CN103450896A - Thulium-doped fluoroaluminate up-conversion fluorescent powder and preparation method thereof - Google Patents

Thulium-doped fluoroaluminate up-conversion fluorescent powder and preparation method thereof Download PDF

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CN103450896A
CN103450896A CN 201210174064 CN201210174064A CN103450896A CN 103450896 A CN103450896 A CN 103450896A CN 201210174064 CN201210174064 CN 201210174064 CN 201210174064 A CN201210174064 A CN 201210174064A CN 103450896 A CN103450896 A CN 103450896A
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mmole
conversion phosphor
preparation
fluorescent powder
thulium doped
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周明杰
王平
陈吉星
张振华
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Abstract

The invention belongs to the field of fluorescent powder, and discloses a thulium-doped fluoroaluminate up-conversion fluorescent powder and a preparation method thereof. The fluorescent powder has the molecular general formula of MLiAlF6:xTm<3+>, wherein M represents Mg, Ca, Sr, Ba or Zn elements, Tm<3+> is a doping ion, and x is in a range of 0.02-0.1. The prepared thulium-doped fluoroaluminate up-conversion fluorescent powder can realize short-wavelength luminescence of blue light through excitation by long-wavelength radiation from infrared light to green light. Therefore, the fluorescent powder can make up for the lack of blue light materials in current display and luminescent materials; and an outer layer of an OLED (organic light emitting diode) device which originally emits red green light can be excited a part of the blue light after being added with the fluorescent powder, and the blue light is mixed with the original red green light so as to form white light.

