CN106433633A - Method for preparing novel Mn (IV) ion activated red luminescence material - Google Patents
Method for preparing novel Mn (IV) ion activated red luminescence material Download PDFInfo
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- CN106433633A CN106433633A CN201510467959.0A CN201510467959A CN106433633A CN 106433633 A CN106433633 A CN 106433633A CN 201510467959 A CN201510467959 A CN 201510467959A CN 106433633 A CN106433633 A CN 106433633A
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Abstract
The invention relates to the field of white light emitting diodes, and discloses a method for preparing a novel Mn (IV) ion activated red luminescence material. The novel Mn (IV) ion activated red luminescence material disclosed by the invention has the chemical composition of AB4-xO9:xMn<4+>, wherein A refers to one or more of alkaline-earth metals ions such as Ba<2+>, Ca<2+> and Mg<2+>; B refers to one or more of alkaline-earth metals ions such as Ge<4+>, Ti<4+> and Zr<4+>; x refers to a molar percentage coefficient of correspondingly doped Mn<4+> relative to B<4+>; x is more than 0 and less than or equal to 0.10. The red luminescence material disclosed by the invention has the principle red emission of 667nm under blue light excitation and has high luminous efficiency. The novel Mn (IV) ion activated red luminescence material disclosed by the invention is prepared by a high temperature solid state method.
Description
Technical field
The present invention relates to a kind of ion-activated method for preparing red luminescence material of new Mn (IV), specifically, it is that one kind can be by blue light activated red illuminating material of blue light and preparation method thereof.Belong to inorganic functional material preparation field.
Background technology
Mn (IV) ion is a kind of efficient centre of luminescence, thus being widely used in the middle of some inorganic red luminescent materials.The ion-activated red illuminating material of these Mn (IV) can be applied to the fields such as illumination, light storage.The current ion-activated red illuminating material of Mn (IV) mainly includes two big class：Fluoride red light material and composite oxides red light material.The ion-activated fluoride red light material of Mn (IV) is due to can use substantial amounts of Fluohydric acid. in its preparation process, and fluoride has certain toxicity, thus limiting their application prospect.The ion-activated composite oxides of Mn (IV) due to its Stability Analysis of Structures, cause the extensive concern of people the features such as luminous efficiency is high.
Content of the invention
It is an object of the invention to provide composition of the light activated red fluorescence powder of a kind of new indigo plant and preparation method thereof.
To achieve these goals, involved in the present invention be applied to blue light activated red illuminating material, its chemical composition is：AB4-xO9:xMn4+；A is alkaline-earth metal ions Ba2+、Ca2+、Mg2+One or more of；B is alkaline-earth metal ions Ge4+、Ti4+、Zr4+One or more of；X is corresponding doping Mn4+Ion is relative to B4+Molar percentage coefficient shared by ion, 0< x ≤ 0.10.The weight/mass percentage composition of raw material type used in the present invention and each raw material is respectively：Brium carbonate：0~ 35.0 %；Calcium Carbonate：0~ 19.0 %；Magnesium oxide：0 ~ 8.0 %；Germanium dioxide： 0 ~ 68.0 %；Zirconium dioxide： 0 ~ 71.0 %；Titanium dioxide： 0 ~ 62.0 %；Manganese dioxide： 0.2 ~ 1.6 %.
Blue light wavelength of the present invention is 410～450 nm.
The preparation method of above-mentioned red illuminating material is to adopt high temperature solid-state method, specifically includes following steps：Above-mentioned various raw materials are stoichiometrically mixed in agate mortar all, then in high temperature Muffle furnace at 600 DEG C pre-burning 4-8 hour, calcine 4-8 hour at 1000 ~ 1400 DEG C, the white powder obtaining is final products.
The red illuminating material of the present invention has very strong red emission under blue light excites（Emission peak is located at 667 nm）, luminous efficiency height.
