CN110229668B - Europium-doped orange-red fluorescent material and preparation method and application thereof - Google Patents
Europium-doped orange-red fluorescent material and preparation method and application thereof Download PDFInfo
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- CN110229668B CN110229668B CN201910547918.0A CN201910547918A CN110229668B CN 110229668 B CN110229668 B CN 110229668B CN 201910547918 A CN201910547918 A CN 201910547918A CN 110229668 B CN110229668 B CN 110229668B
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Abstract
本发明公开了一种铕掺杂的橙红色荧光材料的制备方法与应用，涉及照明材料领域，其化学组成为LiNa2B5P2O14:xR，其中，x为摩尔分数，0.01≤x≤0.13。该材料以硼磷酸盐为基质，掺杂铕后发射橙红色荧光。该荧光材料具有结晶性好，性能稳定的特点。将其应用于近紫外LED时，具有色温低、色纯度高，发光效率高的特点。本发明还提供了该铕掺杂的橙红色荧光材料的制备方法，该方法操作简单，反应条件温和，适合大规模产业化生产。
The invention discloses a preparation method and application of a europium - doped orange - red fluorescent material, and relates to the field of lighting materials. ≤0.13. The material is based on borophosphate and emits orange-red fluorescence after doping with europium. The fluorescent material has the characteristics of good crystallinity and stable performance. When applied to near-ultraviolet LEDs, it has the characteristics of low color temperature, high color purity and high luminous efficiency. The invention also provides a preparation method of the europium-doped orange-red fluorescent material, which is simple in operation, mild in reaction conditions and suitable for large-scale industrial production.
Description
Technical Field
The invention relates to the field of lighting materials, in particular to a europium-doped orange-red fluorescent material and a preparation method and application thereof.
Background
In the historical long river of human civilization, human beings have struggled with the diffuse night, and after the light sources of fire, incandescent lamps and fluorescent lamps, the human beings in the 20 th century discovered the phenomenon of "electroluminescence", and thus invented a fourth generation lighting source, Light Emitting Diodes (LEDs). Compared with fluorescent lamps and incandescent lamps, the white light LED has the advantages of stable performance, long service life, small heat productivity, high luminous efficiency, high response speed, small volume, planar packaging, no pollution of toxic substances such as mercury and the like. Therefore, white LEDs are recognized as one of the most promising high-tech fields in the 21 st century as a future generation of illumination light source.
At present, the most important way to realize white light LEDs is the fluorescence conversion technology, i.e. coating a phosphor material on an LED chip, and under the excitation of short waves (blue light, ultraviolet light) emitted by the LED, the phosphor emits visible light, and the white light is formed by mixing three primary colors (red, green, blue). However, the phosphor powder in the phosphor-converted WLED developed by the prior art generally has the problems of low color rendering index, high color temperature, low luminous efficiency and the like. Therefore, there is an urgent need to develop a novel phosphor having high luminous efficiency, low color temperature, high color purity, good stability and excellent performance.
Disclosure of Invention
The first invention of the invention is that: aiming at the existing problems, the europium-doped orange-red fluorescent material is provided, takes borophosphate as a substrate, can emit orange-red fluorescence after being doped with europium, and has the characteristics of good crystallinity, stable performance, low color temperature, high color purity and high luminous efficiency.
The second object of the present invention is to: the preparation method of the europium-doped orange-red fluorescent material is simple to operate, mild in reaction conditions and suitable for large-scale industrial production.
The third invention of the present invention is directed to: provides the application of the europium-doped orange-red fluorescent material in a near ultraviolet LED.
The technical scheme adopted by the invention is as follows:
a europium-doped orange-red fluorescent material has the chemical composition LiNa2B5P2O14:x Eu3+Wherein x is a mole fraction, and x is more than or equal to 0.01 and less than or equal to 0.13.
The europium-doped orange-red fluorescent material comprises Li with the molar ratio of 1 (2-x) to 10:4: x 0.5:1:5:2: x2CO3、Na2CO3、H3BO3、NH4H2PO4And Eu2O3，0.01≤x≤0.13。
The excitation wavelength of the europium-doped orange-red fluorescent material is 360-410nm, and the emission wavelength is 580-700 nm.
The europium-doped orange-red fluorescent material has the strongest excitation wavelength of 394nm and the strongest emission wavelength of 594 nm.
A preparation method of europium-doped orange-red fluorescent material comprises the following steps: uniformly mixing the raw materials, fully grinding, pre-sintering at the temperature of 250-400 ℃ for 8-12 hours, cooling to room temperature along with a furnace, taking out and grinding for 20-40 min; and then preserving the heat at the temperature of 550-600 ℃ for 5-7 days, cooling the sample to room temperature along with the furnace, taking out the sample, grinding the sample for 20-40min, and fully drying the sample to obtain the nano-crystalline silicon dioxide.
