CN107541211B - Blue light-emitting fluorescent powder suitable for near ultraviolet light excitation and preparation method and application thereof - Google Patents
Blue light-emitting fluorescent powder suitable for near ultraviolet light excitation and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to blue luminescent phosphor suitable for near ultraviolet light excitation, a preparation method and application thereof, belonging to the field of luminescent materials. The invention provides blue luminescent phosphor suitable for near ultraviolet light excitation, which has the general formula: sr1‑xMxLu2‑yLnyO4:Ce3+ m,AnWherein M represents one or any combination of Mg, Ca and Ba; ln represents one or any combination of Y, La, Gd and Sc; a represents one or any combination of Li, Na, K, Rb and Cs; x is more than or equal to 0 and less than or equal to 0.5, y is more than or equal to 0 and less than or equal to 1, and m is more than or equal to 0.0001 and less than or equal to 0.01; n is more than or equal to 0 and less than or equal to 0.01. The effective excitation position of the blue luminescence is located in the range of 380-450nm, and the emission peak position is located in the range of 445-480 nm. The preparation method of the blue luminescent phosphor is simple, pollution-free and low in cost. The blue light-emitting fluorescent powder effectively realizes the light conversion function of emitting blue light under the excitation of near ultraviolet light. The fluorescent powder can be used as blue light-emitting fluorescent powder suitable for near ultraviolet excitation to be applied to a blue light-emitting device or device, and can also be mixed with other color light-emitting fluorescent powder to be applied to a white light-emitting device or device.
Description
Technical Field
The invention belongs to the field of luminescent materials, and particularly relates to blue luminescent phosphor suitable for near ultraviolet light excitation, and a preparation method and application thereof.
Background
The white Light LED has the advantages of high efficiency, energy saving, long service life and the like, can be widely used for various lighting facilities such as traffic indicator lamps, street lamps, automobile lamps, outdoor display screens, advertising boards and the like, is an environment-friendly and energy-saving green lighting source, and is a new Light source for replacing the traditional lighting device in the 21 st century.
Currently, the mainstream scheme of white light LED lighting is to coat yellow fluorescent powder on a blue LED chip, and the yellow light emitted by the yellow fluorescent powder and the blue light transmitted by the tube core are mixed to form white light. However, this solution leads to poor color rendering of the device due to the lack of green and red components in the spectrum, and is not suitable for indoor lighting, especially in places such as galleries, living rooms and exhibition halls. In order to improve the color rendering performance of the white light LED, people propose to coat red, green and blue tricolor fluorescent powder by using a near ultraviolet LED chip, realize white light emission by using tricolor light emitted by the tricolor fluorescent powder, and improve the color rendering performance by more than 90%. Among them, it is key to develop red, green and blue phosphors suitable for near ultraviolet light excitation.
Currently, BaMgAl is an accepted blue-light phosphor suitable for near-ultraviolet excitation in the industry10O17:Eu2+(BAM)、Sr2MgSi2O7:Eu2+And Sr5(PO4)3Cl:Eu2+And the like. Recently, patent publication No. CN 105219378B discloses a novel silicate blue fluorescent powder Na2(Ca0.5Sr0.5-x)(SiO4):xEu2+. However, BAM blue powder has poor heat stability, Sr2MgSi2O7:Eu2+、Sr5(PO4)3Cl:Eu2+And Na2(Ca0.5Sr0.5-x)(SiO4):xEu2+The excitation efficiency drops sharply in the near ultraviolet region of 400 nm. Therefore, the novel blue-light fluorescent powder which is suitable for near ultraviolet region excitation and has excellent thermal stability is to be further developed.
Disclosure of Invention
The invention aims to develop a novel blue-light fluorescent powder which is suitable for near ultraviolet region excitation and has excellent thermal stability, and further provides a blue-light fluorescent powder suitable for near ultraviolet light excitation and a preparation method and application thereof.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a blue-emitting phosphor suitable for near-ultraviolet excitation, having the formula: sr1-xMxLu2-yLnyO4:Ce3+ m,AnWherein M represents one or any combination of Mg, Ca and Ba; ln represents one or any combination of Y, La, Gd and Sc; a represents one or any combination of Li, Na, K, Rb and Cs; x is more than or equal to 0 and less than or equal to 0.5, y is more than or equal to 0 and less than or equal to 1, and m is more than or equal to 0.0001 and less than or equal to 0.01; n is more than or equal to 0 and less than or equal to 0.01.