Description

A kind of thulium doped with fluorine aluminate up-conversion phosphor and preparation method thereof
Technical field
The present invention relates to the phosphor material powder field, relate in particular to a kind of thulium doped with fluorine aluminate up-conversion phosphor and preparation method thereof.
Background technology
The full name Organic Light Emitting Diode of OLED, Organic Light Emitting Diode.It has a lot of advantages, and its unit construction is simple, and production cost is cheap, and self luminous characteristic adds that the reaction times of OLED is short, and flexible characteristic is more arranged, and makes its range of application extremely wide.But, because the OLED blue light material that obtains at present stability and high efficiency is more difficult, limited greatly the development of white light OLED device and light source industry.
Upconverting fluorescent material can be launched visible ray under long wave (as infrared) radiation excitation, even UV-light, be with a wide range of applications in fields such as optical fiber communication technology, fibre amplifier, 3 D stereo demonstration, biomolecules fluorescence labelling, infrared detectives.But be prepared into the field that fluorescent material is applied to OLED, still rarely seen report.
Summary of the invention
Based on the problems referred to above, the invention provides a kind of thulium doped with fluorine aluminate up-conversion phosphor
Technical scheme of the present invention is as follows:
A kind of thulium doped with fluorine aluminate up-conversion phosphor, it has general molecular formula: MLiAlF 6: xTm 3+; In formula, M is Mg, Ca, Sr, Ba or Zn element, Tm 3+for dopant ion, the span of x is 0.02 ~ 0.1, and preferably the value of x is 0.06.
The present invention also provides the preparation method of above-mentioned thulium doped with fluorine aluminate up-conversion phosphor, comprises the steps:
S1, according to MLiAlF 6: xTm 3+in each element chemistry stoichiometric coefficient ratio, take respectively MF 2, LiF, AlF 3and TmF 3powder; Wherein, M is Mg, Ca, and Sr, Ba or Zn element, the span of x is 0.02 ~ 0.1;
S2, the powder in step S1 is ground 20 ~ 60 minutes, obtain uniform powder presoma;
S3, the presoma in step S2 is placed in to 800 ~ 1000 ℃ of lower calcinations 0.5 ~ 5 hour, cools to subsequently under 100 ~ 500 ℃ the insulation of carrying out 0.5 ~ 3 hour and process, obtain bulk sample;
S4, the bulk sample in step S3 is ground, obtaining molecular formula is MLiAlF 6: xTm 3+thulium doped with fluorine aluminate up-conversion phosphor, Tm 3+for dopant ion.
In the preparation method of above-mentioned thulium doped with fluorine aluminate up-conversion phosphor, preferably the value of x is 0.06.
In the preparation method's of above-mentioned thulium doped with fluorine aluminate up-conversion phosphor step S2, preferably milling time is 40 minutes.
In the preparation method's of above-mentioned thulium doped with fluorine aluminate up-conversion phosphor step S3, preferably calcination temperature is 950 ℃, and calcination time is 3 hours.
In the preparation method's of above-mentioned thulium doped with fluorine aluminate up-conversion phosphor step S3, temperature when preferably insulation is processed is 250 ℃, and soaking time is 2 hours.
Thulium doped with fluorine aluminate up-conversion phosphor prepared by the present invention, can realize inspiring the blue light shortwave by the infrared long-wave radiation to green glow luminous.Therefore, this fluorescent material can make up the deficiency of blue light material in current demonstration and luminescent material, makes the skin of OLED device of original rubescent green glow after having added this fluorescent material, can inspire the part blue light, with original red-green glow, blendes together white light.
The preparation method of above-mentioned fluorescent material, its preparation technology is simple, with low costly is applicable to production, and reaction process, without three industrial wastes, belongs to environmental protection, less energy-consumption, high benefit industry.
The accompanying drawing explanation
Preparation technology's schema that Fig. 1 is fluorescent material of the present invention;
The photoluminescence spectra figure that Fig. 2 is the fluorescent material that makes of embodiment 1.
Embodiment
Thulium doped with fluorine aluminate up-conversion phosphor provided by the invention, its general molecular formula is: MLiAlF 6: xTm 3+; In formula, M is Mg, Ca, Sr, Ba or Zn element, Tm 3+for dopant ion, the span of x is 0.02 ~ 0.1, and preferably the value of x is 0.06.
