CN103013509A - Bismuth/europium-ion-codoped zirconate fluorescent material and preparation method thereof - Google Patents
Bismuth/europium-ion-codoped zirconate fluorescent material and preparation method thereof Download PDFInfo
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- CN103013509A CN103013509A CN2013100011302A CN201310001130A CN103013509A CN 103013509 A CN103013509 A CN 103013509A CN 2013100011302 A CN2013100011302 A CN 2013100011302A CN 201310001130 A CN201310001130 A CN 201310001130A CN 103013509 A CN103013509 A CN 103013509A
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- zirconate
- bismuth
- fluorescent material
- codoped
- preparation
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- 239000000463 material Substances 0.000 title claims abstract description 34
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 18
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 238000005303 weighing Methods 0.000 claims abstract description 8
- 229910052693 Europium Inorganic materials 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000000843 powder Substances 0.000 abstract description 11
- 230000005284 excitation Effects 0.000 abstract description 10
- 239000000203 mixture Substances 0.000 abstract description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 abstract 2
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- -1 europium ion Chemical class 0.000 description 11
- 229910052593 corundum Inorganic materials 0.000 description 6
- 239000010431 corundum Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 241001025261 Neoraja caerulea Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000012858 packaging process Methods 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Abstract
The invention provides a bismuth/europium-ion-codoped zirconate fluorescent material and a preparation method thereof. The MZrO3:Eu:Bi mol ratio in the material is 1:(0.01-0.1):(0.01-0.1), wherein M is any one of Mg, Ca, Sr and Ba. The preparation method comprises the following steps: weighing MCO3, ZrO2, Bi2O3 and Eu2O3 according to the M:Zr:Eu:Bi mol ratio of 1:1:(0.01-0.1):(0.01-0.1), evenly mixing, precalcining the mixture in the air at 1300 DEG C for 1-4 hours, naturally cooling, calcining at 1000-1300 DEG C in a reducing atmosphere for 1-5 hours, and grinding to obtain the bismuth/europium-ion-codoped zirconate fluorescent material. The fluorescent powder has 470nm wideband emission peak from Bi<3+> and red feature emission of Eu<3+> under the excitation of 340nm ultraviolet light; and the fluorescent powder has wide light-emitting color range under the excitation of ultraviolet light, does not need multiple fluorescent powder ratios, and can not have the problem of color temperature drift.
Description
Technical field
The invention belongs to display and lighting fluorescent material technical field, be specifically related to a kind of ceramic fluorescent powder that under ultraviolet excitation, has the display lighting function.
Background technology
White light LEDs is a kind of novel solid-state illumination energy, and it is energy-conservation with it, long service life, and it is low, pollution-free to consume energy, and the efficient advantages of higher is considered to the new forms of energy that 21 century might replace the traditional lighting light source.Obtain at present white light LEDs and mainly contain two kinds of methods: a kind of is that multi-chip is combined, the LED combination of launching respectively red, green, blue, mixes three kinds of light and forms white light emission.The advantages such as the white light of this scheme has the brightness height, and stability and color developing are good; But cost is high, and driving circuit is complicated, does not have at present large-scale production.Another kind is the fluorescent material conversion hysteria, and with the fluorescent material of blue-ray LED excitation energy emission gold-tinted, remaining blue light and gold-tinted are compounded to form white light.This scheme comparative maturity all on technology and technique is the main product of present industrialization.But the white light that this scheme obtains lacks red composition, and color developing is lower.Because blue light derives from different matrixes with ruddiness, luminous thermostability is undesirable in addition.Mixed fluorescent powder by ultraviolet excitation emission red, green, blue three primary colours, can obtain the white light emission of high-color rendering, cause the problem that heavily absorbs that luminous efficiency descends and the proportioning of fluorescent material to regulate and control masty problem but exist between the different fluorescent material, limited its application.Therefore, if adopt the white light emission fluorescent material of single-matrix, be expected to obtain simultaneously high luminous efficiency and stability of photoluminescence, so that the LED packaging process is simplified greatly, therefore the research of the white emitting fluorescent powder of single-matrix is very active in recent years simultaneously.By contrast, the white light ceramic fluorescent powder material that also lacks in the market the good single-matrix of excellent performance, thermostability and chemical stability.
Summary of the invention
The objective of the invention is narrow for the luminous colour gamut of existing LED lighting fluorescent powder visible light, color developing is lower, the multiple fluorescent material of needs is compound, the problems such as preparation method's cost is high, complicated, adopt Bi, Eu ion as active ions, the preparation bismuth, the zirconate white fluorescent powder material of europium ion codoped has efficient response characteristic to ultraviolet excitation.
The present invention realizes by following technical proposal: the zirconate fluorescent material of a kind of bismuth and europium ion codoped, the MZrO in this material
3: mol ratio=1:0.01 of Eu:Bi～0.1:0.01～0.1; Wherein, M is any one among Mg, Ca, Sr, the Ba.
