CN110157426A - A kind of Mn4+Activate red fluorescence material and preparation method thereof - Google Patents
A kind of Mn4+Activate red fluorescence material and preparation method thereof Download PDFInfo
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- CN110157426A CN110157426A CN201910382391.0A CN201910382391A CN110157426A CN 110157426 A CN110157426 A CN 110157426A CN 201910382391 A CN201910382391 A CN 201910382391A CN 110157426 A CN110157426 A CN 110157426A
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
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- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
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Abstract
The present invention discloses a kind of Mn4+Activate red fluorescence material and preparation method thereof.The chemical constituent general formula of the fluorescent material is Ba6YyGdzW3‑XMnXO18, wherein 0.001≤X≤0.02, y+z=2.It uses high temperature solid-state method to prepare, and simple process, production cost is low, and chemical property is stablized.The fluorescent material highest excitation peak is located at 366nm, can effectively be excited by the light of 300~600nm wave band, issues the feux rouges of 640~750nm.The emission spectrum of the fluorescent material is made of two emission peaks, and peak value is located at 677nm and 692nm, and with the increase of Y content, the emission peak at 677nm is gradually decreased, and the emission peak at 692nm gradually rises.
Description
Technical field
The invention belongs to field of light emitting materials, and being related to one kind can be by the novel Mn of near ultraviolet excitation4+Activate red fluorescence
Material and preparation method thereof.
Background technique
White LED lamp is because its excellent performance is confirmed to be forth generation lighting source, the realization means master of white light LEDs at present
Will there are two types of: one is various chips combine, the second is one chip and RGB phosphor combination.In actual use, due to
The white light colour rendering index that single tri- color chip of RGB is mixed to get is low, so multiple integrated chips can be used.But multi-chip collection
At at high cost, complex process, makes difficulty and limit its use.Therefore, the single-chip of short wavelength emissions and RGB phosphor combination
Obtained white light LEDs are current mainstreams.In such a combination, RGB fluorescent powder plays decision to the luminescent properties of white light LEDs
Effect.
In the RGB fluorescent powder generallyd use at present, red fluorescence powder is mostly the europkium-activated sulfide of rare earth element, sulphur oxidation
Object and nitride.Mostly there is unstable chemcial property in these fluorescent materials, luminous intensity is lacked far below indigo plant, green fluorescence powder etc.
It falls into, and the source of rare earth is barren, raw material are expensive.Therefore, substitution rare-earth europium and the stable new matrix one of physico-chemical property are found
It is directly the direction that researcher makes great efforts.Transition metal manganese is because its raw material sources is abundant, and at low cost, being also easy to produce red emission becomes
Substitute the first choice of rare-earth europium.The tungstates for using physico-chemical property stable makes high-efficiency fluorescence powder as host material, and close
The research hotspot in a little years.
Chinese invention CN20181002461.8 discloses a kind of Mn4+The tungstate red fluorescent powder of doping and its preparation side
Method, the fluorescent powder can effectively be excited by the ultraviolet light of 330nm, issue the dark red light that peak value is located at 695nm.Chinese invention
CN20161108328.0 discloses a kind of ZnWO of rare earth ion codope4:Eu3+,Sm3+Fluorescent powder and preparation method thereof, this is glimmering
Light powder is synthesized using hydro-thermal method, can be by the purple light excited of 408nm, and transmitting optical range is 560~670nm, and peak value is located at 613nm.
Chinese invention CN20161049475.8 discloses a kind of artificial schellite red fluorescence powder and preparation method thereof for adulterating manganese ion,
Chemical composition is Ca1-xLa2WO7:xMn2+；Wherein, x takes 0.005~0.20, which needs under reducing atmosphere using height
Warm Solid phase synthesis.Although the new red fluorescence powder that can be used for white light LEDs continues to bring out, the hair of these red fluorescence powders
Light efficiency need further to improve, and therefore, we have proposed one kind can be by Mn4+The new medium of activation.
Summary of the invention
The purpose of the present invention is to provide a kind of chemical property to stablize, can be by the Mn of near ultraviolet excitation4+Activation is red glimmering
Luminescent material and preparation method thereof.