In the above technical solution, the expression of the blue light-emitting phosphor suitable for near ultraviolet light excitation is as follows: SrLu2O4:Ce3+ 0.002。
A preparation method of blue light-emitting fluorescent powder suitable for near ultraviolet light excitation comprises the following steps:
1) weighing each metal element compound in the general formula according to the stoichiometric ratio, fully grinding and uniformly mixing;
the metal element compound is a metal element oxide or a metal element salt compound;
2) sintering the mixture obtained in the step 1) at the temperature of 1500-1650 ℃ for 4-8 hours in a reducing atmosphere to obtain a sintered body;
3) grinding the sintered body obtained in the step 2), and washing, filtering and drying to obtain the blue light-emitting fluorescent powder suitable for near ultraviolet light excitation.
In the above technical solution, in step 2): the reducing atmosphere is CO or H2And N2The mixed gas is used as reducing atmosphere.
In the above technical solution, in step 2): the sintering temperature is 1550-.
The blue light-emitting phosphor is used as a light conversion material of a near ultraviolet LED and is applied to a blue light-emitting device or a device.
The blue light-emitting phosphor powder is mixed with other color light-emitting phosphor powder and applied to a white light-emitting device or device.
In the above technical solution, the other color luminescent phosphor is green and red luminescent phosphor suitable for near ultraviolet light excitation.
The invention has the beneficial effects that:
the blue luminescent phosphor suitable for near ultraviolet light excitation provided by the invention utilizes rare earth element Ce3+The 4f-5d energy band structure of the ions can emit blue light with the peak position located in the range of 445-480nm under the excitation of light with the wavelength of 380-450nm, and effectively realizes the light conversion function of emitting blue light under the excitation of near ultraviolet light.
The preparation method of the blue luminescent fluorescent powder suitable for near ultraviolet light excitation provided by the invention is simple, pollution-free and low in cost.
The blue luminescent phosphor suitable for near ultraviolet light excitation provided by the invention can be used as a light conversion material of a near ultraviolet light LED to realize a blue light luminescent device or device, or can be mixed with other color luminescent phosphors to realize a white light luminescent device or device. The phosphor may also have certain applications in the fields of FEDs (field emission displays), PDPs (plasma display panels), and the like.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 shows example 1SrLu2O4:Ce3+XRD diffractogram of.
FIG. 2 shows SrLu of example 12O4:Ce3+Emission spectrum (403nm excitation).
FIG. 3 shows SrLu of example 12O4:Ce3+Excitation spectrum of (monitoring 458 nm).
FIG. 4 shows SrLu of example 12O4:Ce3+Graph of varying temperature intensity changes.
FIG. 5 shows SrLu of example 12O4:Ce3+And (3) an electroluminescence spectrogram of the packaged white light LED.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings.
A blue-emitting phosphor suitable for near-ultraviolet excitation, having the formula: sr1-xMxLu2-yLnyO4:Ce3+ m,AnWherein M represents one or any combination of Mg, Ca and Ba; ln represents one or any combination of Y, La, Gd and Sc; a represents one or any combination of Li, Na, K, Rb and Cs; x is more than or equal to 0 and less than or equal to 0.5, y is more than or equal to 0 and less than or equal to 1, and m is more than or equal to 0.0001 and less than or equal to 0.01; n is more than or equal to 0 and less than or equal to 0.01. M and Ln are luminous characteristic regulators, A is a charge compensation agent, and the general expression of the fluorescent powder is as follows: SrLu2O4:Ce3+。
A preparation method of blue light-emitting fluorescent powder suitable for near ultraviolet light excitation comprises the following steps:
1) weighing each metal element compound in the general formula according to the stoichiometric ratio, fully grinding and uniformly mixing;
the metal element compound is a metal element oxide or a metal element salt compound;
2) placing the mixture obtained in the step 1) into a high-purity corundum or other crucible at the temperature of 1500-2And N2Sintering for 4-8 hours under the condition of reducing atmosphere of mixed gas to obtain a sintered body; the sintering time is preferably 1550 ℃ to 1600 ℃ and 4 hours.
