CN112011332A - Far-red fluorescent powder and light-emitting device comprising same - Google Patents
Far-red fluorescent powder and light-emitting device comprising same Download PDFInfo
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Abstract
The invention relates to a far-red fluorescent powder with a luminescent waveband of 720-680-plus-one nm, which can be excited by blue light, ultraviolet light or near-ultraviolet light so as to solve the technical problems of low luminescent efficiency, poor temperature tolerance, poor water resistance and the like of the far-red fluorescent powder in the prior art. The far-red fluorescent powder can be used for preparing a light-emitting device, has the advantage of high luminous efficiency, and can be widely applied to various traditional or novel fields such as full-spectrum healthy illumination, plant illumination, ultrahigh color gamut liquid crystal display backlight sources, calibration light sources and security monitoring fields. In addition, in the light-emitting device, on the basis of matching with the far-red fluorescent powder, the visible light fluorescent powder with the emission wavelength range of 450-680nm and the near-infrared fluorescent powder with the emission wavelength range of 720-1600nm are simultaneously used, so that the light-emitting device has stronger far-red light emission and unique application, and the application field of the light-emitting device is further widened.
Description
Technical Field
The invention relates to the technical field of luminescent materials, in particular to far-red fluorescent powder and a luminescent device comprising the same.
Background
White Light Emitting Diodes (LEDs) as a new generation of Light source products have the advantages of high Light efficiency, low energy consumption, long life, no pollution, etc., have been widely used in the fields of illumination and display, and are a strategic emerging industry of key development in our country. With the continuous development of semiconductor lighting technology and the accelerated penetration of market application, the market demands for white light LED light source performance are shifted from originally pure pursuit of "high color rendering and high brightness" to "high quality" considering performance parameters of light source such as safety, health, color reduction, saturation, spectrum continuity, etc., pursuit of full spectrum "healthy green lighting" similar to sunlight spectrum and ultra-high color gamut liquid crystal display backlight technology.
The full-spectrum healthy illumination which is closer to the spectrum of sunlight can effectively improve the R9 color rendering index, so that the color of an object seen by human eyes is more real, the reading and reading process is more comfortable, the 680-plus 690nm wave band far-red light is beneficial to the release of melatonin to promote sleep and recovery of vision and brain fatigue, and meanwhile, the full-spectrum healthy illumination has the function of promoting the regeneration of human hair and cells, really realizes 'green healthy illumination', and has the effects of illumination in museums and photographyThe LED lamp has wide application prospect in the fields of illumination, eye-protecting desk lamps, classroom illumination and the like. Besides, the full-spectrum light source similar to sunlight also has great application prospects in the fields of plant illumination, calibration light sources and the like: the plant growth needs sufficient sunlight irradiation, wherein the chlorophyll A, B, the phytochrome PR and the PFR not only absorb blue-violet light with the wavelength of 420-500nm, but also absorb red light with the wavelength of 600-780nm and far-red light, and a light source with a sunlight-like spectrum can create a light environment suitable for the growth and development of the plant, promote photosynthesis and is more beneficial to the healthy growth of the plant; all display equipment about to leave factory must use the calibration light source to carry out quick and automatic calibration to ambient light sensor in the equipment, and the calibration light source of class sunlight spectrum can carry out sensor calibration more swiftly, effectively. At present, the technical scheme that an LED chip is matched with fluorescent powder is mainly adopted in a sunlight-like full-spectrum light source, wherein the 450-plus 680nm visible light fluorescent powder excited by a purple light/blue light chip is commercialized, and the research on the near-infrared fluorescent powder for a fluorescence conversion type LED with the wavelength of more than 720nm is increasingly mature. However, the 680-720nm band far-red fluorescent powder material is obviously lost, and the far-red band has obvious proportion imbalance, so that the current full spectrum scheme at home and abroad cannot achieve spectrum continuity in the far-red region, and has a certain difference with the solar spectrum. Liquid crystal display LED backlight is also one of the important application fields of white light LED, which plays a crucial role in LCD color gamut coverage. Currently, wide-color-gamut (display color gamut greater than 92% NTSC) liquid crystal LED backlight display technologies and markets are becoming mature, wherein the only commercial red phosphor that can satisfy the wide-color-gamut liquid crystal display LED backlight technology is fluoride (emission peak wavelength around 630 nm). Further, an ultra-high color gamut liquid crystal display LED backlight (display color gamut greater than 100% NTSC) with higher color reduction capability and more colorful pictures has become an important development trend of white LEDs. In order to realize the development of LCD towards higher color gamut coverage and high-quality color rendering, the emission wavelength of the red phosphor is required to be longer, and the color coordinate is required to be more biased to the far-red region. However, Mn4+The fluoride is in a stable crystal field environment as a luminescence center in the fluoride, so that the fluoride is difficult to obtain a longer emission peak value through matrix control, and an emission waveband is positioned680-720nm far-red fluorescent powder, thereby restricting the further improvement of the color domain coverage rate of the liquid crystal display. Besides, in the field of security monitoring, the 680-720nm far-red light is also needed to supplement the light source for security monitoring.