The preparation method of above-mentioned thulium doped with fluorine aluminate up-conversion phosphor, as shown in Figure 1, comprise the steps:
S1, according to MLiAlF 6: xTm 3+in each element chemistry stoichiometric coefficient ratio, take respectively MF 2, LiF, AlF 3and TmF 3powder; Wherein, M is Mg, Ca, and Sr, Ba or Zn element, the span of x is 0.02 ~ 0.1;
S2, the powder in step S1 is ground 20 ~ 60 minutes, obtain uniform powder presoma;
S3, the presoma in step S2 is placed in to 800 ~ 1000 ℃ of lower calcinations 0.5 ~ 5 hour, cools to subsequently under 100 ~ 500 ℃ the insulation of carrying out 0.5 ~ 3 hour and process, obtain bulk sample;
S4, the bulk sample in step S3 is ground, obtaining molecular formula is MLiAlF 6: xTm 3+thulium doped with fluorine aluminate up-conversion phosphor, Tm 3+for dopant ion.
In the preparation method of above-mentioned thulium doped with fluorine aluminate up-conversion phosphor, preferably the value of x is 0.06.
In the preparation method's of above-mentioned thulium doped with fluorine aluminate up-conversion phosphor step S2, preferably milling time is 40 minutes.
In the preparation method's of above-mentioned thulium doped with fluorine aluminate up-conversion phosphor step S3, preferably calcination temperature is 950 ℃, and calcination time is 3 hours.
In the preparation method's of above-mentioned thulium doped with fluorine aluminate up-conversion phosphor step S3, temperature when preferably insulation is processed is 250 ℃, and soaking time is 2 hours.
Thulium doped with fluorine aluminate up-conversion phosphor prepared by the present invention, can realize inspiring the blue light shortwave by the infrared long-wave radiation to green glow luminous.Therefore, this fluorescent material can make up the deficiency of blue light material in current demonstration and luminescent material, makes the skin of OLED device of original rubescent green glow after having added this fluorescent material, can inspire the part blue light, with original red-green glow, blendes together white light.
The preparation method of above-mentioned fluorescent material, its preparation technology is simple, with low costly is applicable to production, and reaction process, without three industrial wastes, belongs to environmental protection, less energy-consumption, high benefit industry.
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1
Take MgF 2, LiF, AlF 3and TmF 3powder, mol ratio is 0.5 mmole, 0.5 mmole, 0.5 mmole, 0.01 mmole.Grind and within 40 minutes, make its even mixing in the corundum mortar, then 950 ℃ of lower calcinations 3 hours.Then be cooled to 250 ℃ of insulations 2 hours, then naturally cool to room temperature taking-up block product, and, by its pulverizing, obtain MgLiAlF 6: 0.02Tm 3+up-conversion phosphor.
The photoluminescence spectra figure that Fig. 2 is the fluorescent material that makes of embodiment 1; In figure, can find out, excitation wavelength is 796nm, and that the glow peak of the 475nm obtained is corresponding is Tm 3+ion 1g 4→ 3h 6transition radiation luminous.
Embodiment 2
Take MgF 2, LiF, AlF 3and TmF 3powder, mol ratio is 0.5 mmole, 0.5 mmole, 0.5 mmole, 0.05 mmole.Grind and within 20 minutes, make its even mixing in the corundum mortar, then 800 ℃ of lower calcinations 5 hours.Then be cooled to 100 ℃ of insulations 3 hours, then naturally cool to room temperature taking-up block product, and, by its pulverizing, obtain MgLiAlF 6: 0.1Tm 3+up-conversion phosphor.
Embodiment 3
Take MgF 2, LiF, AlF 3and TmF 3powder, mol ratio is 0.5 mmole, 0.5 mmole, 0.5 mmole, 0.03 mmole.Grind and within 60 minutes, make its even mixing in the corundum mortar, then 1000 ℃ of lower calcinations 0.5 hour.Then be cooled to 500 ℃ of insulations 0.5 hour, then naturally cool to room temperature taking-up block product, and, by its pulverizing, obtain MgLiAlF 6: 0.06Tm 3+up-conversion phosphor.
Embodiment 4
Take CaF 2, LiF, AlF 3and TmF 3powder, mol ratio is 0.5 mmole, 0.5 mmole, 0.5 mmole, 0.01 mmole.Grind and within 40 minutes, make its even mixing in the corundum mortar, then 950 ℃ of lower calcinations 3 hours.Then be cooled to 250 ℃ of insulations 2 hours, then naturally cool to room temperature taking-up block product, and, by its pulverizing, obtain CaLiAlF 6: 0.02Tm 3+up-conversion phosphor.
Embodiment 5