3) Grinding the sintered body obtained in the step 2), and washing, filtering and drying to obtain the blue light-emitting fluorescent powder suitable for near ultraviolet light excitation.
The blue light-emitting fluorescent powder is used as a light conversion material of a near ultraviolet LED and applied to a blue light-emitting device or device, or the blue light-emitting fluorescent powder is mixed with other color light-emitting fluorescent powder and applied to a white light-emitting device or device. The other color emitting phosphors may be green and red phosphors suitable for near ultraviolet excitation.
Example 1: preparation of Sr1-xMxLu2-yLnyO4:Ce3+ m,AnWherein x is 0; y is 0; m is 0.002; n is 0; the expression is as follows: SrLu2O4:Ce3+ 0.002. Weighing SrCO according to stoichiometric ratio3，Lu2O3And CeO2Fully grinding and uniformly mixing the weighed raw materials, putting the mixture into a high-purity corundum crucible, and putting the corundum crucible at 1600 ℃ and H2And N2Sintering for 4 hours under the condition of reducing atmosphere, slightly grinding after cooling and discharging, and washing, filtering and drying to obtain the blue luminescent phosphor sample. The XRD diffraction pattern is shown in figure 1, and compared with the data of a standard card, the sample is pure-phase SrLu2O4And (5) structure. The emission spectrum and the excitation spectrum are shown in figures 2 and 3, the effective excitation range of the excitation spectrum covers 380-450nm, and the excitation peak position is near 403 nm; the emission spectrum covers 417 nm and 600nm, and the emission peak position is positioned near 458 nm. FIG. 4 is a temperature-variable spectrum of the sample, and the luminous intensity is still 86% at 25 ℃ at 150 ℃, which shows that the sample has excellent thermal stability and application performance. FIG. 5 shows the spectrum of a white LED obtained by combining yellow and red phosphors with the sample in cooperation with a 405nm UV chip, and white light with high color rendering index at different color temperatures can be obtained through different proportions of components.
Example 2 to example 122: the preparation steps are the same as those of example 1, the chemical formula, synthesis temperature, firing time and luminescent color are shown in the attached table 1, example 2 is carried out under the condition of CO reducing atmosphere, and the raw materials used in examples 2 to 122 are oxides or salt compounds of each metal element.
TABLE 1 attached chemical formulas, synthesis temperatures, firing times and luminescence colors of examples 1-122
The embodiments show that the fluorescent material of the invention has simple preparation method, no pollution, low cost and stable chemical performance. The material becomes a blue light luminescent material which has very practical value and is suitable for near ultraviolet light excitation.
The method for packaging the blue light emitting device by using the blue light emitting fluorescent powder and the near ultraviolet light LED tube core provided by the invention comprises the following steps:
1) bonding a near ultraviolet light LED chip on an LED support, and connecting the anode and the cathode of the LED chip with the anode and the cathode of the support through metal wires or conductive adhesive;
2) mixing the blue luminescent fluorescent powder provided by the invention with packaging materials such as epoxy resin or silica gel, stirring uniformly, standing for 0.5h to remove air bubbles to form powder gel;
3) coating the powder adhesive in the step 2) in an LED support to cover the LED chip and the metal wire;
4) and (3) placing the LED support in the step 3) into an oven, and curing at the temperature of 120-.