At present, research and development on far-red fluorescent powder are basically in a basic research stage of a laboratory, and the problems of lack of types of the far-red fluorescent powder, low luminous efficiency of the existing system, poor material stability and the like exist, so that no fluorescent powder system capable of being practically applied exists. Therefore, it is urgently needed to develop far-red fluorescent powder with an emission band in the region of 680-720nm to meet the application requirements of various traditional and novel fields including full-spectrum healthy illumination, plant illumination, ultra-high color gamut liquid crystal display backlight, calibration light source, security monitoring and the like.
Disclosure of Invention
Based on the above situation in the prior art, the present invention is directed to provide a far-red phosphor with a luminescent band located at 680-720nm, which can be excited by blue light, ultraviolet light or near-ultraviolet light, so as to solve the technical problems of low luminescent efficiency, poor temperature tolerance, poor water resistance, etc. of the far-red phosphor in the prior art. Another object of the present invention is to provide a light emitting device containing the far-red light emitting material, which can realize efficient far-red light emission under excitation of blue light, ultraviolet light or near-ultraviolet light, so as to solve the problem of low light emitting efficiency of the far-red light emitting device in the prior art.
In order to achieve the above objects, according to one aspect of the present invention, there is provided a far-red phosphor comprising a phosphor of the formula aAO-zZ2O3·eE2O3·gGO·hMnO2·mM2The compound of O, wherein, A element is one or two of Ca, Sr and Ba elements, and at least contains Ca element; the Z element is one or two of Y, La, Lu and Gd elements; the element E is one or two of Al, Ga, In and Sc, and at least comprises Al; g element is one or two of Zn and Mg; the M element is one or two of Na, K and Li; a +2z +2m is more than or equal to 13 and less than or equal to 15, and 2z/(a +2z) is more than or equal to 0 and less than or equal to 0.1，9≤2e+h≤11，5≤g≤7，0<h≤0.4，0<h/(2e+h)≤0.045，0<m<0.9, the far-red fluorescent powder and Ca14Al10Zn6O35Have the same crystal structure.
Furthermore, the element E is an element Al and an element Ga, the mole percentage of the element Ga to the element Al is i, i is more than or equal to 1% and less than or equal to 50%; the G element is Zn element and Mg element, the mol percentage of the Mg element and the Zn element is j, j is more than or equal to 1% and less than or equal to 30%.
Further, in the formula, 2m ═ h +2 z.
Furthermore, in the molecular formula, h is more than or equal to 0.15 and less than or equal to 0.35, and z/(a +2z) is more than or equal to 0 and less than or equal to 0.05.
Further, the particles of the far-red fluorescent powder also comprise a shell, and the shell comprises a molecular formula of SiO2Or Al2O3The compound of (1).
Furthermore, the particle size of the far-red fluorescent powder is 5-45 μm, and the thickness of the shell is 5-100 nm.
Further, the particle size of the far-red fluorescent powder is 15-30 μm, and the thickness of the shell is 10-50 nm.
According to another aspect of the present invention, there is provided a light emitting device comprising a light source and a luminescent material comprising a far-red phosphor as provided hereinbefore in accordance with the first aspect of the present invention.
Further, the light source is a semiconductor chip with an emission peak wavelength range of 250-500 nm.
Further, the light source is a semiconductor chip with an emission peak wavelength range of 400-460 nm.
Furthermore, the luminescent material also comprises visible light fluorescent powder with the emission wavelength range of 450-680nm and near infrared fluorescent powder with the emission wavelength range of 720-1600 nm.
Further, the visible light phosphor is (Ca, Sr, Ba)5(PO4)3(Cl,Br,F):Eu2+、(Mg,Zn)(Ca,Sr,Ba)3Si2O8:Eu2+、(Ca,Sr,Ba)Si2N2O2:Eu2+、β-SiAlON:Eu2+、(Lu,Y,Gd)3(Al,Ga)5O12:Ce3+,Tb3+、(Lu,Y,Gd)3(Al,Ga)5O12:Ce3+、(La,Y,Lu)3Si6N11:Ce3+、(Ca,Sr,Ba)2Si5N8:Eu2+、(Ca,Sr)AlSiN3:Eu2+、K2(Si,Ge)F6:Mn4+、(Sr,Ca,Ba)4(Al,Sc,Ga,In)14O25:Mn4+、(La,Y,Gd,Lu)3(Al,Ga)(Ge,Si)5O16:Mn4+、(Lu,Y,Gd)3(Al,Ga)5O12:Mn4+One or more of.
