CN104312587B - Preparation method of Lu2MgCa2Si3O12:Ce3+ fluorescent film with red light emission - Google Patents
Preparation method of Lu2MgCa2Si3O12:Ce3+ fluorescent film with red light emission Download PDFInfo
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- CN104312587B CN104312587B CN201410527687.4A CN201410527687A CN104312587B CN 104312587 B CN104312587 B CN 104312587B CN 201410527687 A CN201410527687 A CN 201410527687A CN 104312587 B CN104312587 B CN 104312587B
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Abstract
The invention relates to a preparation method of a Lu2MgCa2Si3Ol2: Ce＜3+＞ fluorescent film with red light emission. The preparation method comprises the following steps: (1) by taking cerous nitrate, lutecium nitrate, magnesium nitrate, calcium nitrate and tetraethyl orthosilicate as raw materials, adding the raw materials into a mixed solvent to mix uniformly, adding polyvinylpyrrolidone into the uniformly mixed solution and stirring to obtain a transparent spinning solution; (2) carrying out electrostatic spinning to obtain an original fibrous film, and calcining the fibrous film in air at 500-600 DEG C to obtain a precursor Lu-Mg-Ca-Si-O-Ce fibrous film; and (3) calcining in a reducing atmosphere at 1250-1400 DEG C, and preserving the heat for 1-3 hours to obtain the product. The fluorescent film is purely inorganic and the red light emission is broad-peak emission so that the fluorescent film can be applied to the color matching of high-powder white light LED long-distance encapsulation.
Description
Technical field
The invention belongs to large power white light LED uses fluorescent material field, particularly to a kind of, there is red emission
Lu2MgCa2Si3O12：Ce3+The preparation method of fluorescent film.
Background technology
As lighting source of new generation, white light LEDs develop to high efficiency and high-power direction.Remotely it is encapsulated into solution
Certainly another feasible way of large power white light LED light decay and color drift.LED long-distance fluorescent powder device is to be attached to fluorescent material
On substrate (typically silicon rubber), separate with blue light LED light source, thus reducing the heat of chip generation to light-emitting phosphor performance
Impact.
Business-like remote fluorescence component powder is that with silicon rubber (or resin), fluorescent material is mixed film forming at present, and is attached to
On transparency carrier, it is then encapsulated in the top of LED chip reflector.But the LED power with research and development is constantly lifted, illuminate the life-span
Constantly extend, fluorescent material is also gradually manifested with the shortcoming of silicon rubber mixing thin film-forming method, the problem of aging of silicon rubber；Fluorescent powder
Scattering problem in silica gel etc..
Controlled preparation process, size uniform are had by fluorescent fiber film prepared by electrostatic spinning technique, dispersiveness is good
Good, luminescent properties are also better than simple fluorescent powder grain film (GU Yun-Xing et al.Journal of
Materials Chemistry, 2011,21 (44)：17790-17797).But single fluorescent material cannot meet high colour developing to be referred to
The demand of number lighting source is it would be desirable to the fluorescent film having different-waveband transmitting cooperates.The phosphor of wherein red band
Material is particularly important.
Content of the invention
The technical problem to be solved is to provide a kind of Lu with red emission2MgCa2Si3O12：Ce3+Fluorescence
The preparation method of film, the method achieves the quick preparation of red fluorescence film by electrostatic spinning technique, simple to operate, enriches
Scheme of colour in long-range encapsulation for the white light LEDs.
A kind of Lu with red emission of the present invention2MgCa2Si3O12：Ce3+The preparation method of fluorescent film, including
(1) preparation of spinning liquid as precursor：
With lutecium nitrate, magnesium nitrate, calcium nitrate, cerous nitrate, tetraethyl orthosilicate as raw material, it is added in mixed solvent, mix
Close and in uniform solution, add polyvinylpyrrolidone, stirring obtains transparent spinning solution；
(2) electrostatic spinning prepares protofibre film：
Under room temperature, electrostatic spinning is carried out using above-mentioned spinning solution；
(3) preparation of precursor fibre film：
Tunica fibrosa is placed in be calcined in air atmosphere, is warming up to 500～600 DEG C, is incubated 2～4h, obtains presoma
Lu-Mg-Ca-Si-O-Ce tunica fibrosa；
(4) calcine in the atmosphere of ammonia or nitrogen and hydrogen mixture：
After being down to room temperature, the presoma Lu-Mg-Ca-Si-O-Ce tunica fibrosa that will obtain after step (3) calcining is continuing
It is passed through in ammonia or the atmosphere of nitrogen and hydrogen mixture, is warming up to 1250～1400 DEG C, be incubated 1～3h, obtain that there is red emission
Lu2MgCa2Si3O12：Ce3+Fluorescent film.