The method for packaging the white light emitting device by using the blue light emitting fluorescent powder and the near ultraviolet light LED tube core provided by the invention comprises the following steps:
1) bonding a near ultraviolet light LED chip on an LED support, and connecting the anode and the cathode of the LED chip with the anode and the cathode of the support through metal wires or conductive adhesive;
2) the blue luminescent phosphor provided by the invention is uniformly mixed with green light and red luminescent phosphor suitable for near ultraviolet excitation according to a certain proportion;
3) mixing the uniformly mixed blue-green-red fluorescent mixed powder in the step 2) with packaging materials such as epoxy resin or silica gel, stirring uniformly, standing for 0.5h to remove air bubbles and form powder gel;
4) coating the powder adhesive in the step 3) in an LED bracket to cover the LED chip and the metal wire;
5) and (3) placing the LED support in the step 4) into an oven, and curing at the temperature of 120-.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (8)
1. A blue light-emitting phosphor suitable for near ultraviolet light excitation, characterized in that the general formula is: sr1-xMxLu2- yLnyO4:Ce3+ m,AnWherein M represents one or any combination of Mg, Ca and Ba; ln represents one or any combination of Y, La, Gd and Sc; a represents one or any combination of Li, Na, K, Rb and Cs; x is more than or equal to 0 and less than or equal to 0.5, y is more than or equal to 0 and less than or equal to 1, and m is more than or equal to 0.0001 and less than or equal to 0.01; n is more than or equal to 0 and less than or equal to 0.01.
2. The blue emitting phosphor adapted for near ultraviolet excitation according to claim 1, characterized by the expression: SrLu2O4:Ce3+ 0.002。
3. A method for preparing a blue-emitting phosphor suitable for near-uv excitation according to claim 1 or 2, comprising the steps of:
1) weighing each metal element compound in the general formula according to the stoichiometric ratio, fully grinding and uniformly mixing;
the metal element compound is a metal element oxide or a metal element salt compound;
2) sintering the mixture obtained in the step 1) at the temperature of 1500-1650 ℃ for 4-8 hours in a reducing atmosphere to obtain a sintered body;
3) grinding the sintered body obtained in the step 2), and washing, filtering and drying to obtain the blue light-emitting fluorescent powder suitable for near ultraviolet light excitation.
4. The production method according to claim 3, wherein in step 2): the reducing atmosphere is CO or H2And N2The mixed gas is used as reducing atmosphere.
5. The production method according to claim 3, wherein in step 2): the sintering temperature is 1550-.
6. Use of a blue-emitting phosphor suitable for near-uv excitation according to claim 1 or 2, as a light conversion material of a near-uv LED in a blue light emitting device or apparatus.
7. Use of a blue-emitting phosphor suitable for near-uv excitation according to claim 1 or 2, wherein the blue-emitting phosphor is mixed with other color-emitting phosphors for application to a white light emitting device or apparatus.
8. Use of a blue-emitting phosphor adapted for near-ultraviolet excitation according to claim 7, wherein the other color-emitting phosphors are green and red phosphors adapted for near-ultraviolet excitation.
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| CN201710777752.2A CN107541211B (en) | 2017-09-01 | 2017-09-01 | Blue light-emitting fluorescent powder suitable for near ultraviolet light excitation and preparation method and application thereof |
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| CN107541211B true CN107541211B (en) | 2020-05-22 |
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| CN110330971B (en) * | 2019-07-17 | 2022-04-22 | 重庆理工大学 | High-sensitivity up-conversion temperature measurement material and preparation method and application thereof |
| CN111139074B (en) * | 2020-01-21 | 2022-07-08 | 济南大学 | Temperature-sensitive fluorescent powder and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102994084A (en) * | 2012-12-12 | 2013-03-27 | 中国科学院长春光学精密机械与物理研究所 | Submicron rodlike calcium scandate-based up-conversion luminescent material and preparation method thereof |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102994084A (en) * | 2012-12-12 | 2013-03-27 | 中国科学院长春光学精密机械与物理研究所 | Submicron rodlike calcium scandate-based up-conversion luminescent material and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| Intense upconversion luminescence and energy-transfer mechanism of Ho3+/Yb3+ co-doped SrLu2O4 phosphor;Songbin Liu等;《J Am Ceram Soc》;20170331;第3530-3539页 * |
| Synthesis of SrLu2O4:Eu2+ red phosphors and their photoluminescence properties;Kyeong-Ho Kim等;《Journal of Luminescence》;20161111;第183卷;第13-16页 * |
| Synthesis, structure and photoluminescence properties of Ce3+-doped SrSc2O4: a new scandate green-emitting phosphor with blue excitation;Gen Li等;《New J.Chem.》;20170517;第41卷;第5565—5571页 * |
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