Wherein, in each substance, the term "indicates that the element in parentheses may be a single component or a solid solution containing more than one element, for example: (Ca, Sr) AlSiN3:Eu2+Is represented as CaAlSiN3:Eu2+、SrAlSiN3:Eu2+And Ca1-αSrαAlSiN3:Eu2+(0<α<1) One or more of them. The fluorescent powder disclosed by the invention is matched with the fluorescent powder for use, so that the light-emitting device can emit light with high luminous efficiency and high color rendering, and the application requirements of various traditional and novel fields including the fields of full-spectrum healthy illumination, plant illumination, ultrahigh color gamut liquid crystal display backlight sources, calibration light sources, security monitoring and the like are met.
Further, the near-infrared fluorescent powder is (Lu, Y, Gd)3(Al,Ga)5O12:Cr3+、Sc2O3·Ga2O3·(Cr,Yb,Nd,Er)2O3、(La,Y,Gd,Lu)3(Al,Ga)5(Ge,Si)O14:Cr3+、(Sc,Ga,Al,In)BO3:Cr3+、(La,Lu,Y,Gd)(Sc,Ga,Al,In)3B4O12:Cr3+One or more of.
In summary, the present invention provides a far-red phosphor with a luminescent band located at 680-720nm, which can be excited by blue light, ultraviolet light or near-ultraviolet light, so as to solve the technical problems of low luminescent efficiency, poor temperature tolerance, poor water resistance, etc. of the far-red phosphor in the prior art. The far-red fluorescent powder can be used for preparing a light-emitting device, the light-emitting device can obtain far-red light with an emission waveband of 680-720nm under excitation of different blue light, ultraviolet light or near ultraviolet light, can avoid the defects of other far-red light obtaining modes, has the advantage of high luminous efficiency, and can be widely applied to various traditional or novel fields such as full-spectrum healthy illumination, plant illumination, ultrahigh color gamut liquid crystal display backlight sources, calibration light sources and security monitoring fields. In addition, on the basis of matching with the far-red fluorescent powder, the luminescent device simultaneously uses the visible light fluorescent powder with the emission wavelength range of 450-680nm and the near-infrared fluorescent powder with the emission wavelength range of 720-1600nm, so that the luminescent device has stronger far-red light emission and unique application, and further widens the application field.
Drawings
FIG. 1 is a diagram showing the excitation and emission spectra of a far-red phosphor sample prepared in example 1 of the present invention;
fig. 2 is a structural view of a light emitting device, reference numerals illustrating: 1-luminescent material, 2-semiconductor chip, 3-pin, 4-heat sink, 5-base, 6-glass cover.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings in conjunction with the following detailed description. It should be understood that the description is intended to be exemplary only, and is not intended to limit the scope of the present invention. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present invention.
According to an embodiment of the present invention, there is provided a far-red phosphor comprising a phosphor having a molecular formula of aAO-zZ2O3·eE2O3·gGO·hMnO2·mM2O, wherein the element A is one or two of Ca, Sr and Ba, orContains little Ca element; the Z element is one or two of Y, La, Lu and Gd elements; the element E is one or two of Al, Ga, In and Sc, and at least comprises Al; g element is one or two of Zn and Mg; the M element is one or two of Na, K and Li; a is more than or equal to 13 and less than or equal to 15 plus 2m, 0 is more than or equal to 2z/(a plus 2z) and less than or equal to 0.1, 9 is more than or equal to 2e plus h is less than or equal to 11, 5 is more than or equal to g is less than or equal to 7, 0<h≤0.4，0<h/(2e+h)≤0.045，0<m<0.9, the far-red fluorescent powder and Ca14Al10Zn6O35Have the same crystal structure. Further, the phosphor comprises a compound represented by the formula aAO-zZ2O3·eE2O3·gGO·hMnO2·mM2In addition to the compound of O, may contain NH4Cl、H3BO3、BaF2And the like.
Preferably, in the far-red fluorescent powder, the element E is an element Al and an element Ga, the mole percentage of the element Ga to the element Al is i, and i is more than or equal to 1% and less than or equal to 50%; the G element is Zn element and Mg element, the mol percentage of the Mg element and the Zn element is j, j is more than or equal to 1 percent and less than or equal to 30 percent.
Preferably, in the formula, 2m ═ h +2 z.
Preferably, in the molecular formula, h is more than or equal to 0.15 and less than or equal to 0.35, and z/(a +2z) is more than or equal to 0 and less than or equal to 0.05.
According to some embodiments, the particles of the far-red phosphor further comprise a shell to enhance the temperature and water resistance of the far-red phosphor, wherein the shell comprises a compound of formula SiO2Or Al2O3The compound of (1).
Preferably, the particle size of the far-red fluorescent powder is 5-45 μm, and the thickness of the shell is 5-100 nm; more preferably, the particle size of the far-red fluorescent powder is 15-30 μm, and the thickness of the shell is 10-50 nm. The thickness of the outer shell is preferably 10-50nm because if the outer shell is too thin, the effect of improving the stability of the product is limited, and if the outer shell is too thick, the light shielding effect is generated, and the luminous efficiency of the product is reduced.
According to another embodiment of the present invention, there is provided a light emitting device comprising a light source and a luminescent material comprising a far-red phosphor as provided in the first embodiment hereinabove.
