CN116814263B - Single-phase white light fluorescent material and preparation method and application thereof - Google Patents
Single-phase white light fluorescent material and preparation method and application thereof Download PDFInfo
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- 239000000843 powder Substances 0.000 claims description 21
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- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 claims description 4
- 229910003443 lutetium oxide Inorganic materials 0.000 claims description 4
- ZIKATJAYWZUJPY-UHFFFAOYSA-N thulium (III) oxide Inorganic materials [O-2].[O-2].[O-2].[Tm+3].[Tm+3] ZIKATJAYWZUJPY-UHFFFAOYSA-N 0.000 claims description 4
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Abstract
The invention belongs to the technical field of rare earth luminescent materials, and relates to a single-phase white light fluorescent material, a preparation method and application thereof. A single-phase white light fluorescent material, which comprises a chemical composition general formula shown in the following formula (1) or formula (2): lu 1‑x‑yNbO4:xBi3+,yDy3+ formula (1), or Lu 1‑x‑y‑z‑t BitNbO4:xTm3+,yTb3+,zEu3+ formula (2); wherein 0.005< x <0.04,0.01< y <0.02 in said formula (1); in the formula (2), 0.01< t <0.10,0.002< x <0.05,0.05< y <0.15, and 0.002< z <0.12. The single-phase white light fluorescent material can stably and efficiently emit light under the excitation of near ultraviolet light, and the energy consumption of a WLED luminescent device prepared by using the single-phase white light fluorescent material is reduced, so that the purposes of efficiency improvement and energy saving are achieved.
Description
Technical Field
The invention belongs to the technical field of rare earth luminescent materials, and particularly relates to a single-phase white light fluorescent material, a preparation method and application thereof.
Background
According to the report of the world energy report 2022, about 20% of energy consumption is derived from luminescent products worldwide, which means that developing efficient luminescent materials and devices is one of important strategies for coping with energy crisis and realizing energy conservation and emission reduction. In the fields of general illumination, high-quality display and the like, a light conversion type White Light Emitting Diode (WLED) is a light emitting device which is most widely applied and occupies most of market share of light emitting products, a semiconductor LED chip is adopted to excite fluorescent powder, white light emission is realized through light-light conversion, the white light fluorescent powder is a core material for realizing the light conversion function of the WLED device, and the light conversion efficiency of the fluorescent powder is one of key factors for determining the luminous efficiency of the device, so that the light conversion efficiency of the fluorescent powder is greatly improved and is an internal requirement for reducing the energy consumption of the WLED device.
At present, the commercial WLED mainly adopts two light conversion technologies to realize white light emission, and one of the most widely adopted methods is that YAG is excited by blue light of an InGaN chip, and the color of the light emitted by the device is changed along with the driving voltage and the thickness of a fluorescent powder coating, and the color rendering of fluorescence is poor due to the lack of red light components; in the other method, the mixed fluorescent powder of red light, green light and blue light is excited by an ultraviolet-near ultraviolet chip to emit white light, and the ratio of the three primary colors is difficult to regulate and control due to the existence of fluorescence reabsorption among different materials, so that the luminous efficiency is low, and the color reproducibility, the color stability and the like are greatly influenced; meanwhile, the preparation difficulty of the WLED is increased by a coating process of mixing several fluorescent powders, and the production cost is high. It is clear that these conventional WLED techniques emit white light through a combination of multiple fluorescent materials, which is the source of various drawbacks. In order to solve the technical problem, a new method for manufacturing the WLED by exciting the single-phase white light fluorescent powder based on the ultraviolet/near ultraviolet LED chip is provided, and the development of the single-phase white light fluorescent powder capable of stably and efficiently emitting light becomes the key of technical breakthrough.