The europium-doped orange-red fluorescent material is applied to a near ultraviolet LED.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
the invention provides a europium-doped orange-red fluorescent material, which takes borophosphate as a matrix and emits orange-red fluorescence after being doped with europium. The fluorescent material has the characteristics of good crystallinity and stable performance. When the fluorescent material is applied to a near ultraviolet LED, the fluorescent material has the characteristics of low color temperature, high color purity and high luminous efficiency. The invention also provides a preparation method of the europium-doped orange-red fluorescent material, and the method is simple to operate, mild in reaction conditions and suitable for large-scale industrial production.
Drawings
The invention will now be described, by way of example, with reference to the accompanying drawings, in which:
FIG. 1 shows different Eu in the present invention3+An emission spectrogram of the fluorescent powder with doping concentration and a relation curve chart of the luminous intensity of the fluorescent powder and the value of x;
FIG. 2 is a LiNa according to the present invention2B5P2O14:0.07Eu3+The powder diffraction pattern of (a);
FIG. 3-A is LiNa according to the present invention2B5P2O14:0.07Eu3+3-B is a graph of its emission spectrum at different excitation wavelengths;
FIG. 4 is a LiNa according to the present invention2B5P2O14:0.07Eu3+A CIE color coordinate diagram of;
Detailed Description
All of the features disclosed in this specification, or all of the steps in any method or process so disclosed, may be combined in any combination, except combinations of features and/or steps that are mutually exclusive.
Any feature disclosed in this specification (including any accompanying claims, abstract) may be replaced by alternative features serving equivalent or similar purposes, unless expressly stated otherwise. That is, unless expressly stated otherwise, each feature is only an example of a generic series of equivalent or similar features.
Example 1
This example provides a europium-doped orange-red phosphor powder, which comprises 0.185g of Li as the raw material2CO30.511g of Na2CO31.546g of H3BO31.150g of NH4H2PO4And 0.062g of Eu2O3。
The europium-doped orange-red fluorescent powder is prepared by the following method:
uniformly mixing the raw materials, fully grinding, putting into a furnace for presintering at 300 ℃ for 10 hours, cooling to room temperature along with the furnace, taking out and grinding for 30 min; and then preserving heat at 570 ℃ for 6 days, cooling to room temperature along with the furnace, taking out the sample, grinding for 30min, and fully drying to obtain the product.
The europium-doped orange-red fluorescent powder provided by the embodiment has the following chemical composition by identification:
LiNa2B5P2O14:0.07Eu3+。
example 2
This example provides a europium-doped orange-red phosphor powder, which comprises raw material packageIncluding 0.185g of Li2CO30.522g of Na2CO31.546g of H3BO31.150g of NH4H2PO4And 0.026g of Eu2O3。
The europium-doped orange-red fluorescent powder is prepared by the following method:
uniformly mixing the raw materials, fully grinding, putting into a furnace for presintering at 250 ℃ for 12 hours, cooling to room temperature along with the furnace, taking out and grinding for 20 min; and then preserving heat for 5 days at 600 ℃, cooling to room temperature along with the furnace, taking out the sample, grinding for 40min, and fully drying to obtain the product.
The europium-doped orange-red fluorescent powder provided by the embodiment has the following chemical composition by identification:
LiNa2B5P2O14:0.03Eu3+。
example 3
This example provides a europium-doped orange-red phosphor powder, which comprises 0.185g of Li as the raw material2CO30.517g of Na2CO31.546g of H3BO31.150g of NH4H2PO4And 0.044g of Eu2O3。
The europium-doped orange-red fluorescent powder is prepared by the following method:
uniformly mixing the raw materials, fully grinding, putting into a furnace for presintering for 8 hours at 400 ℃, cooling to room temperature along with the furnace, taking out and grinding for 40 min; and then preserving heat at 550 ℃ for 7 days, cooling to room temperature along with the furnace, taking out the sample, grinding for 20min, and fully drying to obtain the product.
The europium-doped orange-red fluorescent powder provided by the embodiment has the following chemical composition by identification:
LiNa2B5P2O14:0.05Eu3+。
example 4
This example provides a europium-doped orange-red phosphor powder, which comprises 0.185g of Li as the raw material2CO30.506g of Na2CO31.546g of H3BO31.150g of NH4H2PO4And 0.079g of Eu2O3。
The europium-doped orange-red fluorescent powder is prepared by the following method:
uniformly mixing the raw materials, fully grinding, putting into a furnace for presintering for 9 hours at 350 ℃, cooling to room temperature along with the furnace, taking out and grinding for 30 min; and then preserving heat at 580 ℃ for 6 days, cooling to room temperature along with the furnace, taking out the sample, grinding for 40min, and fully drying to obtain the product.