Preferably, in the light emitting device, the light source is a semiconductor chip with an emission peak wavelength range of 250-500 nm. Preferably, the light source is a semiconductor chip with an emission peak wavelength range of 400-460 nm.
Preferably, the luminescent material may further include visible light phosphor powder with an emission wavelength range of 450-680nm and near infrared phosphor powder with an emission wavelength range of 720-1600 nm. Specifically, the visible light phosphor may be (Ca, Sr, Ba)5(PO4)3(Cl,Br,F):Eu2+、(Mg,Zn)(Ca,Sr,Ba)3Si2O8:Eu2+、(Ca,Sr,Ba)Si2N2O2:Eu2 +、β-SiAlON:Eu2+、(Lu,Y,Gd)3(Al,Ga)5O12:Ce3+,Tb3+、(Lu,Y,Gd)3(Al,Ga)5O12:Ce3+、(La,Y,Lu)3Si6N11:Ce3+、(Ca,Sr,Ba)2Si5N8:Eu2+、(Ca,Sr)AlSiN3:Eu2+、K2(Si,Ge)F6:Mn4+、(Sr,Ca,Ba)4(Al,Sc,Ga,In)14O25:Mn4+、(La,Y,Gd,Lu)3(Al,Ga)(Ge,Si)5O16:Mn4+、(Lu,Y,Gd)3(Al,Ga)5O12:Mn4+One or more of. The near infrared fluorescent powder can be (Lu, Y, Gd)3(Al,Ga)5O12:Cr3+、Sc2O3·Ga2O3·(Cr,Yb,Nd,Er)2O3、(La,Y,Gd,Lu)3(Al,Ga)5(Ge,Si)O14:Cr3+、(Sc,Ga,Al,In)BO3:Cr3+、(La,Lu,Y,Gd)(Sc,Ga,Al,In)3B4O12:Cr3+One or more of. Wherein, in each substance, the term "indicates that the element in parentheses may be a single component or a solid solution containing more than one element, for example: (Ca, Sr) AlSiN3:Eu2+Is represented as CaAlSiN3:Eu2+、SrAlSiN3:Eu2+And Ca1-αSrαAlSiN3:Eu2+(0<α<1) One or more of them. The fluorescent powder disclosed by the invention is matched with the fluorescent powder for use, so that the light-emitting device can emit light with high luminous efficiency and high color rendering, and the application requirements of various traditional and novel fields including the fields of full-spectrum healthy illumination, plant illumination, ultrahigh color gamut liquid crystal display backlight sources, calibration light sources, security monitoring and the like are met.
The far-red phosphor provided in the above embodiment has a luminescence center Mn4+The specific energy level has forbidden transition emission with an emission spectrum positioned in the band of 680-720nm, namely, the position of an emission peak is not easy to change along with the change of the matrix. Partially substituting Ca element by rare earth element and partially substituting Zn element by Mg element in the matrix; the Ga element partially replaces the Al element, so that the in-situ improvement of the luminous intensity in the band range of 680-720nm can be realized, and more efficient far-red light emission can be obtained. The material structure and the band gap can be effectively improved by appropriate element substitution in the matrix, the distortion degree of matrix crystal lattices is reduced, and a more stable environment is provided for a luminous center, so that the luminous efficiency is enhanced; however, when the amount of element substitution exceeds a certain limit value, because the structure has certain "tolerance" for element substitution, excessive element substitution can cause the structure of the matrix to be damaged or impurities to appear, so that the luminous efficiency of the material is deteriorated.
Meanwhile, in the far-red fluorescent powder, the luminescent center Mn is4+Occupy Ga3+The charge imbalance of the lattice sites easily causes the reduction of the luminescence property of the material. According to the luminescence center Mn4+The doping amount of the sodium is doped into Na according to a certain proportion+、K+、Li+By using Na+、K+、Li+The ions are subjected to charge compensation, so that the distortion degree of crystal lattices can be effectively reduced, and the stability and rigidity of the crystal structure are improved, thereby realizing obvious light effect enhancement. Moreover, the far-red fluorescent powder has a strong broadband absorption peak in an ultraviolet-blue light region, and compared with the existing fluorescent powderThe far-red fluorescent powder has better luminous performance.
Further, the far-red phosphor of the present invention contains an oxide of Ca and Mn4+Leading the fluorescent powder product to easily react in a humid and high-temperature environment, leading the material structure and the luminescence center Mn4+The valence state of the compound is destroyed, and the luminescent performance of the material is reduced. By utilizing ethyl orthosilicate or aluminate coupling agent and designing a layer of compact nano shell on the surface of the far-red fluorescent powder crystal grain, the phenomenon that the luminous efficiency of the fluorescent powder is reduced due to the fact that the fluorescent powder is corroded in a high-temperature and high-humidity environment can be effectively prevented, the water resistance of the fluorescent powder is remarkably enhanced, and the stability of a product is greatly improved.