The preparation of high-efficiency luminous single-phase white light fluorescent material requires the selection of proper matrix materials and matched activators. A method for preparing single-phase white light fluorescent material is to dope rare earth Dy 3+ ion with characteristic of yellow light into LuNbO 4 matrix capable of emitting blue light to prepare white light fluorescent material Lu 0.99NbO4:xDy3+, adopting electron transition of 261nm ultraviolet light excited matrix to generate blue light emission band with center wavelength of 402nm, simultaneously sensitizing Dy 3+ ion to emit yellow light with center wavelength of 578nm, mixing light of two colors to realize white light emission of single-phase fluorescent material (Liang Hong, liu Chunmeng, a single-matrix doped white light emitting material and preparation method and application thereof, 201610879137.8; tao Wang Yihua Hu et al journal ofLuminescence181 (2017): 189-195). Although the method provides a thought for developing single-phase white light fluorescent materials, because the band gap of the matrix material is wider, the excitation spectrum range of the excitation material for emitting white light is in the deep ultraviolet region and is not matched with the wavelength ranges of the blue light chip and the near ultraviolet chip which can be produced in a mass way at present, so that the practical application of the material is limited. Meanwhile, in order to meet the requirements of device application of the material, the luminous efficiency of the material needs to be further improved. Another idea for preparing single-phase white light fluorescent materials is to dope various rare earth ions with characteristic emission of red light, green light and blue light (three primary colors) into the same matrix material to prepare single-phase fluorescent materials, and then excite the doped ions by using near ultraviolet light and simultaneously emit the three primary colors to realize white light emission. For example: tm 3+ featuring blue light emission, tb 3+ featuring green light emission, and Eu 3+ featuring red light emission can be simultaneously involved in GdNbO 4 matrix to prepare single-phase white light fluorescent material GdNbO4:xTm3+,yTb3+,zEu3+(Xiaoming Liu,Chen Chen et al.Inorganic Chemistry 2016,55:10383-10396.)., however, due to energy loss generated by energy transfer between various ions, etc., the quantum efficiency of light emission of such white light fluorescent material is often low, for example: the quantum yield of white light emitted by the single-phase white light fluorescent material GdNbO 4:xTm3+,yTb3+,zEu3+ is only 21.5 percent (the external quantum efficiency is lower) to the maximum, and the requirements of practical device application are far from being met.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a single-phase white light fluorescent material and a preparation method and application thereof. The single-phase white light fluorescent material can stably and efficiently emit light under the excitation of near ultraviolet light, and the energy consumption of a WLED luminescent device prepared by using the single-phase white light fluorescent material is reduced, so that the purposes of efficiency improvement and energy saving can be achieved.
To this end, the first aspect of the present invention provides a single-phase white light fluorescent material, which comprises a chemical composition general formula shown in the following formula (1) or formula (2):
lu 1-x-yNbO4:xBi3+,yDy3+ formula (1),
Or, lu 1-x-y-z-t BitNbO4:xTm3+,yTb3+,zEu3+ formula (2);
Wherein 0.005< x <0.04,0.01< y <0.02 in said formula (1); in the formula (2), 0.01< t <0.10,0.002< x <0.05,0.05< y <0.15, and 0.002< z <0.12.
In some embodiments of the present invention, the single-phase white light fluorescent material shown in formula (1) further includes Gd 3+, and the chemical composition formula shown in formula (3) below:
(Lu 1-mGdm)1-x-yNbO4:xBi3+,yDy3+ formula (3);
Wherein 0< m <0.006,0.005< x <0.04,0.01< y <0.02 in the formula (3).
In some embodiments of the invention, 0.005< x <0.03,0.01< y <0.015 in formula (1). Preferably 0.005< x <0.02,0.01< y <0.014; more preferably 0.005< x <0.01,0.01< y <0.012. In some examples, x in formula (1) may be, but is not limited to, 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.02, 0.03, or 0.04. In some examples, y in the formula (1) may be, but is not limited to, 0.01, 0.011, 0.012, 0.013, 0.014, 0.015, 0.016, 0.017, 0.018, 0.019 or 0.02.
In some embodiments of the invention, 0.03< t <0.10,0.002< x <0.03,0.05< y <0.10,0.005< z <0.12 in formula (2). Preferably 0.05< t <0.10,0.002< x <0.02,0.05< y <0.09,0.008< z <0.12; more preferably 0.07< t <0.10,0.002< x <0.01,0.05< y <0.08,0.01< z <0.12. In some examples, t in formula (2) may be, but is not limited to, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, or 0.10. In some examples, x in the formula (2) may be, but is not limited to, 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.02, 0.03, or 0.04. In some examples, y in the formula (2) may be, but is not limited to, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14, or 0.15. In some examples, z in formula (2) may be, but is not limited to, 0.002、0.003、0.004、0.005、0.006、0.007、0.008、0.009、0.01、0.02、0.03、0.04、0.05、0.06、0.07、0.08、0.09、0.10、0.11 or 0.12.
In some embodiments of the invention, 0.001< m <0.006,0.005< x <0.03,0.01< y <0.015 in the formula (3). Preferably 0.001< m <0.005,0.005< x <0.02,0.01< y <0.014; more preferably 0.001< m <0.004,0.005< x <0.01,0.01< y <0.012. In some examples, m in the formula (3) may be, but is not limited to, 0.001, 0.002, 0.003, 0.004,0.005, or 0.006. In some examples, x in formula (3) may be, but is not limited to, 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.02, 0.03, or 0.04. In some examples, y in the formula (3) may be, but is not limited to, 0.01, 0.011, 0.012, 0.013, 0.014, 0.015, 0.016, 0.017, 0.018, 0.019 or 0.02.
According to the invention, the single-phase white light fluorescent material comprises a chemical composition general formula shown as follows: lu 1-x-yNbO4:xBi3+,yDy3+, where 0.005< x <0.04,0.01< y <0.02; preferably, x is 0.01 or 0.03 and y is 0.015.