Take CaF 2, LiF, AlF 3and TmF 3powder, mol ratio is 0.5 mmole, 0.5 mmole, 0.5 mmole, 0.05 mmole.Grind and within 20 minutes, make its even mixing in the corundum mortar, then 800 ℃ of lower calcinations 5 hours.Then be cooled to 100 ℃ of insulations 3 hours, then naturally cool to room temperature taking-up block product, and, by its pulverizing, obtain CaLiAlF 6: 0.1Tm 3+up-conversion phosphor.
Embodiment 6
Take CaF 2, LiF, AlF 3and TmF 3powder, mol ratio is 0.5 mmole, 0.5 mmole, 0.5 mmole, 0.03 mmole.Grind and within 60 minutes, make its even mixing in the corundum mortar, then 1000 ℃ of lower calcinations 0.5 hour.Then be cooled to 500 ℃ of insulations 0.5 hour, then naturally cool to room temperature taking-up block product, and, by its pulverizing, obtain CaLiAlF 6: 0.06Tm 3+up-conversion phosphor.
Embodiment 7
Take SrF 2, LiF, AlF 3and TmF 3powder, mol ratio is 0.5 mmole, 0.5 mmole, 0.5 mmole, 0.01 mmole.Grind and within 40 minutes, make its even mixing in the corundum mortar, then 950 ℃ of lower calcinations 3 hours.Then be cooled to 250 ℃ of insulations 2 hours, then naturally cool to room temperature taking-up block product, and, by its pulverizing, obtain SrLiAlF 6: 0.02Tm 3+up-conversion phosphor.
Embodiment 8
Take SrF 2, LiF, AlF 3and TmF 3powder, mol ratio is 0.5 mmole, 0.5 mmole, 0.5 mmole, 0.05 mmole.Grind and within 20 minutes, make its even mixing in the corundum mortar, then 800 ℃ of lower calcinations 5 hours.Then be cooled to 100 ℃ of insulations 3 hours, then naturally cool to room temperature taking-up block product, and, by its pulverizing, obtain SrLiAlF 6: 0.1Tm 3+up-conversion phosphor.
Embodiment 9
Take SrF 2, LiF, AlF 3and TmF 3powder, mol ratio is 0.5 mmole, 0.5 mmole, 0.5 mmole, 0.03 mmole.Grind and within 60 minutes, make its even mixing in the corundum mortar, then 1000 ℃ of lower calcinations 0.5 hour.Then be cooled to 500 ℃ of insulations 0.5 hour, then naturally cool to room temperature taking-up block product, and, by its pulverizing, obtain SrLiAlF 6: 0.06Tm 3+up-conversion phosphor.
Embodiment 10
Take BaF 2, LiF, AlF 3and TmF 3powder, mol ratio is 0.5 mmole, 0.5 mmole, 0.5 mmole, 0.01 mmole.Grind and within 40 minutes, make its even mixing in the corundum mortar, then 950 ℃ of lower calcinations 3 hours.Then be cooled to 250 ℃ of insulations 2 hours, then naturally cool to room temperature taking-up block product, and, by its pulverizing, obtain BaLiAlF 6: 0.02Tm 3+up-conversion phosphor.
Embodiment 11
Take BaF 2, LiF, AlF 3and TmF 3powder, mol ratio is 0.5 mmole, 0.5 mmole, 0.5 mmole, 0.05 mmole.Grind and within 20 minutes, make its even mixing in the corundum mortar, then 800 ℃ of lower calcinations 5 hours.Then be cooled to 100 ℃ of insulations 3 hours, then naturally cool to room temperature taking-up block product, and, by its pulverizing, obtain BaLiAlF 6: 0.1Tm 3+up-conversion phosphor.
Embodiment 12
Take BaF 2, LiF, AlF 3and TmF 3powder, mol ratio is 0.5 mmole, 0.5 mmole, 0.5 mmole, 0.03 mmole.Grind and within 60 minutes, make its even mixing in the corundum mortar, then 1000 ℃ of lower calcinations 0.5 hour.Then be cooled to 500 ℃ of insulations 0.5 hour, then naturally cool to room temperature taking-up block product, and, by its pulverizing, obtain BaLiAlF 6: 0.06Tm 3+up-conversion phosphor.
Embodiment 13
Take ZnF 2, LiF, AlF 3and TmF 3powder, mol ratio is 0.5 mmole, 0.5 mmole, 0.5 mmole, 0.01 mmole.Grind and within 40 minutes, make its even mixing in the corundum mortar, then 950 ℃ of lower calcinations 3 hours.Then be cooled to 250 ℃ of insulations 2 hours, then naturally cool to room temperature taking-up block product, and, by its pulverizing, obtain ZnLiAlF 6: 0.02Tm 3+up-conversion phosphor.
Embodiment 14
Take ZnF 2, LiF, AlF 3and TmF 3powder, mol ratio is 0.5 mmole, 0.5 mmole, 0.5 mmole, 0.05 mmole.Grind and within 20 minutes, make its even mixing in the corundum mortar, then 800 ℃ of lower calcinations 5 hours.Then be cooled to 100 ℃ of insulations 3 hours, then naturally cool to room temperature taking-up block product, and, by its pulverizing, obtain ZnLiAlF 6: 0.1Tm 3+up-conversion phosphor.
Embodiment 15
Take ZnF 2, LiF, AlF 3and TmF 3powder, mol ratio is 0.5 mmole, 0.5 mmole, 0.5 mmole, 0.03 mmole.Grind and within 60 minutes, make its even mixing in the corundum mortar, then 1000 ℃ of lower calcinations 0.5 hour.Then be cooled to 500 ℃ of insulations 0.5 hour, then naturally cool to room temperature taking-up block product, and, by its pulverizing, obtain ZnLiAlF 6: 0.06Tm 3+up-conversion phosphor.
Should be understood that, the above-mentioned statement for preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, and scope of patent protection of the present invention should be as the criterion with claims.