The europium-doped orange-red fluorescent powder provided by the embodiment has the following chemical composition by identification:
LiNa2B5P2O14:0.09Eu3+。
the performance of the europium-doped orange-red fluorescent powder is represented in the figure 1-4.
FIG. 1 is a LiNa according to the present invention2B5P2O14:xEu3+And x is more than or equal to 0.01 and less than or equal to 0.13, and the emission spectrum of the fluorescent powder under the excitation wavelength of 394nm and a relation curve graph of the luminous intensity of the fluorescent powder and the value of x. As can be seen from the figure, Eu3+The optimum doping amount of (3) is 0.07 mol.
FIG. 2 is a LiNa according to the preferred embodiment of the present invention2B5P2O14:0.07Eu3+Powder diffraction pattern of (2).
FIG. 3-A shows LiNa according to the preferred embodiment of the present invention2B5P2O14:0.07Eu3+Excitation spectra obtained at monitoring wavelengths of 594, 588 and 621nm, respectively. As can be seen from the figure, the excitation peaks are located at 361, 376, 382 and 394nm, respectively, corresponding to Eu, respectively3+Ion from ground state7F0To an excited state5D4、5G2、5G4And5L6characteristic 4f-4f electron transitions. Of these, the strongest excitation peak is located at 394 nm. FIG. 3-B is LiNa2B5P2O14:0.07Eu3+Emission spectra obtained at excitation wavelengths of 317, 361 and 394nm, respectively, as can be seen from the figure, emission centers are located at 588, 594, (613, 621), 654 and (686, 700) nm, respectively; respectively correspond to Eu3+Ion from excited state5D0To the ground state7F0、7F1、7F2、7F3And7F4characteristic 4f-4f electron transitions. Wherein the maximum luminescence intensity is at 594nm and the optimal excitation wavelength is 394 nm.
FIG. 4 shows LiNa which is a preferred embodiment of the present invention2B5P2O14:0.07Eu3+The CIE color coordinate diagram of (0.5467,0.4473) is located at the edge of the orange-red region. Further calculation to obtain LiNa2B5P2O14:0.07Eu3+Has a Correlated Color Temperature (CCT) of 1980K and a Color Purity (CP) of 89%, indicating LiNa2B5P2O14:0.07Eu3+Is orange red fluorescent powder which can be applied to a warm white LED.
The invention is not limited to the foregoing embodiments. The invention extends to any novel feature or any novel combination of features disclosed in this specification and any novel method or process steps or any novel combination of features disclosed.
Claims (5)
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Citations (3)
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|---|---|---|---|---|
| US3586637A (en) * | 1968-06-22 | 1971-06-22 | Philips Corp | Europium activated barium and strontium borophosphate luminescent material |
| CN106281325A (en) * | 2015-06-02 | 2017-01-04 | 中国海洋大学 | A kind of novel metal boron phosphate luminescent powder and preparation method thereof |
| CN107043625A (en) * | 2017-05-08 | 2017-08-15 | 陕西科技大学 | A near-ultraviolet-excited charge-compensated red-light borophosphate luminescent material and its preparation method |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3586637A (en) * | 1968-06-22 | 1971-06-22 | Philips Corp | Europium activated barium and strontium borophosphate luminescent material |
| CN106281325A (en) * | 2015-06-02 | 2017-01-04 | 中国海洋大学 | A kind of novel metal boron phosphate luminescent powder and preparation method thereof |
| CN107043625A (en) * | 2017-05-08 | 2017-08-15 | 陕西科技大学 | A near-ultraviolet-excited charge-compensated red-light borophosphate luminescent material and its preparation method |
Non-Patent Citations (3)
| Title |
|---|
| High color purity orange-emitting KBaBP2O8:Eu3+ phosphor: Synthesis, characterization and photoluminescence properties;Bing Han et al.;《Journal of Luminescence》;20140617;第115卷;第15-20页 * |
| Photoluminescence investigation of novel reddish-orange phosphor Li2NaBP2O8:Sm3+ with high CP and low CCT;Jiyun Xiang et al.;《Ceramics International》;20181228;第45卷;第7018-7024页 * |
| Synthesis and crystal structure analysis of Li2NaBP2O8 and LiNa2B5P2O14;Synthesis and crystal structure analysis of Li2NaBP2O8 and LiNa2;《Journal of Solid State Chemistry》;20141208;第225卷;第65-71页 * |
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