In the LuNbO 4 matrix with the ABO 4 type crystal structure, nb atoms and O atoms form 4-coordinated BO 4 tetrahedra, lu and BO 8 polyhedron with 8 coordination with O atoms, the valence band of the material is mainly composed of p electrons of oxygen atoms, and the conduction band is composed of d electrons of Nb. Bi 3+ ion has 6S 2 electron configuration, a small amount of Bi 3+ ion (0.005 < x < 0.04) is substituted for Lu and then is positioned in a BiO 8 polyhedron, the ground state energy level of the Bi 3+ ion is 1 S0, the excited state electron configuration 6S6p has 3P0、3P1、3P2 and 1P1 states, the effect of the crystal field enables the ground state energy level 1S0 of the Bi 3+ ion to be slightly higher than the p electron energy level of O atoms, while Bi 3+ ion excited state energy level 3P1 is distributed near the d electron energy level of Nb, which causes the energy to excite electrons from the Bi 3+ ion ground state energy level to the conduction band of the host to be much smaller than the band gap of the host, allowing the wavelength range to excite light emission of the Bi 3+ ion doped LuNbO 4 host to go from the deep ultraviolet region to the near ultraviolet region. Although transitions 1S0→3P0 and 1S0→3P2 of Bi 3+ ions from the ground to the excited state are spin forbidden, 1S0→3P1 and 1S0→1P1 transitions are allowed so that a stronger broadband light absorption can be obtained, which provides the necessary preconditions for efficient luminescence of the material. Therefore, under the excitation of near ultraviolet light, the Bi 3+ doped LuNbO 4 matrix can emit blue light with the wavelength range of 375nm-575nm (the central wavelength is 460 nm), and the wavelength range of the emission spectrum is completely matched with the characteristic excitation peak of Dy 3+ ions, so that conditions are provided for the resonance energy transfer of Bi 3+ ions and LuNbO 4 matrix to Dy 3+ ions, and the efficiency of yellow light emission by the matrix sensitized Dy 3+ is extremely high. The process of matrix sensitized rare earth ion luminescence is completed through exciton mediated energy conduction, when near ultraviolet light excites Lu 1-x-yNbO4:xBi3+,yDy3+ electron transition, excitons are generated first, excitation energy is transferred to rare earth ions by the matrix under the assistance of exciton movement, rare earth luminescence is excited, and blue light emitted by the matrix and yellow light emitted by Dy 3+ are mixed together to form high-brightness white light.
According to the invention, the single-phase white light fluorescent material comprises a chemical composition general formula shown as follows: (Lu 1- mGdm)1-x-yNbO4:xBi3+,yDy3+, wherein 0< m <0.006,0.005< x <0.04,0.01< y <0.02; preferably, m is 0.001, x is 0.01 or 0.03, y is 0.015.
Gd 3+ ions are added on the basis, a very small amount of Gd 3+ ions (0.001 < m < 0.006) are doped into the matrix instead of Lu 3+, and the Gd 3+ ions and the Bi 3+ cooperate to further regulate the crystal field environment and the energy transfer channel where Dy 3+ is located, so that the energy conduction from the matrix to Dy 3+ ions is promoted, and the luminous efficiency of the material is further improved.
According to the invention, the single-phase white light fluorescent material comprises a chemical composition general formula shown as follows: lu 1-x-y-z-tBitNbO4:xTm3+,yTb3+,zEu3+, where 0.01< t <0.10,0.002< x <0.05,0.05< y <0.15,0.002< z <0.12; preferably, t is 0.03, x is 0.03, y is 0.1, and z is 0.005 or 0.01.
The wavelength range of light emission of the matrix can be adjusted to a near ultraviolet (270 nm-330 nm) region by doping Bi 3+ ions into the LuNbO 4 matrix, and electron transitions 1S0→3P1 and 1S0→1P1 excited by ultraviolet light are spin-allowed, so that stronger broadband light absorption is caused, so that the material can obtain excitation energy as much as possible, energy loss in the light excitation process is reduced, and the external quantum efficiency of light emission of the material is improved. Meanwhile, the matrix can emit blue light with the wavelength range of 375nm-575nm (the central wavelength is 460 nm) under the excitation of near ultraviolet light, and the wavelength range of the emission spectrum can overlap with the wavelength range of the characteristic excitation peak of the rare earth ions Tm 3+,Tb3+,Eu3+, so that Bi 3+ ions and LuNbO 4 matrix can simultaneously transmit energy to three ions through resonance energy transmission, thereby sensitizing the three rare earth ions to emit light simultaneously. Since the process of sensitizing rare earth ion luminescence is completed by exciton movement assistance, energy exchange transfer between three ions is suppressed to a certain extent. Because the main characteristic emission of Tm 3+,Tb3+,Eu3+ is blue light, green light and red light respectively, the atomic proportion of three ions is regulated and controlled, and a single-phase material can emit three primary colors at the same time, and white light with high color rendering property can be obtained by combining. Meanwhile, in order to obtain excitation energy as much as possible, promote energy transfer, and avoid the influence of concentration quenching on the luminous efficiency of the material, more Bi 3+ ions are doped in LuNbO 4 substrates, so that the doping concentration t of Bi 3+ ions reaches the range of 0.01< t <0.10, and the technical aim of improving the luminous external quantum efficiency of the material can be fulfilled.