Cerous nitrate and lutecium nitrate x in molar ratio in described step (1)：(2-x) mix, x=0.01～0.08.
In described step (1), Lu, Mg, Ca, Si are stoichiometrically mixed with the ratio of mol ratio 2: 1: 2: 3, error control
System is within 5%.
In described step (1), mixed solvent is ultra-pure water and the absolute ethyl alcohol photograph of volume ratio 1～2: 18.
In described step (1), raw material is dissolved in mixed solvent and makes NO3 -Concentration reaches 0.2mol/L～0.8mol/L.
In described step (2), spinning technology parameter is voltage 6-12kV, spinning speed 0.2-1.5mL/h, receiving range 10-
18cm, humid control is below 20%.
In described step (4), the flow velocity of ammonia or nitrogen and hydrogen mixture is 50～200mL/min, the volume ratio of nitrogen and hydrogen
For 95: 5.
0.5～1 DEG C/min of heating rate in described step (3), 2～3 DEG C/min of heating rate in described step (4).
Beneficial effect
First passage electrostatic spinning technique of the present invention is prepared for the Lu with red emission2MgCa2Si3O12：Ce3+Fluorescence
Film, enriches scheme of colour in long-range encapsulation for the white light LEDs.
Brief description
Fig. 1. the obtained Lu with red emission after the lower 1300 DEG C of insulation 1h of nitrogen and hydrogen mixture atmosphere2MgCa2Si3O12：
Ce3+The excitation-emission spectrum of fluorescent film.
Obtained after .500 DEG C of Fig. 2 heat treatment 4h obtain presoma Lu-Mg-Ca-Si-O-Ce tunica fibrosa SEM photograph；
Fig. 3. the obtained Lu with red emission after the lower 1400 DEG C of insulation 1h of nitrogen and hydrogen mixture atmosphere2MgCa2Si3O12：
Ce3+Fluorescent film SEM photograph；
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than restriction the scope of the present invention.In addition, it is to be understood that after having read the content of present invention instruction, people in the art
Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Scope.
Embodiment 1
Take 1mL ultra-pure water and the mixing of 18mL absolute ethyl alcohol；By 1.43g lutecium nitrate, 0.87g magnesium nitrate, 0.397g calcium nitrate,
0.015g cerous nitrate is dissolved in mixed solvent, adds 1mL TEOS.After continuously stirred 30min, under high velocity agitation slowly
Add 0.9g PVP (molecular weight 1300000) and 2.4g PVP (molecular weight 50000), continue stirring 6h, solution clear.
The precursor solution obtaining is carried out electrostatic spinning：At room temperature, control humidity to be 20%, spinning voltage is arranged
For 6kv, the fltting speed advancing pump is 0.2mL/h, and receiving range is 10cm.
Calcine as-spun fibre obtained above in air atmosphere, heating rate is 0.5 DEG C/min, 500 DEG C of calcining heat
For after insulation 4h, Temperature fall obtains the Lu-Mg-Ca-Si-O-Ce tunica fibrosa with hollow structure.
Tunica fibrosa after calcining is transferred to tube-type atmosphere furnace, is passed through nitrogen and hydrogen mixture (95: 5), throughput is 200mL/
Min, the heating rate of tube-type atmosphere furnace is 3 DEG C/min, is warming up to 1250 DEG C, and is incubated 3h, under flowing nitrogen and hydrogen mixture, cold
But to room temperature, obtain the Lu with red emission2MgCa2Si3O12：Ce3Fluorescent fiber film.
Embodiment 2
Take 1.5mL ultra-pure water and the mixing of 18mL absolute ethyl alcohol；By 2.734g lutecium nitrate, 1.572g magnesium nitrate, 0.767g nitre
Sour calcium, 0.033g cerous nitrate is dissolved in mixed solvent, adds 1.9mL TEOS..After continuously stirred 30min, in high-speed stirring
Mix down and be slowly added to 1g PVP (molecular weight 1300000) and 2g PVP (molecular weight 50000), continue stirring 6h, solution clarification is thoroughly
Bright.
The precursor solution obtaining is carried out electrostatic spinning：At room temperature, control humidity to be 20%, spinning voltage is arranged
For 8kv, the fltting speed advancing pump is 0.8mL/h, and receiving range is 14cm.
Calcine as-spun fibre obtained above in air atmosphere, heating rate is 0.8 DEG C/min, 550 DEG C of calcining heat
For after insulation 4h, Temperature fall obtains the Lu-Mg-Ca-Si-O-Ce tunica fibrosa with hollow structure.