The technical solution of the present invention is as follows:
A kind of Mn4+Red fluorescence material is activated, chemical constituent general formula is Ba6YyGdzW3-XMnXO18, wherein 0.001≤X
≤ 0.02, y+z=2.
Above-mentioned Mn4+The preparation method for activating red fluorescence material, includes the following steps:
(1) claim sample: pressing Formula B a6YyGdzW3-XMnXO18, wherein 0.001≤X≤0.02, y+z=2, corresponding chemistry
Metering ratio weighs oxide spinel barium, manganese carbonate, yttrium oxide, gadolinium oxide and tungsten oxide；
(2) mixing: weighed raw material is mixed, and grinds to obtain mixture；
(3) it calcines: mixture obtained by step (2) is calcined；
(4) natural cooling, discharging crush to obtain Mn4+Activate red fluorescence material, i.e. Ba6YyGdzW3-XMnXO18, wherein
0.001≤X≤0.02, y+z=2.
Further, in step (2), milling time is 0.5~2 hour.
Further, in step (3), calcination temperature is 1400~1500 DEG C, preferably 1400 DEG C；Calcination time is 6~8
Hour, preferably 7 hours.
Fluorescent material highest excitation peak of the invention is located at 366nm, can effectively be excited by the light of 300~600nm wave band, hair
The feux rouges of 640~750nm out.The emission spectrum of the fluorescent material is made of two emission peaks, and peak value is located at 677nm
And 692nm.The emission peak of 677nm is higher than 692nm when y=0, z=2, with the increase of Y content, emission peak at 677nm by
It gradually reduces, the emission peak at 692nm gradually rises, and as x=0.006, the luminous intensity of the fluorescent material reaches maximum value.
In Mn4+In the case that doping concentration is constant, the content of fluorescent integrated intensity and Y, Gd are without obvious relation.
Compared with prior art, the invention has the following beneficial effects:
(1) the present invention provides a kind of novel manganese activated tungstate luminescent material, the chemical groups of the luminescent ceramic matrix
As Ba6(Y,Gd)2W3O18, structure is structure of double perovskite, belongs to cubic system, and space group is Fm-3m (225), wherein
Ba2+Ion is by 12 oxygen atom ligands, Gd3+And W6+Ion is combined with 6 oxygen atoms, forms GdO6And WO6Octahedron, this
A little octahedrons are alternately present in the unit cell, and are connected with each other by way of shared nonadjacent oxygen atom, incorporation and by shared
The mode of nonadjacent oxygen atom is connected with each other, the Mn of incorporation4+Ion occupies Ba6(Y,Gd)2W3O18W5+Ion site and form hair
Light center.
(2) red fluorescence material of the invention is prepared using high-temperature solid phase reaction method, and raw material is easy to get, simple process, and raw
Production process is environmentally friendly, no waste gas and waste liquid discharge.
Detailed description of the invention
Fig. 1 is the fluorescence intensity and Mn of fluorescent material of the present invention4+The relationship of doping concentration, as x=0.006, the fluorescence
The luminous intensity of material reaches maximum value.
Fig. 2 is 1 gained Ba of embodiment6Y2W2.99Mn0.01O18The exciting light spectrogram of sample monitoring 692nm.
Fig. 3 is the launching light spectrogram of embodiment 1,3 and 4 gained samples under 366nm excitation.
Fig. 4 is 5 gained Ba of embodiment6Gd2W2.98Mn0.02O18The exciting light spectrogram of sample monitoring 677nm.
Specific embodiment
The present invention is described in further details combined with specific embodiments below, but the present invention is not limited thereto.