According to a second aspect of the present invention, there is provided a method for preparing a single-phase white light fluorescent material according to the first aspect of the present invention, comprising: weighing raw materials comprising elements in the formula (1), the formula (2) or the formula (3) according to chemical dosage, fully grinding and mixing, and heating to perform solid phase reaction.
In some embodiments of the present invention, the preparation method of the single-phase white light fluorescent material represented by formula (1) or formula (3) includes the following specific steps:
S1: weighing raw materials Lu 2O3、Nb2O5、Bi2O3 and Dy 2O3 according to chemical dosage; or weighing the raw materials Lu 2O3、Nb2O5、Bi2O3、Gd2O3 and Dy 2O3 according to the chemical dosage;
s2: fully grinding and uniformly mixing the raw materials weighed in the step S1, reacting at 1000 ℃ for 6-8h, naturally cooling to room temperature, and then ball milling for 12h;
S3: and (3) placing the material treated in the step (S2) at 1250 ℃ for reaction for 8-12h, cooling to room temperature, and grinding into powder.
In some embodiments of the present invention, the preparation method of the single-phase white light fluorescent material represented by formula (2) includes the following specific steps:
s1: weighing raw materials Lu2O3、Nb2O5、Bi2O3、Tm2O3、Tb4O7 and Eu 2O3 according to chemical dosage;
s2: fully grinding and uniformly mixing the raw materials weighed in the step S1, reacting at 1000 ℃ for 10-14h, naturally cooling to room temperature, and then ball milling for 12h;
S3: and (2) placing the material treated in the step (S2) at 1250 ℃ for reaction for 10-14h, cooling to room temperature, and grinding into powder.
According to the invention, the starting oxide is pre-burned in advance at 800 ℃ for 2 hours.
A third aspect of the present invention provides an application of the single-phase white light fluorescent material according to the first aspect of the present invention or the single-phase white light fluorescent material prepared by the preparation method according to the second aspect of the present invention in preparing a light conversion type White Light Emitting Diode (WLED).
In some embodiments of the present invention, the single-phase white light fluorescent material is coated on a near ultraviolet chip having a light emission wavelength of 270nm to 330nm to prepare a light conversion type white light emitting diode.
According to the invention, the single-phase white light fluorescent material is uniformly mixed with silica gel and then coated on the surface of a near ultraviolet chip with the luminous wavelength of 270-330 nm.
In some embodiments of the invention, the silica gel is mixed with a single-phase white light fluorescent material according to a mass ratio of 1:1.2-1.6; preferably 1:1.4-1.6. In some examples, the silica gel may be mixed with the single-phase white light fluorescent material in a mass ratio of, but not limited to, 1:1.2, 1:1.3, 1:1.4, 1:1.5, or 1:1.6.
In some embodiments of the present invention, the thickness of the coating layer coated on the surface of the near ultraviolet chip after the single-phase white light fluorescent material is mixed with silica gel is 130-160 μm; preferably 140-150 μm. In some examples, the thickness of the coating applied to the near-UV chip surface after mixing the single-phase white light fluorescent material with silica gel may be, but is not limited to, 130 μm, 135 μm, 140 μm, 145 μm, 150 μm, 155 μm, or 160 μm.
The invention has the beneficial effects that:
(1) The invention provides a single-phase white light fluorescent material, which can adjust the excitation spectrum range from a deep ultraviolet region to a near ultraviolet region by doping Bi 3+ and Dy 3 + in LuNbO-substrate simultaneously, and can stably and efficiently emit light under the excitation of near ultraviolet.
(2) The preparation method provided by the invention is used for preparing the single-phase white light fluorescent material, is simple and convenient to operate, and has low production cost.
(3) The single-phase white light fluorescent material provided by the invention is applied to the preparation of WLED, and can solve the problems of low luminous efficiency, high energy consumption and the like caused by the mismatching of the excitation spectrum range of the traditional fluorescent material and the wavelength ranges of the blue light chip and the near ultraviolet chip which can be produced in mass at present or the energy loss generated by the energy transfer between various ions. The single-phase white light fluorescent material provided by the invention has the characteristics of stable and efficient light emission, can be applied to the prepared WLED to stably and efficiently emit light, is suitable for the fields of daily illumination, high-end display and the like, and is suitable for large-scale production.
