak of any dephasign, and this shows that the sample synthesized by us has single crystalline phase.
Attached room temperature excitation spectrum (monitoring wavelength is 634 nm) and the emmission spectrum (excitation wavelength is 460 nm) that Figure 2 shows that sample.Sample has very strong broadband excitation at ultraviolet region (320 nm ~ 390 nm) and blue light district (420 nm ~ 480 nm).Under 460 nm optical excitation, the transmitting of sample is based on the red emission of about 634 nm, this Mn corresponded to
4+'s
2e
g-
4a
2gtransition.Spectrum CIE coordinate figure is:
x=0.69,
y=0.31.Our sample CIE value close to ruddiness NTSC (National Television Standard Committee) standard value (
x=0.67,
y=0.33)
Accompanying drawing 3 is the luminescent spectrum of red LED device under 20 mA electric currents excite being coated with our sample.In figure ~ emission peak of 460 nm sends by GaN chip and not by the blue light that fluorescent material absorbs, launching the most by force of fluorescent material is positioned at 634 nm places.The red emission of this LED is very strong.
Embodiment 2:
Take barium carbonate (BaCO
3): 0.996 g, germanium oxide (GeO
2): 0.523 g, potassium permanganate (KMnO
4): 10 mL (40 %) hydrofluoric acid (HF) are then joined above-mentioned solid mixture stirring and dissolving, then add 40 mL distilled water by 0.063g.Reacted 8 hours at 180 DEG C in autoclave by gained solution subsequently, be chilled to room temperature, with distilled water wash gained solid, then in vacuum drying oven dry 24 hours, the last pink powder that obtains was final BaGeF
6: Mn
4+fluorescent material.
Embodiment 3:
Take barium carbonate (BaCO
3): 0.996 g, germanium oxide (GeO
2): 0.523 g, potassium permanganate (KMnO
4): 0.033 g, then joins above-mentioned solid mixture stirring and dissolving by 10 mL (40%) hydrofluoric acid (HF), then adds 40 mL distilled water.Reacted 8 hours at 180 DEG C in autoclave by gained solution subsequently, be chilled to room temperature, with distilled water wash gained solid, then in vacuum drying oven dry 24 hours, the last pink powder that obtains was final BaGeF
6: Mn
4+fluorescent material.
Embodiment 4:
Take barium carbonate (BaCO
3): 0.996 g, germanium oxide (GeO2): 0.523 g, potassium permanganate (KMnO
4): 0.063g, then joins above-mentioned solid mixture stirring and dissolving by 10 mL (40%) hydrofluoric acid (HF), then adds 40 mL distilled water.Reacted 12 hours at 120 DEG C in autoclave by gained solution subsequently, be chilled to room temperature, with distilled water wash gained solid, then in vacuum drying oven dry 24 hours, the last pink powder that obtains was final BaGeF
6: Mn
4+fluorescent material.
Embodiment 5:
Take barium carbonate (BaCO
3): 0.896 g, Strontium carbonate powder (SrCO
3): 0.074 g, germanium oxide (GeO
2): 0.523 g, potassium permanganate (KMnO
4): 0.063g, then joins above-mentioned solid mixture stirring and dissolving by 10 mL (40%) hydrofluoric acid (HF), then adds 40 mL distilled water.Reacted 12 hours at 180 DEG C in autoclave by gained solution subsequently, be chilled to room temperature, with distilled water wash gained solid, then in vacuum drying oven dry 24 hours, the last pink powder that obtains was final Ba
0.90sr
0.10geF
6: Mn
4+fluorescent material.
Embodiment 6:
Take barium carbonate (BaCO
3): 0.896 g, calcium carbonate (CaCO
3): 0.051 g, germanium oxide (GeO
2): 0.523 g, potassium permanganate (KMnO
4): 20 mL (40 %) hydrofluoric acid (HF) are then joined above-mentioned solid mixture stirring and dissolving, then add 30 mL distilled water by 0.033g.Reacted 12 hours at 180 DEG C in autoclave by gained solution subsequently, be chilled to room temperature, with distilled water wash gained solid, then in vacuum drying oven dry 24 hours, the last pink powder that obtains was final Ba
0.90ca
0.10geF
6: Mn
4+fluorescent material.
Embodiment 7:
Take barium carbonate (BaCO
3): 0.896 g, zinc oxide (ZnO): 0.041 g, germanium oxide (GeO
2): 0.523 g, potassium permanganate (KMnO
4): 0.063g, then joins above-mentioned solid mixture stirring and dissolving by 50 mL (40%) hydrofluoric acid (HF).Reacted 12 hours at 180 DEG C in autoclave by gained solution subsequently, be chilled to room temperature, with distilled water wash gained solid, then in vacuum drying oven dry 24 hours, the last pink powder that obtains was final Ba
0.90zn
0.10geF
6: Mn
4+fluorescent material.
