CN112094644A - Ultraviolet excited Eu (II) ion single-doped single-phase full-spectrum fluorescent powder and preparation and application thereof - Google Patents
Ultraviolet excited Eu (II) ion single-doped single-phase full-spectrum fluorescent powder and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to an ultraviolet excited Eu (II) ion single-doped single-phase full-spectrum fluorescent powder, and a preparation method and an application thereof, wherein the chemical formula of the single-phase full-spectrum fluorescent powder is (Ca)9‑xEux)MgK(PO4)7Wherein x is 0.5 to 5.0 percent by mol%. The specific preparation process comprises the following steps: weighing raw material powder according to a metering ratio, uniformly mixing, grinding, calcining to obtain a precursor, carrying out reduction sintering on the precursor by an Al reduction method to realize full-spectrum emission modulation of the fluorescence conversion material, and cooling to obtain the single-phase full-spectrum fluorescent powder for the LED. Compared with the prior art, the invention can cover the wave band of 420-800nm and has a specific full-spectrum white light solution of ultra-wide continuous spectrum emission; the prepared single-phase full-spectrum fluorescent powder and a 375nm ultraviolet chip are packaged into an LED device, the LED device is lightened under the drive of 30mA current, and the color rendering index of a light source is 95.
Description
Technical Field
The invention relates to the field of leading-edge photoelectric materials, in particular to ultraviolet excited Eu (II) ion single-doped single-phase full-spectrum fluorescent powder and preparation and application thereof.
Background
As a new generation of solid-state light source, LEDs have been widely used in the fields of illumination and display due to their advantages of high efficiency, energy saving, small size, fast response, long lifetime, no pollution, etc. However, with the development of LEDs, the problems of blue light hazard, human rhythm disorder and human retina damage caused by LEDs are gradually emerging, so that the LED industry is not aware of the popularization of healthy lighting. Natural is healthy, and natural light, i.e. light like the sun, is healthy light in contrast to industrial light. Under the irradiation of light closer to the sunlight, the visual sense, the physiological rhythm and the psychological mood of a human are better. Therefore, to achieve healthy illumination based on LEDs, a Full spectrum white Light emission (sun Light) must be achieved.
Currently, there are two main implementation schemes for a full-spectrum LED: (1) the full spectrum technology of the blue light chip is that a mode of exciting the fluorescent powder by a 450-plus 460nm blue light chip is adopted, and the color rendering index (Ra) and the light effect are improved by improving the fluorescent powder. However, this white light scheme still shows a blue peak with higher intensity, except that the coverage band of the phosphor is wider than that of the ordinary LED to improve Ra and R9 (saturated red), the spectrum continuity is not perfect, and there is a great difference between the intensity ratio of each band and the solar energy. The advantages of this solution for healthy lighting are therefore not obvious. (2) The ultraviolet chip full spectrum technology, namely, the purple light chip is used for exciting RGB multicolor fluorescent powder to realize continuous spectrum, so that the ultraviolet chip full spectrum technology is close to the solar spectrum to the maximum extent, high reduction degree and high saturation degree are realized, and the occurrence of short-wave blue light is avoided. Therefore, ultraviolet chip full spectrum LEDs are considered as an ideal solution for healthy lighting. However, since the human eye is not sensitive to ultraviolet light, a fluorescent conversion material must be relied upon to achieve full spectrum emission based on an ultraviolet chip.
The current fluorescent conversion materials for full-spectrum LEDs can be divided into mixed phosphor systems and single-matrix phosphor (single-phase white light emitting phosphor) systems. As the name suggests, the mixed system fluorescent powder mixes the fluorescent powder emitted by different colors together, and the full spectrum emission is realized through the color matching of the fluorescent powder of each color. However, the mixed phosphor system is inevitably limited by the matching degree of the phosphor (the inevitable difference in the luminescent properties of the phosphor, such as the thermal stability of fluorescence and the luminous efficiency), the difference in the physical and chemical properties (such as the moisture resistance and the stability), and the reduction in the luminous efficiency caused by the mutual absorption among the colors, which affects the light emitting quality of the LED light source. The full-spectrum LED implementation scheme based on the single-matrix white light emission fluorescent powder can effectively avoid various problems caused by the performance difference and mutual absorption of the fluorescent powder. However, the multi-color emission of the current single-matrix white light emitting phosphor is mainly realized by means of the co-doping of multiple luminescent centers. The complex interaction such as energy transfer among the co-doped luminescent centers can cause the reduction of the whole quantum efficiency of the fluorescent powder.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an ultraviolet excited Eu (II) ion single-doped single-phase full-spectrum fluorescent powder, and preparation and application thereof, wherein Eu is doped independently2+Under the condition of ions, Eu is realized by a topological chemical reaction method and a local area regular reaction method2+Ion crystal field regulation and control, and finally realize Eu2+Ion white light emission.