Another object of the present invention is to provide the preparation method of the zirconate fluorescent material of a kind of bismuth and europium ion codoped, through following each step:
(1) presses mol ratio=1:1:0.01 of M:Zr:Eu:Bi～0.1:0.01～0.1, weighing MCO
3, ZrO
2, Bi
2O
3And Eu
2O
3, remix is even, and wherein, M is any one among Mg, Ca, Sr, the Ba;
(2) compound with step (1) gained places in the corundum crucible, in air in 1300 ℃ of lower precalcining 1～4h, behind naturally cooling, in reducing atmosphere, in 1000～1300 ℃ of lower calcining 1～5h, namely obtain the zirconate fluorescent material of bismuth and europium ion codoped after the grinding.
The reducing atmosphere of described step (2) is H
2+ N
2
The present invention compares with existing phosphor material powder, has following outstanding advantage:
Adopt Bi, Eu ion as active ions, the preparation bismuth, the zirconate white fluorescent powder material of europium ion codoped has efficient response characteristic to ultraviolet excitation, can transmitting white under ultraviolet excitation.Illuminant colour field width under ultraviolet excitation need not multiple fluorescent material proportioning, colour temperature drift problem can not occur.This fluorescent material has the Bi of coming under the 340nm ultraviolet excitation
3+Be positioned at 470nm broadband emission peak and Eu
3+Red characteristic emission; This material is expected to become novel fluorescence illumination display material.
Description of drawings
Fig. 1 is the BaZrO of the embodiment of the invention 1 gained
3: the emission spectrogram of 0.025Eu:0.05Bi fluorescent material.
Embodiment
Further illustrate content of the present invention below in conjunction with embodiment, but these examples do not limit protection scope of the present invention.
Embodiment 1
(1) presses mol ratio=1:1:0.025:0.05 of Ba:Zr:Eu:Bi, weighing BaCO
3, ZrO
2, Bi
2O
3And Eu
2O
3, remix is even;
(2) compound with step (1) gained places in the corundum crucible, in air in 1300 ℃ of lower precalcining 3h, behind naturally cooling, at reducing atmosphere H
2+ N
2In in 1300 ℃ of lower calcining 3h, namely obtain the zirconate fluorescent material BaZrO of bismuth and europium ion codoped after the grinding
3: 0.025Eu:0.05Bi.
Embodiment 2
(1) presses mol ratio=1:1:0.01:0.01 of Mg:Zr:Eu:Bi, weighing MgCO
3, ZrO
2, Bi
2O
3And Eu
2O
3, remix is even, and wherein, M is any one among Mg, Ca, Sr, the Ba;
(2) compound with step (1) gained places in the corundum crucible, in air in 1300 ℃ of lower precalcining 4h, behind naturally cooling, at reducing atmosphere H
2+ N
2In in 1200 ℃ of lower calcining 5h, namely obtain the zirconate fluorescent material MgZrO of bismuth and europium ion codoped after the grinding
3: 0.01Eu:0.01Bi.
Embodiment 3
(1) presses mol ratio=1:1:0.03:0.08 of Ca:Zr:Eu:Bi, weighing CaCO
3, ZrO
2, Bi
2O
3And Eu
2O
3, remix is even;
(2) compound with step (1) gained places in the corundum crucible, in air in 1300 ℃ of lower precalcining 1h, behind naturally cooling, at reducing atmosphere H
2+ N
2In in 1000 ℃ of lower calcining 1h, namely obtain the zirconate fluorescent material CaZrO of bismuth and europium ion codoped after the grinding
3: 0.03Eu:0.08Bi.
Embodiment 4
(1) presses mol ratio=1:1:0.1:0.1 of Sr:Zr:Eu:Bi, weighing SrCO
3, ZrO
2, Bi
2O
3And Eu
2O
3, remix is even;
(2) compound with step (1) gained places in the corundum crucible, in air in 1300 ℃ of lower precalcining 3h, behind naturally cooling, at reducing atmosphere H
2+ N
2In in 1300 ℃ of lower calcining 4h, namely obtain the zirconate fluorescent material SrZrO of bismuth and europium ion codoped after the grinding
3: 0.1Eu:0.1Bi.
Embodiment 5
(1) presses mol ratio=1:1:0.1:0.05 of Ca:Zr:Eu:Bi, weighing CaCO
3, ZrO
2, Bi
2O
3And Eu
2O
3, remix is even, and wherein, M is any one among Mg, Ca, Sr, the Ba;
(2) compound with step (1) gained places in the corundum crucible, in air in 1300 ℃ of lower precalcining 4h, behind naturally cooling, at reducing atmosphere H
2+ N
2In in 1100 ℃ of lower calcining 2h, namely obtain the zirconate fluorescent material CaZrO of bismuth and europium ion codoped after the grinding
3: 0.1Eu:0.05Bi.