Tunica fibrosa after calcining is transferred to tube-type atmosphere furnace, is passed through nitrogen and hydrogen mixture (95: 5), throughput is 100mL/
Min, the heating rate of tube-type atmosphere furnace is 3 DEG C/min, is warming up to 1300 DEG C, and is incubated 2h, under flowing nitrogen and hydrogen mixture, cold
But to room temperature, obtain the Lu with red emission2MgCa2Si3O12：Ce3Fluorescent fiber film.
Embodiment 3
Take 2mL ultra-pure water and the mixing of 18mL absolute ethyl alcohol；By 3.067g lutecium nitrate, 2.142g magnesium nitrate, 1.034g nitric acid
Calcium, 0.043g cerous nitrate is dissolved in mixed solvent, adds 2.6mL TEOS.After continuously stirred 30min, under high velocity agitation
It is slowly added to 1.3g PVP (molecular weight 1300000) and 1.7g PVP (molecular weight 50000), continue stirring 6h, solution clarification is thoroughly
Bright.
The precursor solution obtaining is carried out electrostatic spinning：At room temperature, control humidity to be 20%, spinning voltage is arranged
For 12kv, the fltting speed advancing pump is 1.5mL/h, and receiving range is 18cm.
Calcine as-spun fibre obtained above in air atmosphere, heating rate is 1 DEG C/min, and 600 DEG C of calcining heat is,
After insulation 2h, Temperature fall obtains the Lu-Mg-Ca-Si-O-Ce tunica fibrosa with hollow structure.
Tunica fibrosa after calcining is transferred to tube-type atmosphere furnace, is passed through nitrogen and hydrogen mixture (95: 5), throughput is 50mL/
Min, the heating rate of tube-type atmosphere furnace is 3 DEG C/min, is warming up to 1400 DEG C, and is incubated 1h, under flowing nitrogen and hydrogen mixture, cold
But to room temperature, obtain the Lu with red emission2MgCa2Si3O12：Ce3Fluorescent fiber film.
Claims (5)
1. a kind of Lu with red emission2MgCa2Si3O12:Ce3+The preparation method of fluorescent film, including：
(1) with lutecium nitrate, magnesium nitrate, calcium nitrate, cerous nitrate, tetraethyl orthosilicate as raw material, it is added in mixed solvent, mixing
Polyvinylpyrrolidone is added, stirring obtains transparent spinning solution in uniform solution；Wherein, mixed solvent be volume ratio 1～
2:18 ultra-pure water and absolute ethyl alcohol；Dissolution of raw material makes NO in mixed solvent3 -Concentration reaches 0.2mol/L～0.8mol/L；
(2), under room temperature, electrostatic spinning is carried out using above-mentioned spinning solution；Spinning technology parameter is voltage 6-12kV, spinning speed
0.2-1.5mL/h, receiving range 10-18cm, humid control is below 20%；
(3) tunica fibrosa is placed in and is calcined in air atmosphere, is warming up to 500～600 DEG C, is incubated 2～4h, obtains presoma
Lu-Mg-Ca-Si-O-Ce tunica fibrosa；
(4), after being down to room temperature, the presoma Lu-Mg-Ca-Si-O-Ce tunica fibrosa obtaining after step (3) calcining is persistently being led to
Enter in ammonia or the atmosphere of nitrogen and hydrogen mixture, be warming up to 1250～1400 DEG C, be incubated 1～3h, obtain that there is red emission
Lu2MgCa2Si3O12:Ce3+Fluorescent film.
2. a kind of Lu with red emission according to claim 12MgCa2Si3O12:Ce3+The preparation method of fluorescent film,
It is characterized in that：Cerous nitrate and lutecium nitrate x in molar ratio in described step (1):(2-x) mix, x=0.01～0.08.
3. a kind of Lu with red emission according to claim 12MgCa2Si3O12:Ce3+The preparation method of fluorescent film,
It is characterized in that：In described step (1), Lu, Mg, Ca, Si are stoichiometrically with mol ratio 2:1:2:3 ratio mixing, error
Control within 5%.
4. a kind of Lu with red emission according to claim 12MgCa2Si3O12:Ce3+The preparation method of fluorescent film,
It is characterized in that：In described step (4), the flow velocity of ammonia or nitrogen and hydrogen mixture is 50～200mL/min, the body of nitrogen and hydrogen
Long-pending ratio is 95:5.
5. a kind of Lu with red emission according to claim 12MgCa2Si3O12:Ce3+The preparation method of fluorescent film,
It is characterized in that：0.5～1 DEG C/min of heating rate in described step (3), 2～3 DEG C/min of heating rate in described step (4).
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| CN101798505A (en) * | 2010-03-09 | 2010-08-11 | 张家港市龙杰特种化纤有限公司 | Method for preparing fluorescent fiber film |
| US20110227476A1 (en) * | 2010-03-19 | 2011-09-22 | Nitto Denko Corporation | Light emitting device using orange-red phosphor with co-dopants |
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