Embodiment 1
Prepare Ba6Y2W2.99Mn0.01O18Material
By chemical constituent Formula B a6Y2W2.99Mn0.01O18Corresponding stoichiometric ratio weighs oxide spinel barium
2.36803g, yttrium oxide 0.45162g, tungsten oxide 1.38639g, manganese carbonate 0.00230g, are sufficiently mixed stirring, and grinding 1 is small
When, gained mixture is calcined 7 hours at 1400 DEG C, natural cooling, and discharging crushes up to Mn4+Activate red fluorescence material
Ba6Y2W2.99Mn0.01O18.Fig. 2 is the excitation spectrum of the sample, from Fig. 2, it can be seen that broadband character is presented in excitation spectrum, from
300nm is extended to always 600nm, is made of two excitation bands, and maximum excitation peak is located at 366nm, and secondary excitation peak is located at
518nm.Strigula is emission spectrum of the sample under 366nm excitation in Fig. 3, and peak value is located at 692nm.
Embodiment 2
Prepare Ba6Y2W2.98Mn0.02O18Material
By chemical constituent Formula B a6Y2W2.98Mn0.02O18Corresponding stoichiometric ratio weighs oxide spinel barium
2.60483g, yttrium oxide 0.49678g, tungsten oxide 1.51993g, manganese carbonate 0.00506g, are sufficiently mixed stirring, and grinding 1 is small
When, gained mixture is calcined 8 hours at 1400 DEG C, natural cooling, and discharging crushes up to Mn4+Activate red fluorescence material
Ba6Y2W2.98Mn0.02O18。
Embodiment 3
Prepare Ba6Y1Gd1W2.99Mn0.01O18Material
By chemical constituent Formula B a6Y1Gd1W2.99Mn0.01O18Corresponding stoichiometric ratio weighs oxide spinel barium
2.36803g, yttrium oxide 0.22581, gadolinium oxide 0.36250g, tungsten oxide 1.38639g, manganese carbonate 0.00230g, are sufficiently mixed
Stirring is ground 1 hour, and gained mixture is calcined 6 hours at 1500 DEG C, natural cooling, and discharging crushes up to Mn4+Activation is red
Fluorescent material Ba6Y1Gd1W2.99Mn0.01O18.Fig. 3 dot-dashed line is emission spectrum of the sample under 366nm excitation, by two
The emission peak of overlapping is constituted, and peak value is located at 689nm.
Embodiment 4
Prepare Ba6Gd2W2.99Mn0.01O18Material
By chemical constituent Formula B a6Gd2W2.99Mn0.01O18Corresponding stoichiometric ratio weighs oxide spinel barium
2.36803g, gadolinium oxide 0.72500g, tungsten oxide 1.38639g, manganese carbonate 0.00230g, are sufficiently mixed stirring, and grinding 1 is small
When, gained mixture is calcined 6 hours at 1500 DEG C, natural cooling, and discharging crushes up to Mn4+Activate red fluorescence material
Ba6Gd2W2.99Mn0.01O18.Solid line is emission spectrum of the sample under 366nm excitation in Fig. 3, and peak value is located at 677nm.
Embodiment 5
Prepare Ba6Gd2W2.98Mn0.02O18Material
By chemical constituent Formula B a6Gd2W2.98Mn0.02O18Corresponding stoichiometric ratio weighs oxide spinel barium
2.36803g, gadolinium oxide 0.72500g, tungsten oxide 1.38176g, manganese carbonate 0.00460g, are sufficiently mixed stirring, and grinding 1 is small
When, gained mixture is calcined 7 hours at 1400 DEG C, natural cooling, and discharging crushes up to Mn4+Activate red fluorescence material
Ba6Gd2W2.98Mn0.02O18.Fig. 4 is the excitation spectrum of the sample, compared with 1 gained sample of embodiment, maximum excitation peak position
Constant, secondary excitation peak is blue shifted to 512nm, and peak strength slightly improves.
Embodiment 6
Prepare Ba6Y2W2.994Mn0.006O18Material
By chemical constituent Formula B a6Y2W2.994Mn0.006O18Corresponding stoichiometric ratio weighs oxide spinel barium
5.92008g, yttrium oxide 1.12905g, tungsten oxide 3.47062g, manganese carbonate 0.00345g, are sufficiently mixed stirring, and grinding 1 is small
When, gained mixture is calcined 7 hours at 1400 DEG C, natural cooling, and discharging crushes up to Mn4+Activate red fluorescence material
Ba6Y2W2.994Mn0.006O18.At this point, luminous intensity reaches maximum value.