The purpose of the invention can be realized by the following technical scheme:
the single-phase full-spectrum fluorescent powder is formed by singly doping Eu (II) ions excited by ultraviolet, and the chemical formula of the single-phase full-spectrum fluorescent powder is (Ca)9-xEux)MgK(PO4)7Wherein x is 0.5-5.0% mol%;
in the technical scheme, x is preferably 3.0%;
based on the fact that the spectrum of the Eu ion source can obviously change along with the change of the composition and the structure of the matrix material, the Eu ion source is used for Eu2+The doping amount of (a) is preferably selected, and if the doping amount is less than 0.5%, the luminous intensity of the sample is too low; if the doping amount is more than 5.0%, the color coordinate value of the sample deviates from the white light range, and white light cannot be obtained.
Eu in the single-phase full-spectrum fluorescent powder2+Ion as a single activation center, Ca9MgK(PO4)7Is a matrix material;
the single-phase full-spectrum fluorescent powder can emit full-spectrum white light with a spectrum range of 420-800nm under the excitation of ultraviolet light.
The preparation method of the Eu (II) ion single-doped single-phase full-spectrum fluorescent powder comprises the following steps:
s1: weighing CaCO according to a metering ratio3，(MgCO3)4·Mg(OH)2·5H2O，K2CO3，NH4H2PO4，Eu2O3Uniformly mixing, grinding and calcining to obtain a precursor;
s2: and (4) carrying out reduction sintering on the precursor obtained in the step S1 by an Al reduction method to realize full-spectrum emission modulation of the fluorescence conversion material, and cooling to obtain the single-phase full-spectrum fluorescent powder.
Further, the grinding time in S1 is 15-20 min.
Further, the calcination time in S1 is 2-96 h, and the calcination temperature is 800-1100 ℃. The calcination temperature is preferably 1050 ℃ and the calcination time is preferably 10 hours.
Further, the reduction sintering described in S2 is a non-contact reduction.
Further, the non-contact reduction process is as follows:
placing Al powder and the precursor obtained in S1 in two open containers respectively, then placing the two open containers in a sealed container, vacuumizing the sealed container, and then carrying out reduction sintering at 1000 ℃.
Further, the ratio of the Al powder to the precursor (0.3-10) is 1.
Further, the distance between the centers of the two open containers is 1-5 cm;
the time for reduction sintering is 0.1-96 h, and the time for reduction sintering is preferably 8 h.
Further, vacuumizing to the pressure of less than minus 0.1MPa in the sealed container.
When the preparation method of the Eu (II) ion single-doped single-phase full-spectrum fluorescent powder is applied, the prepared single-phase full-spectrum fluorescent powder and a 375nm ultraviolet chip are packaged into an LED device, the LED device is lightened under the drive of current of 30mA, and the color rendering index of a light source is 95.
Compared with the prior art, the invention has the following technical advantages:
1) different from the traditional white light source with high color rendering index, the invention provides a solution of full-spectrum white light which has a spectral range covering 420-800nm and has specific ultra-wide continuous spectrum emission;
2) different from a mixed fluorescent powder fluorescent conversion system, the invention uses one fluorescent powder to realize full-spectrum white light emission;
3) unlike the solution of ion-codoped single-phase white light emitting phosphor, the present invention uses only Eu2+Under the condition of ion as a luminescent center, full spectrum emission is realized, and the problem that Eu needs to be used in the prior art is solved2+Besides, the doping of other ions, thereby improving the overall quantum efficiency of the fluorescent powder.
4) Different from the traditional atmosphere reduction preparation method, the invention adopts a topological chemical reaction method as a synthesis preparation means. Compared with the traditional atmosphere reduction, the method realizes Eu2+Ion in Ca9MgK(PO4)7The full-spectrum luminescence modulation in the process can effectively regulate and control the local coordination number and the chemical pressure of a crystal field through topological chemical reaction, thereby realizing the optimization of the spectral performance of the single-doped single-phase white light emitting fluorescent powder.