The following are specific examples of the present invention, and are only for the purpose of illustrating the far-red phosphor and the optical device according to the present invention, but the present invention is not limited to the following examples.
Example 1
The far-red phosphor provided in this example contains a compound having a composition formula of 12.6CaO 4.4Al2O3·5ZnO·0.4MnO2·0.2Na2And O. Grinding and mixing the weighed oxide raw materials according to the stoichiometric ratio of the chemical formula to obtain a mixture; grinding and uniformly mixing the mixture, calcining at 1300 ℃ for 5h, and cooling to obtain a roasted product; and carrying out post-treatment such as crushing, grinding, grading, screening and washing on the obtained roasted product to obtain the far-red fluorescent powder intermediate.
Then, liquid phase coating is carried out on the intermediate by utilizing tetraethoxysilane, and the specific process is as follows: firstly, alcohol and deionized water are utilized, and the ratio of alcohol: deionized water in a mass ratio of 1:1 to obtain a mixed solution; and then, by using the mixed solution and the far-red fluorescent powder intermediate, according to the far-red fluorescent powder intermediate: putting the far-red fluorescent powder intermediate into the mixed solution at a mass ratio of 1:5, magnetically stirring, and adjusting the mixed solution to an acid environment by using nitric acid while stirring; then according to the far-red fluorescent powder intermediate: adding tetraethoxysilane into the tetraethoxysilane in a mass ratio of 2:1, and continuously stirring for about 5 hours by magnetic force; and finally, draining the solution, drying the powder, and roasting in a vacuum oven to obtain the final far-red fluorescent powder product.
The fluorescence spectrometer is used for carrying out excitation and emission spectrum tests on the obtained far-red light sample, an excitation and emission spectrum of the far-red light fluorescent powder sample prepared in the embodiment 1 is shown in fig. 1, and as can be seen from fig. 1, the obtained far-red light fluorescent powder sample can be effectively excited in the ranges of 260-410nm and 420-490nm, the emission wavelength covers 680-720nm, and the emission peak position is 713 nm.
Dispersing the obtained far-red light fluorescent powder into organic silica gel, wherein the mass ratio of the far-red light luminescent material to the silica gel is 1.5: 1, coating the mixture obtained after defoaming treatment on a blue LED (with the emission wavelength of 460nm), and drying at 150 ℃ for 3 hours to finish packaging to obtain the LED device. And (3) introducing 350mA current into the white light LED device under the conditions of 85% humidity and 85 ℃ to light for 500h, testing the change of the luminous flux, calculating the luminous flux attenuation rate, and dividing the value obtained by dividing the difference between the initial luminous flux and the luminous flux after 500h by the initial luminous flux. The results obtained are shown in Table 1.
TABLE 1
The preparation method and characterization method of the far-red phosphor in examples 2-20 are the same as those in example 1, and only by selecting compounds with appropriate amount according to the target compounds and the composition of the chemical formula of the outer shell (as described in table 1) in each example, mixing, grinding, and selecting appropriate calcination conditions, the obtained far-red phosphor samples can be effectively excited within the ranges of 260-410nm and 420-490nm, and the emission wavelength covers 680-720 nm.
Comparative example
The far-red phosphor powder of this comparative example contains a compound having a compositional formula of 15.1CaO 11.1Al2O3·4.9MgO·0.5MnO2. Accurately weighing oxide raw materials according to the stoichiometric ratio of the chemical formula, and grinding and mixing the weighed oxide raw materials to obtain a mixture; (ii) a Grinding and uniformly mixing the mixture, calcining at 1300 ℃ for 5h, and cooling to obtain a roasted product; and carrying out post-treatment such as crushing, grinding, grading, screening and washing on the obtained roasted product to obtain a far-red fluorescent powder sample. The obtained far-red light sample is subjected to excitation and emission spectrum tests, and it can be seen that the obtained far-red light fluorescent powder sample can be effectively excited in the ranges of 260-410nm and 420-490nm, the emission wavelength covers 680-720nm, and the emission peak position is 713 nm.
Dispersing the obtained far-red light fluorescent powder into organic silica gel, wherein the mass ratio of the far-red light luminescent material to the silica gel is 1.5: 1, coating the mixture obtained after defoaming treatment on a blue LED (with the emission wavelength of 460nm), and drying at 150 ℃ for 3 hours to finish packaging to obtain the LED device. And (3) introducing 350mA current into the white light LED device under the conditions of 85% humidity and 85 ℃ to light for 500h, testing the change of the luminous flux, calculating the luminous flux attenuation rate, and dividing the value obtained by dividing the difference between the initial luminous flux and the luminous flux after 500h by the initial luminous flux. The results obtained are shown in Table 1.
The materials and the luminescence property characterization results of the far-red phosphors prepared in the above examples 1 to 20 and comparative examples are shown in table 1. (note: the relative luminescence intensity of the examples is the actual luminescence intensity divided by the actual luminescence intensity of the comparative example multiplied by 100, taking the luminescence intensity of the comparative example as the reference value of 100.)