Claims (5)
1. be applicable to a blue-light excited high color purity red illuminating material, its chemical constitution is M
iIge
1-xf
6: xMn
4+; M
iIfor alkaline-earth metal ions Ba
2+, Sr
2+, Ca
2+, Mg
2+in one or more; X is corresponding doped with Mn
4+ion Phase is to Ge
4+molar percentage coefficient shared by ion, 0.0 < x≤0.10.
2. be applicable to blue-light excited high color purity red illuminating material as claimed in claim 1, it is characterized in that described blue light refers to that wavelength is the light of 420 ~ 470nm.
3. be applicable to blue-light excited high color purity red illuminating material as claimed in claim 1, it is characterized in that described high color purity refer to the emmission spectrum CIE value of sample close to ruddiness NTSC (National Television Standard Committee) standard value (
x=0.67,
y=0.33).
4. the preparation method of high color purity red illuminating material blue-light excited as claimed in claim 1, it is characterized in that preparation method is hydrothermal method, comprise the steps: stoichiometrically, each component raw material is dissolved in hydrofluoric acid solution, be mixed with mixing solutions, then react 4 ~ 12 hours at mixing solutions being placed in autoclave 120 ~ 180 DEG C, be chilled to room temperature, with distilled water wash gained solid, then in vacuum drying oven dry 24 hours, the last pink powder that obtains was the finished product.
5. the preparation method of high color purity red illuminating material blue-light excited as claimed in claim 4, is characterized in that the kind of used raw material and the mass percentage of each raw material are respectively: barium carbonate (BaCO
3): 23.39 ~ 46.79 %; Strontium carbonate powder (SrCO
3): 0 ~ 17.46 %; Calcium carbonate (CaCO
3): 0 ~ 11.87 %; Magnesium oxide (MgO): 0 ~ 4.79 %; Zinc oxide (ZnO): 0 ~ 9.58 %; Germanium oxide (GeO
2): 22.23 ~ 24.61 %; Hydrofluoric acid (HF): 28.50 ~ 57.10 %; Potassium permanganate (KMnO
4): 0.38 ~ 3.81 %.
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Cited By (6)
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|---|---|---|---|---|
| CN106433624A (en) * | 2015-08-04 | 2017-02-22 | 云南民族大学 | Uniform-appearance and high-color-purity Mn4+ activated red fluoride luminescent material prepared by using micro-emulsion method |
| CN107353899A (en) * | 2017-06-15 | 2017-11-17 | 华南理工大学 | A kind of Mn4+Doped fluoride monocrystalline red light material and preparation method and application |
| WO2018132998A1 (en) * | 2017-01-19 | 2018-07-26 | 云南民族大学 | Method for preparing red luminescent material excited by blue light |
| CN110499157A (en) * | 2019-09-10 | 2019-11-26 | 云南民族大学 | A kind of light activated fluogermanate infrared lumious material for mixing Cr3+ of indigo plant |
| CN110511746A (en) * | 2019-09-11 | 2019-11-29 | 云南民族大学 | One kind mixing Cr3+Fluoride near-infrared light-emitting material and its synthetic method |
| CN110791282A (en) * | 2019-10-31 | 2020-02-14 | 云南民族大学 | Mn-doped steel wire4+Alkali metal fluoferrite red luminescent material and preparation method thereof |
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Cited By (10)
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| CN106433624A (en) * | 2015-08-04 | 2017-02-22 | 云南民族大学 | Uniform-appearance and high-color-purity Mn4+ activated red fluoride luminescent material prepared by using micro-emulsion method |
| CN106433624B (en) * | 2015-08-04 | 2018-06-12 | 云南民族大学 | Microemulsion method prepares the uniform Mn of pattern4+The high color purity fluoride red illuminating material of activation |
| WO2018132998A1 (en) * | 2017-01-19 | 2018-07-26 | 云南民族大学 | Method for preparing red luminescent material excited by blue light |
| CN107353899A (en) * | 2017-06-15 | 2017-11-17 | 华南理工大学 | A kind of Mn4+Doped fluoride monocrystalline red light material and preparation method and application |
| CN110499157A (en) * | 2019-09-10 | 2019-11-26 | 云南民族大学 | A kind of light activated fluogermanate infrared lumious material for mixing Cr3+ of indigo plant |
| CN110499157B (en) * | 2019-09-10 | 2023-03-31 | 云南民族大学 | Blue light excited Cr3+ doped fluorogermanate infrared luminescent material |
| CN110511746A (en) * | 2019-09-11 | 2019-11-29 | 云南民族大学 | One kind mixing Cr3+Fluoride near-infrared light-emitting material and its synthetic method |
| CN110511746B (en) * | 2019-09-11 | 2023-05-19 | 云南民族大学 | Cr-doped steel 3+ Fluoride near infrared luminescent material and synthesis method thereof |
| CN110791282A (en) * | 2019-10-31 | 2020-02-14 | 云南民族大学 | Mn-doped steel wire4+Alkali metal fluoferrite red luminescent material and preparation method thereof |
| CN110791282B (en) * | 2019-10-31 | 2022-07-12 | 云南民族大学 | Mn-doped steel wire4+Alkali metal fluoferrite red luminescent material and preparation method thereof |
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Application publication date: 20150218 |