Drawings
FIG. 1 is an XRD diagram of a Eu (II) ion single-doped single-phase full spectrum phosphor in different embodiments;
FIG. 2 is a diagram showing the photoluminescence (. lamda.) of Eu (II) ion single-doped single-phase full-spectrum phosphor in different embodimentsex365nm) spectrogram;
fig. 3 is an EL spectrum of a white LED packaged in example 2.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1:
1) selecting CaCO3，(MgCO3)4·Mg(OH)2·5H2O，K2CO3，NH4H2PO4，Eu2O3As a raw material, according to (Ca)9- xEux)MgK(PO4)7(x is 0.5%, mol%) 2g of the mixed raw materials were weighed out in a stoichiometric ratio. The mass of each raw material is respectively as follows: CaCO3：0.9615g，(MgCO3)4·Mg(OH)2·5H2O：0.1037g，K2CO3：0.0738g，NH4H2PO4：0.8600g，Eu2O3：0.0009g。
2) And grinding the raw material mixture in an agate mortar for 15-20 minutes, loading the mixture into an alumina crucible after the materials are uniformly mixed, placing the alumina crucible into a muffle furnace, and calcining the mixture for 10 hours at 1050 ℃. And taking out the calcined sample, and putting the calcined sample into an agate mortar to be ground into powder to obtain a precursor sample.
3) Mixing the precursor and aluminum powder according to the mass ratio of 1: after weighing in a proportion of 0.3, the materials are respectively contained in crucibles and are parallelly and side by side placed in a tube furnace (the aluminum powder is not contacted with the sample).
4) And (4) sealing the tube furnace, and vacuumizing. The heating temperature is set to 1000 ℃, and the temperature is kept for 8 hours. And after the furnace temperature is cooled to room temperature, taking out the sample, and grinding uniformly to obtain a final product.
An X-ray diffractometer (Ultima IV-185) is used for testing the crystal structure of the fluorescent powder, Cu-Ka is used for testing as a target material, and the scanning angle 2 theta is 5-80Obtaining XRD test pattern (shown in figure 1) of the sample, and finding out diffraction peak and Ca of the long-distance Al powder reduction sample9MgK(PO4)7The standard cards of the crystal correspond one to one, showing that Eu2+The doping of ions does not bring obvious influence on the crystal structure, and the obtained fluorescent powder is Ca9MgK(PO4)7Isomorphic pure phase material.
The spectrum property of the system fluorescent powder is tested by using a fluorescence spectrometer (HITACHI F-7000) (as shown in figure 2), and the result shows that the emission spectrum of the system fluorescent powder is continuous visible light covering a wave band of 420-800nm under the excitation of 365nm ultraviolet light.
The following table shows a comparison of data for specific examples of the invention.
Example 2:
1) selecting CaCO3，(MgCO3)4·Mg(OH)2·5H2O，K2CO3，NH4H2PO4，Eu2O3As a raw material, according to (Ca)9- xEux)MgK(PO4)7(x is 3.0%, mol%) 2g of the mixed raw materials were weighed out in a stoichiometric ratio. The mass of each raw material is respectively as follows: CaCO3：0.9579g，(MgCO3)4·Mg(OH)2·5H2O：0.1036g，K2CO3：0.0737g，NH4H2PO4：0.8591g，Eu2O3：0.0056g。
2) And grinding the raw material mixture in an agate mortar for 15-20 minutes, loading the mixture into an alumina crucible after the materials are uniformly mixed, placing the alumina crucible into a muffle furnace, and calcining the mixture for 10 hours at 1050 ℃. Taking out the calcined sample, and putting the calcined sample into an agate mortar to be ground into powder to obtain a precursor sample;
3) mixing the precursor and aluminum powder according to the mass ratio of 1: weighing in a proportion of 0.3, respectively placing in crucibles, and placing in a tube furnace in parallel (aluminum powder is not in contact with a sample);
4) and (4) sealing the tube furnace, and vacuumizing. The heating temperature is set to 1000 ℃, and the temperature is kept for 8 hours. And after the furnace temperature is cooled to room temperature, taking out the sample, and grinding uniformly to obtain a final product.