By comparing the data of examples 1 to 20 with those of the comparative example in Table 1 above, it can be readily found that: due to luminescence center Mn4+The specific energy level has forbidden transition emission with an emission spectrum positioned in the band of 680-720nm, namely, the position of an emission peak is not easy to change along with the change of the matrix. By using rare earth elements in the matrixProper amount of element replaces Ca element, and proper amount of Mg element replaces Zn element; the Ga element replaces Al element in a proper amount, and the in-situ improvement of the luminous intensity in the band range of 680-720nm can be realized, so that more efficient far-red light emission can be obtained.
Meanwhile, in the far-red fluorescent powder, the luminescent center Mn is4+Occupy Ga3+The charge imbalance of the lattice sites easily causes the reduction of the luminescence property of the material. According to the luminescence center Mn4+The doping amount of the sodium is doped into Na according to a certain proportion+、K+、Li+The ions perform charge compensation, and obvious light effect enhancement can be realized.
Further, the far-red phosphor of the present invention contains an oxide of Ca and Mn4+Leading the fluorescent powder product to easily react in a humid and high-temperature environment, leading the material structure and the luminescence center Mn4+The valence state of the compound is destroyed, and the luminescent performance of the material is reduced. By designing a layer of compact nano shell with proper thickness on the surface of the far-red fluorescent powder crystal grain, the phenomenon that the luminous efficiency of the fluorescent powder is reduced due to the fact that the fluorescent powder is corroded in a high-temperature high-humidity environment can be effectively prevented, and the stability of a product is greatly improved (the double 85 light-pass attenuation rate is reduced).
The following examples 21 to 35 are light-emitting devices made of the far-red phosphor of the present invention as a light-emitting material, and take the structure of a light-emitting device known in the art as an example, and in some embodiments, as shown in fig. 2, the light-emitting device includes a light-emitting material 1, a semiconductor chip 2, leads 3, a heat sink 4, a base 5, and a glass cover 6. The heat sink 4 is fixed on the base 5, the semiconductor chip 2 is fixed on the heat sink 4, the lead pins 3 are led out, the luminescent material 1 covers the semiconductor chip 2, the visible light luminescent material layer 6 covers the far-red light luminescent material layer 1, and the glass cover 6 covers the exterior of the luminescent material 1.
Example 21
The light-emitting device described in example 21 uses a semiconductor chip having a wavelength of 460nm as a light source, and the light-emitting material is a far-red phosphor having a chemical formula of 13.8CaO · 4.5Al2O3·0.5Ga2O3·MgO·5ZnO·0.2MnO2·0.1K2O, accurately weighing the oxide raw materials according to the stoichiometric ratio, and grinding and mixing the weighed oxide raw materials to obtain a mixture; calcining the mixture at 1300 ℃ for 5h, and cooling to obtain a calcined product; and (3) carrying out crushing, grinding, grading, screening and washing on the obtained roasted product, and then processing to obtain the far-red light luminescent intermediate. Then, liquid phase coating is carried out on the intermediate by utilizing tetraethoxysilane, and the specific process is as follows: firstly, alcohol and deionized water are utilized, and the ratio of alcohol: deionized water in a mass ratio of 1:1 to obtain a mixed solution; and then, by using the mixed solution and the far-red fluorescent powder intermediate, according to the far-red fluorescent powder intermediate: putting the far-red fluorescent powder intermediate into the mixed solution at a mass ratio of 1:5, magnetically stirring, and adjusting the mixed solution to an acid environment by using nitric acid while stirring; then according to the far-red fluorescent powder intermediate: adding tetraethoxysilane into the tetraethoxysilane in a mass ratio of 2:1, and continuously stirring for about 5 hours by magnetic force; and finally, draining the solution, drying the powder, and roasting in a vacuum oven to obtain the final far-red fluorescent powder material.
The molecular formula is (Lu, Y, Gd)3(Al,Ga)5O12:Ce3+The oxide visible light fluorescent powder material is prepared by the following method: weighing oxide raw materials according to the stoichiometric ratio of the chemical formula, and mixing to obtain a mixture; grinding and uniformly mixing the mixture, calcining the mixture for 10 hours in reducing atmosphere at 1500 ℃, and cooling to obtain a roasted product; and carrying out post-treatment such as crushing, grinding, grading, screening and washing on the obtained roasted product to obtain the intermediate of the oxide visible light fluorescent powder material. Then, liquid phase coating is carried out on the intermediate by utilizing tetraethoxysilane, and the specific process is as follows: firstly, using deionized water, and oxidizing a visible light emitting material intermediate: putting the oxide visible light luminescent material intermediate into deionized water at a mass ratio of 1:5, magnetically stirring, and adjusting the solution to an acidic environment by using nitric acid while stirring; then according to the oxide visible light luminescent material intermediate: adding tetraethoxysilane into the tetraethoxysilane in a mass ratio of 2:1, and continuously stirring for about 5 hours by magnetic force; finally, the solution is drained, andand drying the powder, and roasting in a vacuum oven to obtain the final oxide visible light fluorescent powder material.