Brief description
Fig. 1 is the XRD diffraction pattern of red illuminating material of the present invention；
Fig. 2 is the room temperature excitation spectrum of red illuminating material of the present invention（Monitoring wavelength is 667 nm）And emission spectrum（Excitation wavelength is 430 nm）；
Fig. 3 is red illuminating material fluorescence lifetime attenuation curve of the present invention
Specific embodiment
Embodiment 1：
1.9734 g brium carbonates, 4.0976 g germanium dioxides, 0.0522 g manganese dioxide are mixed all in agate mortar, then in high temperature Muffle furnace at 600 DEG C pre-burning 4 hours, at 1200 DEG C calcine 4 hours, the white powder obtaining be final products.
The XRD diffraction pattern of this fluorescent material as shown in Figure 1, with standard card JCPDS 43-0644（BaGe4O9）Contrast, both are completely the same, the diffraction maximum of any dephasign is not observed, this shows that we have single crystalline phase by synthesized sample.
Accompanying drawing 2 show the room temperature excitation spectrum of sample（Monitoring wavelength is 667 nm）And emission spectrum（Excitation wavelength is 430 nm）.Sample is in ultraviolet region（240 nm ~ 380 nm）With blue light area（400 nm ~ 500 nm）There is very strong broadband excitation.Under 430 nm light excite, the transmitting of sample be with 667 nm about red emission based on, this Mn corresponding to4+'s2Eg-4A2gTransition.
Accompanying drawing 3 is the fluorescence lifetime curve of the sample using our synthesis.About 1.7 ms of this sample.
Embodiment 2：
1.7761 g brium carbonates, 0.1000 g Calcium Carbonate, 4.0976 g germanium dioxides, 0.0348 g manganese dioxide are mixed all in agate mortar, then in high temperature Muffle furnace at 600 DEG C pre-burning 4 hours, calcine 4 hours at 1300 DEG C, the white powder obtaining is final products.
Embodiment 3：
1.9734 g brium carbonates, 3.6879 g germanium dioxides, 0.3200 g titanium dioxide, 0.0522 g manganese dioxide are mixed all in agate mortar, then in high temperature Muffle furnace at 600 DEG C pre-burning 4 hours, calcine 6 hours at 1400 DEG C, the white powder obtaining is final products.
Embodiment 4：
1.000 g Calcium Carbonate, 4.8462 g zirconium dioxides, 0.0522 g manganese dioxide are mixed all in agate mortar, then in high temperature Muffle furnace at 600 DEG C pre-burning 4 hours, at 1400 DEG C calcine 8 hours, the white powder obtaining be final products.
Embodiment 5：
1.9734 g brium carbonates, 3.1680 g titanium dioxide, 0.0348 g manganese dioxide are mixed all in agate mortar, then in high temperature Muffle furnace at 600 DEG C pre-burning 6 hours, at 1400 DEG C calcine 8 hours, the white powder obtaining be final products.
Embodiment 6：
1.7761 g brium carbonates, 0.0400 g magnesium oxide, 3.1680 g titanium dioxide, 0.0522 g manganese dioxide are mixed all in agate mortar, then in high temperature Muffle furnace at 600 DEG C pre-burning 6 hours, calcine 8 hours at 1400 DEG C, the white powder obtaining is final products.
Embodiment 7：
1.7761 g brium carbonates, 0.0400 g magnesium oxide, 4.0976 g germanium dioxides, 0.0522 g manganese dioxide are mixed all in agate mortar, then in high temperature Muffle furnace at 600 DEG C pre-burning 8 hours, calcine 8 hours at 1000 DEG C, the white powder obtaining is final products.
Embodiment 8：
0.900 g Calcium Carbonate, 0.0400 g magnesium oxide, 4.8462 g zirconium dioxides, 0.0522 g manganese dioxide are mixed all in agate mortar, then in high temperature Muffle furnace at 600 DEG C pre-burning 6 hours, calcine 8 hours at 1300 DEG C, the white powder obtaining is final products.
Embodiment 9：
1.5787g brium carbonate, 0.100 g Calcium Carbonate, 0.0400 g magnesium oxide, 4.8462 g zirconium dioxides, 0.0522 g manganese dioxide are mixed all in agate mortar, then in high temperature Muffle furnace at 600 DEG C pre-burning 8 hours, calcine 8 hours at 1200 DEG C, the white powder obtaining is final products.