An X-ray diffractometer (Ultima IV-185) is used for testing the crystal structure of the fluorescent powder, Cu-Ka is used as a target material for testing, the scanning angle 2 theta range is 5-80 degrees, the XRD test pattern of the sample (shown in figure 1) is obtained, and the diffraction peak and Ca of the long-distance Al powder reduction sample can be seen9MgK(PO4)7The standard cards of the crystal correspond one to one, showing that Eu2+The doping of ions does not bring obvious influence on the crystal structure, and the obtained fluorescent powder is Ca9MgK(PO4)7Isomorphic pure phase material.
The spectral properties of the phosphor of the system are tested by using a fluorescence spectrometer (HITACHI F-7000) (as shown in figure 2), and the results show that the phosphor of the system emits continuous visible light covering a waveband of 420-800nm under the excitation of 365nm ultraviolet light, and the color coordinates are (0.350, 0.358).
And uniformly mixing the sample with silica gel, coating the mixture on an ultraviolet chip with the wavelength of 375nm, and packaging the ultraviolet chip into an LED. Under the current drive of 30mA, the LED is lightened. The optical properties (as shown in fig. 3) of the LED were measured using an integrating sphere (HAAS-2000), and the LED showed a white light color rendering index of 95 and a color temperature of 4725K.
Example 3:
1) selecting CaCO3，(MgCO3)4·Mg(OH)2·5H2O，K2CO3，NH4H2PO4，Eu2O3As a raw material, according to (Ca)9- xEux)MgK(PO4)7(x is 5.0%, mol%) 2g of the mixed raw materials were weighed out in a stoichiometric ratio. Each one ofThe raw materials are respectively as follows by mass: CaCO3：0.9550g，(MgCO3)4·Mg(OH)2·5H2O：0.1035g，K2CO3：0.0737g，NH4H2PO4：0.8584g，Eu2O3：0.0094g)。
2) And grinding the raw material mixture in an agate mortar for 15-20 minutes, loading the mixture into an alumina crucible after the materials are uniformly mixed, placing the alumina crucible into a muffle furnace, and calcining the mixture for 10 hours at 1050 ℃. And taking out the calcined sample, and putting the calcined sample into an agate mortar to be ground into powder to obtain a precursor sample.
3) Mixing the precursor and aluminum powder according to the mass ratio of 1: after weighing in a proportion of 0.3, the materials are respectively contained in crucibles and are parallelly and side by side placed in a tube furnace (the aluminum powder is not contacted with the sample).
4) And (4) sealing the tube furnace, and vacuumizing. The heating temperature is set to 1000 ℃, and the temperature is kept for 8 hours. And after the furnace temperature is cooled to room temperature, taking out the sample, and grinding uniformly to obtain a final product.
An X-ray diffractometer (Ultima IV-185) is used for testing the crystal structure of the fluorescent powder, Cu-Ka is used as a target material for testing, the scanning angle 2 theta range is 5-80 degrees, the XRD test pattern of the sample (shown in figure 1) is obtained, and the diffraction peak and Ca of the long-distance Al powder reduction sample can be seen9MgK(PO4)7The standard cards of the crystal correspond one to one, showing that Eu2+The doping of ions does not bring obvious influence on the crystal structure, and the obtained fluorescent powder is Ca9MgK(PO4)7Isomorphic pure phase material.
The spectrum property of the system fluorescent powder is tested by using a fluorescence spectrometer (HITACHI F-7000) (as shown in figure 2), and the result shows that the emission spectrum of the system fluorescent powder is continuous visible light covering a wave band of 420-800nm under the excitation of 365nm ultraviolet light.
Comparative example 1
For Ca already disclosed in the prior art9MgM(PO4)7:Eu2+,Xn+(M ═ Li, Na, K; X is other elements) materials, although all of them are single-phase structures, and can implement full spectrum luminescenceLight, and the white light can not be realized after any component in the codopant is removed, but the (Ca) prepared in the technical scheme9-xEux)MgK(PO4)7In the case of single doping of Eu2+The fluorescent powder can realize full-spectrum luminescence, only one luminescence center is doped in the fluorescent powder, the integral quantum efficiency of the fluorescent powder is improved, and the fluorescent powder has remarkable advantages.
Meanwhile, both the preparation method and the traditional reduction method adopted in the prior technical scheme can not form a relatively ideal crystal field environment, Eu2+The transition type of the ion depends on the crystal field environment and different light-emitting behaviors, which indicate that the crystal field environment of the ion is different, therefore, even if the ion is under the condition of pure phase, the microstructure is different compared with the technical scheme, the difference of the microstructure mainly depends on the topological chemical reaction treatment process in the technical scheme, and a reduction system must be considered by a person skilled in the art to realize the ideal effect of the technical scheme.