The molecular formula is (Ca, Sr) AlSiN3:Eu2+The nitride visible light fluorescent powder material is prepared by the following method: weighing nitride raw materials according to the stoichiometric ratio of the chemical formula, and uniformly mixing to obtain a mixture; grinding the mixture, calcining the mixture for 10 hours in reducing atmosphere at 1600 ℃ respectively, and cooling to obtain a roasted product; and carrying out post-treatment such as crushing, grinding, grading, screening and washing on the obtained roasted product to obtain the intermediate of the nitride visible light fluorescent powder material. Then, liquid phase coating is carried out on the intermediate by utilizing tetraethoxysilane, and the specific process is as follows: firstly, deionized water is utilized, and a nitride visible light emitting material intermediate: putting the nitride visible light luminescent material intermediate into deionized water at a mass ratio of 1:5, magnetically stirring, and adjusting the solution to an acidic environment by using nitric acid while stirring; then according to the nitride visible light luminescent material intermediate: adding tetraethoxysilane into the tetraethoxysilane in a mass ratio of 2:1, and continuously stirring for about 5 hours by magnetic force; and finally, draining the solution, drying the powder, and roasting the powder in a vacuum oven to obtain the final nitride visible light fluorescent powder material.
The phosphor material of this embodiment is packaged with a semiconductor chip to obtain a light emitting device, and the package structure of the light emitting device is shown in fig. 2. The light emitting device provided by the embodiment is tested to obtain the luminous efficiency of 46lm/W by adopting a high-precision rapid spectral radiometer integrating sphere testing system and using constant current to light the light sources of the optical devices provided by the embodiments.
The light emitting device packages and characterization methods of examples 22-35 are the same as example 21, and the desired light emitting devices were obtained by packaging according to the compositions of the light emitting material and the semiconductor chip material (as described in table 2) in each example. The results of measuring the luminous efficacy of the light emitting devices obtained in the above-mentioned examples 21 to 35 are shown in Table 2.
TABLE 2
In summary, the present invention relates to a far-red phosphor with a luminescent band located at 680-720nm, which can be excited by blue light, ultraviolet light or near-ultraviolet light, so as to solve the technical problems of low luminescent efficiency, poor temperature tolerance, poor water resistance and the like of the far-red phosphor in the prior art. The far-red fluorescent powder can be used for preparing a light-emitting device, the light-emitting device can obtain far-red light with an emission waveband of 680-720nm under excitation of different blue light, ultraviolet light or near ultraviolet light, can avoid the defects of other far-red light obtaining modes, has the advantage of high luminous efficiency, and can be widely applied to various traditional or novel fields such as full-spectrum healthy illumination, plant illumination, ultrahigh color gamut liquid crystal display backlight sources, calibration light sources and security monitoring fields. In addition, on the basis of matching with the far-red fluorescent powder, the luminescent device simultaneously uses the visible light fluorescent powder with the emission wavelength range of 450-680nm and the near-infrared fluorescent powder with the emission wavelength range of 720-1600nm, so that the luminescent device has stronger far-red light emission and unique application, and further widens the application field. The light-emitting device manufactured by the far-red fluorescent powder can be applied to various traditional and novel fields including the fields of full-spectrum healthy illumination, plant illumination, calibration light sources, ultra-high color gamut liquid crystal display backlight sources, security monitoring and the like.
It is to be understood that the above-described embodiments of the present invention are merely illustrative of or explaining the principles of the invention and are not to be construed as limiting the invention. Therefore, any modification, equivalent replacement, improvement and the like made without departing from the spirit and scope of the present invention should be included in the protection scope of the present invention. Further, it is intended that the appended claims cover all such variations and modifications as fall within the scope and boundaries of the appended claims or the equivalents of such scope and boundaries.
Claims (13)
1. The far-red fluorescent powder is characterized by comprising the molecular formula of aAO-zZ2O3·eE2O3·gGO·hMnO2·mM2The compound of O, wherein, A element is one or two of Ca, Sr and Ba elements, and at least contains Ca element; the Z element is one or two of Y, La, Lu and Gd elements; the element E is one or two of Al, Ga, In and Sc, and at least comprises Al; g element is one or two of Zn and Mg; the M element is one or two of Na, K and Li; a is more than or equal to 13 and less than or equal to 15 plus 2m, 0 is more than or equal to 2z/(a plus 2z) and less than or equal to 0.1, 9 is more than or equal to 2e plus h is less than or equal to 11, 5 is more than or equal to g is less than or equal to 7, 0<h≤0.4，0<h/(2e+h)≤0.045，0<m<0.9, the far-red fluorescent powder and Ca14Al10Zn6O35Have the same crystal structure.