Embodiment 10：
1.9734 g brium carbonates, 3.9936 g germanium dioxides, 0.0800 g titanium dioxide, 0.0522 g manganese dioxide are mixed all in agate mortar, then in high temperature Muffle furnace at 600 DEG C pre-burning 6 hours, calcine 6 hours at 1300 DEG C, the white powder obtaining is final products.
Embodiment 11：
1.9734 g brium carbonates, 3.7774 g germanium dioxides, 0.080 g titanium dioxide, 0.1230 g zirconium dioxide, 0.0522 g manganese dioxide are mixed all in agate mortar, then in high temperature Muffle furnace at 600 DEG C pre-burning 6 hours, calcine 6 hours at 1400 DEG C, the white powder obtaining is final products.
Embodiment 12：
Just 1.5787g brium carbonate, 0.100 g Calcium Carbonate, 0.0400 g magnesium oxide, 3.7774 g germanium dioxides, 0.080 g titanium dioxide, 0.1230 g zirconium dioxide, 0.0522 g manganese dioxide mix all in agate mortar, then in high temperature Muffle furnace at 600 DEG C pre-burning 8 hours, calcine 8 hours at 1400 DEG C, the white powder obtaining is final products.
Claims (4)
1. the ion-activated red illuminating material of a kind of new Mn (IV), chemical composition is：AB4-xO9:xMn4+；A is alkaline-earth metal ions Ba2+、Ca2+、Mg2+One or more of；B is alkaline-earth metal ions Ge4+、Ti4+、Zr4+One or more of；X is corresponding doping Mn4+Ion is relative to B4+Molar percentage coefficient shared by ion, 0< x ≤ 0.10.
2. it is applied to the ion-activated red illuminating material of blue light activated Mn (IV) as claimed in claim 1 it is characterised in that described blue light refers to the light that wavelength is 410～450 nm.
3. the preparation method of the ion-activated red illuminating material of new Mn (IV), it is characterised in that preparation method is high temperature solid-state method, comprises the steps as claimed in claim 1：Various raw materials are stoichiometrically mixed in agate mortar all, then in high temperature Muffle furnace at 600 DEG C pre-burning 4-8 hour, calcine 4-8 hour at 1000 ~ 1400 DEG C, the white powder obtaining is final products.
4. as claimed in claim 3 the preparation method of the ion-activated red illuminating material of new Mn (IV) it is characterised in that the weight/mass percentage composition of the species of the raw material being used and each raw material is respectively：Brium carbonate：0~ 35.0 %；Calcium Carbonate：0~ 19.0 %；Magnesium oxide：0 ~ 8.0 %；Germanium dioxide： 0 ~ 68.0 %；Zirconium dioxide： 0 ~ 71.0 %；Titanium dioxide： 0 ~ 62.0 %；Manganese dioxide：0.2 ~ 1.6 %.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080061674A1 (en) * | 2006-09-12 | 2008-03-13 | National Chiao Tung University | Highly saturated red-emitting Mn (IV) activated phosphors and method of fabricating the same |
| CN104087298A (en) * | 2014-06-20 | 2014-10-08 | 华南理工大学 | Light conversion material and light conversion film, and preparation methods thereof |
| CN104403666A (en) * | 2014-12-07 | 2015-03-11 | 井冈山大学 | Quadrivalent manganese ion-doped red fluorescent material and preparation method thereof |
-
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- 2015-08-04 CN CN201510467959.0A patent/CN106433633A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080061674A1 (en) * | 2006-09-12 | 2008-03-13 | National Chiao Tung University | Highly saturated red-emitting Mn (IV) activated phosphors and method of fabricating the same |
| CN104087298A (en) * | 2014-06-20 | 2014-10-08 | 华南理工大学 | Light conversion material and light conversion film, and preparation methods thereof |
| CN104403666A (en) * | 2014-12-07 | 2015-03-11 | 井冈山大学 | Quadrivalent manganese ion-doped red fluorescent material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| FUMITO NISHI: "Strontium Tetragermanate, SrGe4O9", 《ACTA CRYSTALLOGRAPHICA SECTION C》 * |
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