For another single-doped single-phase full-spectrum fluorescent powder in the prior art, such as single-doped Eu2+Ca of (2)9MgNa(PO4)7Although only Na is replaced in the host material, the fluorescent powder shows different light-emitting behaviors, and the light-emitting position and the light-emitting intensity are obviously changed. Such as the literature "Kim J S, Park Y H, Kim S M, et al2SiO4:Eu2+(M＝Ca,Sr,Ba)phosphors for green and greenish white LEDs[J]M described in Solid State Communications,2005,133(7), 445-2SiO4:Eu2+(M ═ Ca, Sr, Ba) material, although it is different from Ca, Sr, Ba, M is clearly seen2SiO4:Eu2+But showed distinct luminescence behavior, the Sr salt sample showed directly a bimodal emission compared to the Ca and Ba samples.
Therefore, when implementing the technical solution, a person skilled in the art needs to pay attention to the following points: in Eu2+Doped phosphor Ca9MgM(PO4)7:Eu2+In different host materials, different crystal field environments will result in Eu2+Different light-emitting behaviors are generated, doping substitution of similar elements is easy to think in the paper level, but the method is realized in the field, the optimal crystal field environment is realized, and the requirements of the light-emitting performance of the light-emitting material are met, so that the method is a very important core problem for material design and spectrum regulation in the field and is a core innovation point to be embodied in the technical scheme.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. The ultraviolet excited Eu (II) ion single-doped single-phase full-spectrum fluorescent powder is characterized in that the chemical formula of the single-phase full-spectrum fluorescent powder is (Ca)9-xEux)MgK(PO4)7Wherein x is 0.5-5.0% mol%;
eu in the single-phase full-spectrum fluorescent powder2+Ion as a single activation center, Ca9MgK(PO4)7Is a matrix material;
the single-phase full-spectrum fluorescent powder can emit full-spectrum white light with a spectrum range of 420-800nm under the excitation of ultraviolet light.
2. A method for preparing Eu (II) -ion single-doped single-phase full-spectrum fluorescent powder in claim 1, which comprises the following steps:
s1: weighing CaCO according to a metering ratio3，(MgCO3)4·Mg(OH)2·5H2O，K2CO3，NH4H2PO4，Eu2O3Uniformly mixing, grinding and calcining to obtain a precursor;
s2: and (4) carrying out reduction sintering on the precursor obtained in the step S1 by an Al reduction method to realize full-spectrum emission modulation of the fluorescence conversion material, and cooling to obtain the single-phase full-spectrum fluorescent powder.
3. The method according to claim 2, wherein the grinding time in S1 is 15-20 min.
4. The method for preparing Eu (II) -ion single-doped single-phase full-spectrum phosphor according to claim 2, wherein the calcination time in S1 is 2-96 hours, and the calcination temperature is 800-1100 ℃.
5. The method of claim 2, wherein the reduction sintering in S2 is a non-contact reduction.
6. The method for preparing Eu (II) -ion single-doped single-phase full-spectrum phosphor according to claim 5, wherein the non-contact reduction process comprises:
placing Al powder and the precursor obtained in S1 in two open containers respectively, then placing the two open containers in a sealed container, vacuumizing the sealed container, and then carrying out reduction sintering at 1000 ℃.
7. The method for preparing Eu (II) -ion single-doped single-phase full-spectrum phosphor according to claim 6, wherein the ratio of Al powder to precursor is (0.3-10): 1.
8. The method for preparing Eu (II) -ion single-doped single-phase full-spectrum phosphor according to claim 6, wherein the distance between the centers of the two open containers is 1-5 cm;
the time of reduction sintering is 0.1-96 h.
9. The method of claim 6, wherein the pressure in the sealed container is less than minus 0.1 MPa.
10. The application of the preparation method of the Eu (II) -ion single-doped single-phase full-spectrum fluorescent powder in claim 1 is characterized by comprising the following steps: and packaging the single-phase full-spectrum fluorescent powder and a 375nm ultraviolet chip into an LED device, and lighting the LED device under the drive of a current of 30mA, wherein the color rendering index of a light source is 95.
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| CN113549454A (en) * | 2021-08-24 | 2021-10-26 | 上海应用技术大学 | Eu (II) ion doped single-phase full-spectrum emission fluorescent powder and preparation method and application thereof |
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