2. The far-red phosphor of claim 1, wherein the E element is Al element and Ga element, the mole percentage of Ga element to Al element is i, i is 1% to 50%; the G element is Zn element and Mg element, the mol percentage of the Mg element and the Zn element is j, j is more than or equal to 1% and less than or equal to 30%.
3. The far-red phosphor according to claim 1 or 2, wherein in the formula, 2m ═ h +2 z.
4. The far-red phosphor of claim 3, wherein in the molecular formula, h is 0.15-0.35, and z/(a +2z) is 0-2.05.
5. The far-red phosphor of claim 1, wherein the particles further comprise a shell comprising a compound of formula SiO2Or Al2O3The compound of (1).
6. The far-red phosphor as claimed in claim 5, wherein the far-red phosphor has a particle size of 5 to 45 μm and the thickness of the envelope is 5 to 100 nm.
7. The far-red phosphor as claimed in claim 6, wherein the particle size of the far-red phosphor is 15 to 30 μm and the thickness of the envelope is 10 to 50 nm.
8. A light-emitting device comprising a light source and a luminescent material, wherein the luminescent material comprises the far-red phosphor of any one of claims 1 to 7.
9. The light-emitting device according to claim 8, wherein the light source is a semiconductor chip having an emission peak wavelength range of 250-500 nm.
10. The light-emitting device according to claim 9, wherein the light source is a semiconductor chip having an emission peak wavelength range of 400-460 nm.
11. The light-emitting device according to claim 8, wherein the light-emitting material further comprises a visible light phosphor with an emission wavelength range of 450-680nm and a near-infrared phosphor with an emission wavelength range of 720-1600 nm.
12. The light-emitting device according to claim 11, wherein the visible light phosphor is (Ca, Sr, Ba)5(PO4)3(Cl,Br,F):Eu2+、(Mg,Zn)(Ca,Sr,Ba)3Si2O8:Eu2+、(Ca,Sr,Ba)Si2N2O2:Eu2+、β-SiAlON:Eu2+、(Lu,Y,Gd)3(Al,Ga)5O12:Ce3+,Tb3+、(Lu,Y,Gd)3(Al,Ga)5O12:Ce3+、(La,Y,Lu)3Si6N11:Ce3 +、(Ca,Sr,Ba)2Si5N8:Eu2+、(Ca,Sr)AlSiN3:Eu2+、K2(Si,Ge)F6:Mn4+、(Sr,Ca,Ba)4(Al,Sc,Ga,In)14O25:Mn4+、(La,Y,Gd,Lu)3(Al,Ga)(Ge,Si)5O16:Mn4+、(Lu,Y,Gd)3(Al,Ga)5O12:Mn4+One or more of.
13. The light-emitting device according to claim 11, wherein the near-infrared phosphor is (Lu, Y, Gd)3(Al,Ga)5O12:Cr3+、Sc2O3·Ga2O3·(Cr,Yb,Nd,Er)2O3、(La,Y,Gd,Lu)3(Al,Ga)5(Ge,Si)O14:Cr3+、(Sc,Ga,Al,In)BO3:Cr3+、(La,Lu,Y,Gd)(Sc,Ga,Al,In)3B4O12:Cr3+One or more of.
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| CN114203887A (en) * | 2021-11-10 | 2022-03-18 | 欧普照明股份有限公司 | Light source module and lighting device comprising same |
| CN114196398A (en) * | 2021-12-13 | 2022-03-18 | 江苏师范大学 | Mn for plant lighting4+Doped high-luminous-efficiency aluminate fluorescent material and preparation method thereof |
| CN115232617A (en) * | 2021-04-23 | 2022-10-25 | 有研稀土新材料股份有限公司 | Luminescent material and luminescent device comprising same |
| CN116284818A (en) * | 2023-02-24 | 2023-06-23 | 兰州大学 | Photosensitive Co-MOF material and preparation method and application thereof |
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| CN115232617A (en) * | 2021-04-23 | 2022-10-25 | 有研稀土新材料股份有限公司 | Luminescent material and luminescent device comprising same |
| CN115232617B (en) * | 2021-04-23 | 2023-12-22 | 有研稀土新材料股份有限公司 | Luminescent material and luminescent device comprising same |
| CN114203887A (en) * | 2021-11-10 | 2022-03-18 | 欧普照明股份有限公司 | Light source module and lighting device comprising same |
| CN114203887B (en) * | 2021-11-10 | 2024-06-07 | 欧普照明股份有限公司 | Light source module and lighting device comprising same |
| CN114196398A (en) * | 2021-12-13 | 2022-03-18 | 江苏师范大学 | Mn for plant lighting4+Doped high-luminous-efficiency aluminate fluorescent material and preparation method thereof |
| CN116284818A (en) * | 2023-02-24 | 2023-06-23 | 兰州大学 | Photosensitive Co-MOF material and preparation method and application thereof |
| CN116284818B (en) * | 2023-02-24 | 2024-05-31 | 兰州大学 | Photosensitive Co-MOF material and preparation method and application thereof |
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| CN112011332B (en) | 2022-05-06 |
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