Drawings
Fig. 1 is a graph showing the single-phase white light emitting phosphor prepared in example 2 (Lu 0.999Gd0.001)0.975NbO4:0.01Bi3+,0.015Dy3+ and the single-phase white light emitting phosphor prepared in example 3 (X-ray diffraction pattern of Lu 0.999Gd0.001)0.955NbO4:0.03Bi3+,0.015Dy3+;
FIG. 2 is an X-ray diffraction chart of the single-phase white light emitting phosphor Lu 0.835Bi0.03NbO4:0.03Tm3+,0.1Tb3+,0.005Eu3+ prepared in example 4 and the single-phase white light emitting phosphor Lu 0.83Bi0.03NbO4:0.03Tm3+,0.1Tb3+,0.01Eu3+ prepared in example 5;
Fig. 3 is a light excitation spectrum of the single-phase white light fluorescent material Lu 0.975NbO4:0.01Bi3+,0.015Dy3 + prepared in example 1, the single-phase white light fluorescent material prepared in example 2 (Lu 0.999Gd0.001)0.975NbO4:0.01Bi3+,0.015Dy3+, the single-phase white light fluorescent material prepared in example 3 (Lu 0.999Gd0.001)0.955NbO4:0.03Bi3+,0.015Dy3+, the single-phase white light fluorescent material Lu 0.985NbO4:0.015Dy3+ prepared in comparative example 1), and light emission at 578nm in experimental example 1;
FIG. 4 is a graph showing fluorescence spectra of single-phase white light fluorescent materials prepared in examples 1 to 3 and comparative example 1 in Experimental example 2 excited by 305nm near ultraviolet light; wherein, a-the single-phase white light fluorescent material Lu 0.985NbO4:0.015Dy3+ prepared in comparative example 1, B-the single-phase white light fluorescent material prepared in example 3 (Lu 0.999Gd0.001)0.955NbO4:0.03Bi3+,0.015Dy3+, C-the single-phase white light fluorescent material Lu 0.975NbO4:0.01Bi3+,0.015Dy3+ prepared in example 1, D-the single-phase white light fluorescent material prepared in example 2 (Lu 0.999Gd0.001)0.975NbO4:0.01Bi3+,0.015Dy3+;
FIG. 5 is a color chart of luminescence of the single-phase white light fluorescent material prepared in examples 2-3 excited by 305nm near ultraviolet light in experiment example 2; wherein, a-the single-phase white light fluorescent material prepared in example 2 (Lu 0.999Gd0.001)0.975NbO4:0.01Bi3+,0.015Dy3+, B-the single-phase white light fluorescent material prepared in example 3 (Lu 0.999Gd0.001)0.955NbO4:0.03Bi3+,0.015Dy3 +;
FIG. 6 is a graph showing the quantum efficiency of luminescence of the single-phase white light fluorescent material (Lu 0.999Gd0.001)0.975NbO4:0.01Bi3+,0.015Dy3+) prepared in Experimental example 3 using 305nm near ultraviolet light to excite example 2;
FIG. 7 is a fluorescence spectrum of the single-phase white light fluorescent material prepared in examples 4 to 5 of Experimental example 4 excited by 305nm near ultraviolet light; wherein, A-single-phase white light fluorescent material Lu 0.835Bi0.03NbO4:0.03Tm3+,0.1Tb3+,0.005Eu3+ prepared in example 4, B-single-phase white light fluorescent material Lu 0.83Bi0.03NbO4:0.03Tm3+,0.1Tb3+,0.01Eu3 + prepared in example 5;
FIG. 8 is a color chart of luminescence of the single-phase white light fluorescent materials prepared in examples 4 to 5 excited by 305nm near ultraviolet light in experiment example 4; wherein, A-single-phase white light fluorescent material Lu 0.835Bi0.03NbO4:0.03Tm3+,0.1Tb3+,0.005Eu3+ prepared in example 4, B-single-phase white light fluorescent material Lu 0.83Bi0.03NbO4:0.03Tm3+,0.1Tb3+,0.01Eu3+ prepared in example 5;
FIG. 9 is a graph showing the results of the light flux test conducted on the WLED prepared in example 6 in Experimental example 5; wherein, (a) -the luminous spectrum diagram of the WLED and the inset diagram are the physical photos of the WLED, and (b) -the luminous color rendering index of the WLED;
FIG. 10 is a graph of WLED luminescence prepared in Experimental example 6 driven by different voltages for example 6.
Detailed Description
In order that the invention may be more readily understood, the invention will be described in detail below with reference to the following examples, which are given by way of illustration only and are not limiting of the scope of application of the invention.
Example 1
The embodiment provides a single-phase white light fluorescent material, which comprises the following chemical composition general formula: lu 0.975NbO4:0.01Bi3+,0.015Dy3+.