Claims (7)

1. a thulium doped with fluorine aluminate up-conversion phosphor, is characterized in that, it has general molecular formula: MLiAlF 6: xTm 3+; In formula, M is Mg, Ca, Sr, Ba or Zn element, Tm 3+for dopant ion, the span of x is 0.02 ~ 0.1.
2. thulium doped with fluorine aluminate up-conversion phosphor according to claim 1, is characterized in that, the value of x is 0.06.
3. the preparation method of a thulium doped with fluorine aluminate up-conversion phosphor, is characterized in that, comprises the steps:
S1, according to MLiAlF 6: xTm 3+in each element chemistry stoichiometric coefficient ratio, take respectively MF 2, LiF, AlF 3and TmF 3powder; Wherein, M is Mg, Ca, and Sr, Ba or Zn element, the span of x is 0.02 ~ 0.1;
S2, the powder in step S1 is ground 20 ~ 60 minutes, obtain uniform powder presoma;
S3, the presoma in step S2 is placed in to 800 ~ 1000 ℃ of lower calcinations 0.5 ~ 5 hour, cools to subsequently under 100 ~ 500 ℃ the insulation of carrying out 0.5 ~ 3 hour and process, obtain bulk sample;
S4, the bulk sample in step S3 is ground, obtaining molecular formula is MLiAlF 6: xTm 3+thulium doped with fluorine aluminate up-conversion phosphor, Tm 3+for dopant ion.
4. the preparation method of thulium doped with fluorine aluminate up-conversion phosphor according to claim 3, is characterized in that, the value of x is 0.06.
5. the preparation method of thulium doped with fluorine aluminate up-conversion phosphor according to claim 3, is characterized in that, in step S2, milling time is 40 minutes.
6. the preparation method of thulium doped with fluorine aluminate up-conversion phosphor according to claim 3, is characterized in that, in step S3, calcination temperature is 950 ℃, and calcination time is 3 hours.
7. according to the preparation method of the described thulium doped with fluorine of claim 3 or 6 aluminate up-conversion phosphor, it is characterized in that, in step S3, temperature when insulation is processed is 250 ℃, and soaking time is 2 hours.
CN 201210174064 2012-05-30 2012-05-30 Thulium-doped fluoroaluminate up-conversion fluorescent powder and preparation method thereof Pending CN103450896A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108384536A (en) * 2018-05-16 2018-08-10 长春理工大学 Er3+/Yb3+Codope calcium aluminum fluoride green up conversion luminescent material and preparation method thereof
CN110970541A (en) * 2018-09-29 2020-04-07 有研稀土新材料股份有限公司 Semiconductor light source and optical device prepared by same

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108384536A (en) * 2018-05-16 2018-08-10 长春理工大学 Er3+/Yb3+Codope calcium aluminum fluoride green up conversion luminescent material and preparation method thereof
CN110970541A (en) * 2018-09-29 2020-04-07 有研稀土新材料股份有限公司 Semiconductor light source and optical device prepared by same
CN110970541B (en) * 2018-09-29 2023-04-21 有研稀土新材料股份有限公司 Semiconductor light source and optical device prepared by same

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Application publication date: 20131218