Claims (3)
1. the zirconate fluorescent material of a bismuth and europium ion codoped is characterized in that: the MZrO in this material
3: mol ratio=1:0.01 of Eu:Bi～0.1:0.01～0.1; Wherein, M is any one among Mg, Ca, Sr, the Ba.
2. the preparation method of the zirconate fluorescent material of a bismuth and europium ion codoped is characterized in that through following each step:
(1) presses mol ratio=1:1:0.01 of M:Zr:Eu:Bi～0.1:0.01～0.1, weighing MCO
3, ZrO
2, Bi
2O
3And Eu
2O
3, remix is even, and wherein, M is any one among Mg, Ca, Sr, the Ba;
(2) with the compound of step (1) gained in air in 1300 ℃ of lower precalcining 1～4h, behind naturally cooling, in reducing atmosphere, in 1000～1300 ℃ of lower calcining 1～5h, namely obtain the zirconate fluorescent material of bismuth and europium ion codoped after the grinding.
3. the preparation method of the zirconate fluorescent material of bismuth according to claim 2 and europium ion codoped, it is characterized in that: the reducing atmosphere of described step (2) is H
2+ N
2
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|---|---|---|---|
| CN201310001130.2A CN103013509B (en) | 2013-01-04 | 2013-01-04 | Bismuth/europium-ion-codoped zirconate fluorescent material and preparation method thereof |
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|---|---|
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| CN103013509B CN103013509B (en) | 2014-12-31 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104263363A (en) * | 2014-10-14 | 2015-01-07 | 中国科学院上海硅酸盐研究所 | 7Al2O3*12CaO white light emitting material co-doped with europium and bismuth ions and preparation method of material |
| CN104403667A (en) * | 2014-11-03 | 2015-03-11 | 沈阳化工大学 | A wet chemical coprecipitation method for preparing SrZrO3: (Ce, pr) nanometer luminescent powder |
| CN108483926A (en) * | 2018-03-16 | 2018-09-04 | 华南理工大学 | One kind is from crystallization devitrified glass and its preparation method and application |
| CN108753290A (en) * | 2018-06-05 | 2018-11-06 | 湘南学院 | A kind of bismuth and the coactivated titanium aluminate fluorescent powder of europium ion and its preparation and application |
| CN117327490A (en) * | 2023-09-28 | 2024-01-02 | 昆明理工大学 | Bi-doped europium salt fluorescent powder and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735803A (en) * | 2009-12-01 | 2010-06-16 | 四川大学 | Silicate blue fluorescent powder for white-light LED and preparation method thereof |
-
2013
- 2013-01-04 CN CN201310001130.2A patent/CN103013509B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735803A (en) * | 2009-12-01 | 2010-06-16 | 四川大学 | Silicate blue fluorescent powder for white-light LED and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 张丽霞 等: "CaWO4∶Eu3+，M3+ ( M = Tb，Sm，Bi，Dy)的水热合成及发光性能研究", 《广西大学学报：自然科学版》 * |
| 李玮 等: "铕镝离子掺杂锆酸钡纳米晶的制备及发光性质", 《河南科技大学学报: 自然科学版》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104263363A (en) * | 2014-10-14 | 2015-01-07 | 中国科学院上海硅酸盐研究所 | 7Al2O3*12CaO white light emitting material co-doped with europium and bismuth ions and preparation method of material |
| CN104403667A (en) * | 2014-11-03 | 2015-03-11 | 沈阳化工大学 | A wet chemical coprecipitation method for preparing SrZrO3: (Ce, pr) nanometer luminescent powder |
| CN104403667B (en) * | 2014-11-03 | 2016-07-20 | 沈阳化工大学 | A kind of wet-chemical coprecipitation prepares SrZrO3:(Ce, Pr) method of nano-luminescent powder body |
| CN108483926A (en) * | 2018-03-16 | 2018-09-04 | 华南理工大学 | One kind is from crystallization devitrified glass and its preparation method and application |
| CN108483926B (en) * | 2018-03-16 | 2020-11-24 | 华南理工大学 | Self-crystallization microcrystalline glass and preparation method and application thereof |
| CN108753290A (en) * | 2018-06-05 | 2018-11-06 | 湘南学院 | A kind of bismuth and the coactivated titanium aluminate fluorescent powder of europium ion and its preparation and application |
| CN108753290B (en) * | 2018-06-05 | 2021-01-15 | 湘南学院 | Bismuth and europium ion co-activated titanium aluminate fluorescent powder and preparation and application thereof |
| CN117327490A (en) * | 2023-09-28 | 2024-01-02 | 昆明理工大学 | Bi-doped europium salt fluorescent powder and preparation method and application thereof |
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| CN103013509B (en) | 2014-12-31 |
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