Pre-burning oxide raw materials at 800 ℃ for 2 hours, weighing a proper amount of Lu 2O3、Nb2O5、Bi2O3 and Dy 2O3 according to stoichiometric amount, fully grinding and uniformly mixing, reacting at 1000 ℃ for 6 hours, naturally cooling to room temperature, and ball-milling for 12 hours; then placing the mixture into a muffle furnace to react for 10 hours at 1250 ℃, cooling to room temperature and grinding the mixture into powder.
Example 2
The embodiment provides a single-phase white light fluorescent material, which comprises the following chemical composition general formula: (Lu 0.999Gd0.001)0.975NbO4:0.01Bi3+,0.015Dy3+).
The embodiment also provides a preparation method of the single-phase white light fluorescent material, which comprises the following steps: pre-burning oxide raw materials at 800 ℃ for 2 hours by taking Lu 2O3、Nb2O5、Bi2O3、Gd2O3 and Dy 2O3 as raw materials, weighing a proper amount of Lu 2O3、Nb2O5、Bi2O3、Gd2O3 and Dy 2O3 according to stoichiometric amount, fully grinding and uniformly mixing, reacting at 1000 ℃ for 6 hours, naturally cooling to room temperature, and ball-milling for 12 hours; then placing the mixture into a muffle furnace to react for 10 hours at 1250 ℃, cooling to room temperature and grinding the mixture into powder.
After grinding into powder, the phase and crystal structure of the material were analyzed by X-ray diffraction, and the result is shown in fig. 1, which demonstrates that the single-phase white light fluorescent material (Lu 0.999Gd0.001)0.975NbO4:0.01Bi3+,0.015Dy3+) having the xenotime type crystal structure was prepared in this example.
Example 3
The embodiment provides a single-phase white light fluorescent material, which comprises the following chemical composition general formula: (Lu 0.999Gd0.001)0.955NbO4:0.03Bi3+,0.015Dy3+).
This example uses the same preparation method as example 2 to prepare a single-phase white light fluorescent material.
After grinding into powder, the phase and crystal structure of the material were analyzed by X-ray diffraction, and the result is shown in fig. 1, which demonstrates that the single-phase white light fluorescent material (Lu 0.999Gd0.001)0.955NbO4:0.03Bi3+,0.015Dy3+) having the xenotime type crystal structure was prepared in this example.
Example 4
The embodiment provides a single-phase white light fluorescent material, which comprises the following chemical composition general formula: lu 0.835Bi0.03NbO4:0.03Tm3+,0.1Tb3+,0.005Eu3+.
The embodiment also provides a preparation method of the single-phase white light fluorescent material, which comprises the following steps: taking Lu2O3、Nb2O5、Bi2O3、Tm2O3、Tb4O7 and Eu 2O3 as raw materials, presintering an oxide raw material at 800 ℃ for 2 hours in advance, weighing a certain amount of Lu2O3、Nb2O5、Bi2O3、Tm2O3、Tb4O7 and Eu 2O3 according to stoichiometric amount, fully grinding and uniformly mixing, reacting at 1000 ℃ for 12 hours, naturally cooling to room temperature, and ball-milling for 12 hours; then placing the mixture into a muffle furnace to react for 12 hours at 1250 ℃, cooling to room temperature and grinding the mixture into powder.
After grinding into powder, the phase and crystal structure of the material are analyzed by X-ray diffraction, and the result is shown in fig. 2, which shows that the single-phase white light fluorescent material Lu 0.835Bi0.03NbO4:0.03Tm3 +,0.1Tb3+,0.005Eu3+ with xenotime type crystal structure is prepared in the embodiment.
Example 5
The embodiment provides a single-phase white light fluorescent material, which comprises the following chemical composition general formula: lu 0.83Bi0.03NbO4:0.03Tm3+,0.1Tb3+,0.01Eu3+.
This example uses the same preparation method as example 4 to prepare a single-phase white light fluorescent material.
After grinding into powder, the phase and crystal structure of the material are analyzed by X-ray diffraction, and the result is shown in fig. 2, which shows that the single-phase white light fluorescent material Lu 0.83Bi0.03NbO4:0.03Tm3 +,0.1Tb3+,0.01Eu3+ with xenotime type crystal structure is prepared in the embodiment.
Example 6
The embodiment provides a light conversion type White Light Emitting Diode (WLED), which comprises the following steps:
The single-phase white light fluorescent material Lu 0.835Bi0.03NbO4:0.03Tm3+,0.1Tb3+,0.005Eu3 + prepared in example 4 is taken as a light conversion material, silica gel and single-phase white light fluorescent powder are uniformly mixed according to the mass ratio of 1:1.4 and then coated on the surface of a chip with the light-emitting wavelength of 310nm, the thickness of the coating is 150 mu m, and the WLED is manufactured after drying and solidification.
Comparative example 1
The comparative example provides a single-phase white light fluorescent material, which comprises the following chemical composition general formula: lu 0.985NbO4:0.015Dy3+.