Claims (5)
1. a kind of Mn4+Activate red fluorescence material, which is characterized in that chemical constituent general formula is Ba6YyGdzW3-XMnXO18, wherein
0.001≤X≤0.02, y+z=2.
2. Mn according to claim 14+Activate red fluorescence material, which is characterized in that the transmitted wave of the fluorescent material
Long coverage area is 640~750nm, and peak value is located at 677~692nm.
3. Mn of any of claims 1 or 24+Activate the preparation method of red fluorescence material, which is characterized in that including following step
It is rapid:
(1) claim sample: pressing Formula B a6YyGdzW3-XMnXO18, wherein 0.001≤X≤0.02, y+z=2, corresponding stoichiometry
Than weighing oxide spinel barium, yttrium oxide, gadolinium oxide, tungstic acid, manganese carbonate or manganese dioxide；
(2) mixing: weighed raw material is mixed, and is fully ground to obtain precursor mixture；
(3) it calcines: precursor mixture is calcined in oxidizing atmosphere；
(4) natural cooling, discharging crush and obtain Mn4+Activate red fluorescence material, i.e. Ba6YyGdzW3-XMnXO18, wherein 0.001≤
X≤0.02, y+z=2.
4. Mn according to claim 34+Activate the preparation method of red fluorescence material, which is characterized in that in step (2),
Milling time is 0.5~2 hour.
5. Mn according to claim 34+Activate the preparation method of red fluorescence material, which is characterized in that in step (3),
Calcination temperature is 1400~1500 DEG C；Calcination time is 6~8 hours.
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| CN201910382391.0A CN110157426B (en) | 2019-05-08 | 2019-05-08 | Mn (manganese)4+Activated red fluorescent material and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111004632A (en) * | 2019-12-18 | 2020-04-14 | 湘潭大学 | Agricultural photoluminescent material capable of being simultaneously excited by ultraviolet light and green light and preparation method and application thereof |
| CN111363546A (en) * | 2020-03-26 | 2020-07-03 | 徐州凹凸光电科技有限公司 | Near-infrared fluorescent powder with high thermal stability and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110147595A1 (en) * | 2009-12-22 | 2011-06-23 | Koninklijke Philips Electronics N.V. | Tungstate-based scintillating materials for detecting radiation |
-
2019
- 2019-05-08 CN CN201910382391.0A patent/CN110157426B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110147595A1 (en) * | 2009-12-22 | 2011-06-23 | Koninklijke Philips Electronics N.V. | Tungstate-based scintillating materials for detecting radiation |
Non-Patent Citations (3)
| Title |
|---|
| HUANG, XIAOYONG; GUO, HENG: "Finding a novel highly efficient Mn4+-activated Ca3La2W2O12 far-red emitting phosphor with excellent responsiveness to phytochrome PFR: Towards indoor plant cultivation application", 《DYES AND PIGMENTS》 * |
| NIU, PENGFEI;等: "Photoluminescence properties of a novel red-emitting nanowire phosphor Ba6Gd2W3O18:Eu3+", 《JOURNAL OF LUMINESCENCE》 * |
| 牛朋飞: "稀土钒酸盐和钨酸盐荧光粉的合成及发光性能研究", 《中国优秀硕士学位论文全文数据库》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111004632A (en) * | 2019-12-18 | 2020-04-14 | 湘潭大学 | Agricultural photoluminescent material capable of being simultaneously excited by ultraviolet light and green light and preparation method and application thereof |
| CN111363546A (en) * | 2020-03-26 | 2020-07-03 | 徐州凹凸光电科技有限公司 | Near-infrared fluorescent powder with high thermal stability and preparation method and application thereof |
| CN111363546B (en) * | 2020-03-26 | 2023-01-03 | 徐州凹凸光电科技有限公司 | Near-infrared fluorescent powder with high thermal stability and preparation method and application thereof |
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