This comparative example uses Lu 2O3、Nb2O5、Dy2O3 as a raw material, and a single-phase white light fluorescent material was prepared by the same preparation method as in example 1.
Experimental example 1
The single-phase white light fluorescent materials prepared in examples 1 to 3 and comparative example 1 were each measured for their optical excitation spectra at 578nm (characteristic emission of Dy 3+) using a fluorescence spectrometer, and the results are shown in fig. 3.
As can be seen from the results of FIG. 3, the single-phase white light fluorescent materials prepared in examples 1-3 were excited to emit light in the near ultraviolet region ranging from 270nm to 330 nm; and the excitation spectrum of the single-phase white light fluorescent material prepared in the comparative example 1 is in the deep ultraviolet region of 225nm-275 nm. The excitation spectrum of the single-phase white light fluorescent material prepared by the invention is in the near ultraviolet region of 270nm-330nm, and the excitation spectrum is matched with the wavelength range of a near ultraviolet chip which can be produced in quantity, so that the single-phase white light fluorescent material can be suitable for a large number of practical applications.
Experimental example 2
The fluorescence spectra of the single-phase white light fluorescent materials prepared in examples 1 to 3, which were excited by near ultraviolet light having a wavelength of 305nm, were measured using a fluorescence spectrometer, respectively, and the fluorescence spectra of the single-phase white light fluorescent material prepared in comparative example 1, which were excited by deep ultraviolet light having a wavelength of 248nm, were measured, and the results are shown in fig. 4. The color coordinates of the single-phase white light fluorescent materials prepared in examples 2 to 3 were shown in fig. 5.
As can be seen from the results of FIG. 4, the fluorescence spectrum of the single-phase white light fluorescent material Lu 0.985NbO4:0.015Dy3+ prepared in comparative example 1 is shown as line A in FIG. 4, and the main luminescence peak includes a blue luminescence band with a center wavelength of 405nm and a yellow luminescence band with a wavelength of 578 nm; the single-phase white light fluorescent material prepared in example 3 (the fluorescence spectrum of Lu 0.999Gd0.001)0.955NbO4:0.03Bi3+,0.015Dy3+ luminescence is shown as line B in fig. 4, the main luminescence peak includes blue luminescence band with center wavelength at 460nm and yellow luminescence band with wavelength at 578nm, the fluorescence spectrum of Lu 0.975NbO4:0.01Bi3+,0.015Dy3+ luminescence of the single-phase white light fluorescent material prepared in example 1 is shown as line C in fig. 4, the main luminescence peak includes blue luminescence band with center wavelength at 465nm and yellow luminescence band with wavelength at 578nm, the fluorescence spectrum of Lu 0.999Gd0.001)0.975NbO4:0.01Bi3 +,0.015Dy3+ luminescence is shown as line D in fig. 4, the main luminescence peak includes blue luminescence band with center wavelength at 460nm and yellow luminescence band with wavelength at 578 nm. Comparing the line a and line C in fig. 4. Comparing the spectrum of fig. 4, the excitation spectrum range of Bi 3+ is adjusted from the ultraviolet region to the near ultraviolet region, and the luminescence intensity of Bi 3+ is also enhanced, but the doping of the light is not significantly improved by comparing the line C with the line D in fig. 4, the doping intensity of the light 3+ is not significantly improved, and the doping intensity of Bi is not significantly improved by comparing the doping amount of a small amount of the light with the light spectrum of Bi 3+.
As can be seen from the results of fig. 5, the single-phase white light fluorescent material prepared in example 2 (Lu 0.999Gd0.001)0.975NbO4:0.01Bi3+,0.015Dy3+ and the single-phase white light fluorescent material prepared in example 3 (Lu 0.999Gd0.001)0.955NbO4:0.03Bi3+,0.015Dy3+ emits positive white light under the excitation of near ultraviolet light of 305 nm. Similarly, the color of light emission of the single-phase white light fluorescent material Lu 0.985NbO4:0.015Dy3+ prepared in comparative example 1 excited by deep ultraviolet light of 248nm is also in the white light region, and the color of light emission of the single-phase white light fluorescent material Lu 0.975NbO4:0.01Bi3+,0.015Dy3+ prepared in example 1 excited by near ultraviolet light of 305nm is also in the white light region).
Experimental example 3
The quantum efficiency of the single-phase white light fluorescent material prepared in example 2 was measured at 305nm near-ultraviolet excitation, and the absorption rate of the single-phase white light fluorescent material to excitation light and the quantum yield of the material luminescence were calculated, and the results are shown in fig. 6.
As can be seen from the results of FIG. 6, the absorption rate (AE) of the single-phase white light fluorescent material prepared in example 2 to excitation light reaches 89.8%, and the quantum yield (PLEQ) of the light emission of the measuring material reaches 55.12%. The single-phase white light fluorescent material prepared by the invention has the characteristic of high-efficiency luminescence.
Experimental example 4
The fluorescence spectra of the single-phase white light fluorescent materials prepared in examples 4 to 5, which were excited by near ultraviolet light having a wavelength of 305nm, were measured using a fluorescence spectrometer, respectively, and the results are shown in fig. 7; the color coordinates of the single-phase white light fluorescent material are shown in fig. 8.
As can be seen from the results of fig. 7, the emission spectra of the single-phase white light fluorescent materials prepared in examples 4 to 5 each include the characteristic emission of Tm 3+、Tb3+、Eu3+; as can be seen by comparing the spectra of line A and line B in FIG. 7, increasing the amount of Eu 3+ doped is advantageous for increasing the luminous intensity.
As can be seen from the results of fig. 8, the single-phase white light fluorescent material Lu 0.835Bi0.03NbO4:0.03Tm3+,0.1Tb3+,0.005Eu3+ prepared in example 4 and the single-phase white light fluorescent material Lu 0.83Bi0.03NbO4:0.03Tm3+,0.1Tb3+,0.01Eu3+ prepared in example 5 both emit positive white light under excitation of 305nm near ultraviolet light.
Experimental example 5
The light flux test was performed on the WLED prepared in example 6 using a Hangzhou Hopp light color technology Co., ltd OHSP-350A/M spectral luminance colorimeter, and the results are shown in FIG. 9.
As can be seen from the results of fig. 9, the correlated color temperature of the WLED luminescence prepared in example 6 of the present invention is 4542K, which indicates that the WLED can emit stronger warm white light; FIG. 9 (b) shows the color rendering index of 15 representative color patches, the average of which reaches 85, demonstrating that WLED prepared in example 6 of the present invention has better color rendering.
Experimental example 6
The luminescence results of the WLED prepared in example 6 under different voltage driving were examined and shown in fig. 10.
As can be seen from the results of fig. 10, WLED prepared in example 6 of the present invention can stably emit strong warm white light under different voltage driving.
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (9)
1. A single-phase white light fluorescent material is characterized by comprising a chemical composition general formula shown in a formula (2):
lu 1-x-y-z-tBitNbO4: xTm3+, yTb3+, zEu3+ formula (2);
Wherein 0.01 < t <0.10,0.002< x <0.05,0.05< y <0.15,0.002< z <0.12 in the formula (2).
2. The single-phase white light emitting phosphor of claim 1, wherein 0.03 < t <0.10,0.002< x <0.03,0.05< y <0.10,0.005< z <0.12 in the formula (2).
3. A single-phase white light fluorescent material is characterized by comprising a chemical composition general formula shown in a formula (3):
(Lu 1-mGdm)1-x-yNbO4: xBi3+, yDy3+ formula (3);
Wherein 0 < m <0.006,0.005< x <0.04,0.01< y <0.02 in the formula (3).
4. The single-phase white light emitting phosphor of claim 3, wherein 0.001 < m <0.006,0.005< x <0.03,0.01< y <0.015 in said formula (3).
5. A method of preparing a single-phase white light emitting phosphor according to any one of claims 1 to 4, comprising: weighing raw materials comprising the elements in the formula (2) or the formula (3) according to chemical dosage, fully grinding and mixing, and heating to perform solid phase reaction.
6. The preparation method of the single-phase white light fluorescent material shown in the formula (2) according to claim 5 comprises the following specific steps:
s1: weighing raw materials Lu2O3、Nb2O5、Bi2O3、Tm2O3、Tb4O7 and Eu 2O3 according to chemical dosage;
s2: fully grinding and uniformly mixing the raw materials weighed in the step S1, reacting at 1000 ℃ for 10-14h, naturally cooling to room temperature, and then ball milling for 12h;
S3: and (2) placing the material treated in the step (S2) at 1250 ℃ for reaction for 10-14h, cooling to room temperature, and grinding into powder.
7. The preparation method of the single-phase white light fluorescent material shown in the formula (3) according to claim 5 comprises the following specific steps:
S1: weighing raw materials Lu 2O3、Nb2O5、Bi2O3、Gd2O3 and Dy 2O3 according to chemical dosage;
s2: fully grinding and uniformly mixing the raw materials weighed in the step S1, reacting at 1000 ℃ for 6-8h, naturally cooling to room temperature, and then ball milling for 12h;
S3: and (3) placing the material treated in the step (S2) at 1250 ℃ for reaction for 8-12h, cooling to room temperature, and grinding into powder.
8. Use of a single-phase white light emitting phosphor according to any one of claims 1 to 4 or prepared by a method according to any one of claims 6 to 7 for the preparation of a light-converting white light emitting diode.
9. The use according to claim 8, wherein the single-phase white light fluorescent material is coated on a near ultraviolet chip with a light emission wavelength of 270nm-330nm to prepare a light conversion type white light emitting diode.
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