CN115340366A - High-color-rendering-index full-spectrum fluorescent material and preparation method thereof - Google Patents
High-color-rendering-index full-spectrum fluorescent material and preparation method thereof Download PDFInfo
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 14
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Abstract
The invention discloses a high color rendering index full-spectrum fluorescent material and a preparation method thereof, wherein the molecular formula of the fluorescent material is Lu 2‑ x BaAl 4 SiO 12 :xEu 2+ Wherein x is Eu 2+ Doped Lu 3+ The mole percentage of the position, x is more than or equal to 0.02 and less than or equal to 0.1; by Lu 2 O 3 、Eu 2 O 3 、Al 2 O 3 、BaCO 3 、SiO 2 Grinding and mixing raw material powder, calcining at 7000000 ℃ for 306h to obtain a first sintering product, sieving the first sintering product, drying and pressing in a steel die to obtain a biscuit, sintering the biscuit at constant temperature for 204h in a reducing atmosphere, and cooling to room temperature along with a furnace to obtain the high-temperature-resistant sintered ceramic material. The invention uses Lu 2 BaAl 4 SiO 12 As matrix material, eu is adopted 2+ As the only light-emitting ion, by Eu 2+ With Eu 3+ The valence state of the light-emitting diode is regulated and controlled, and the charge transfer between valences is induced, so that the wide-spectrum light emission under the excitation of ultraviolet light and blue light is realized simultaneously; the fluorescent material has emission wavelength covering 430nm0850nm and color rendering index 03006 under the excitation of an ultraviolet LD chip with the wavelength of 355nm, and emission wavelength covering 500nm0820nm and color rendering index of 85088 under the excitation of a blue LD chip with the wavelength of 455 nm.
Description
Technical Field
The invention relates to the technical field of fluorescent materials, in particular to a high-color-rendering-index full-spectrum fluorescent material and a preparation method thereof.
Background
White light LEDs (WLEDs) have made tremendous progress in solid state lighting and display applications due to their advantages of energy conservation, environmental protection, high brightness, and the like. The method for synthesizing WLED (white light emitting diode) commonly adopted at present is to mix blue InGaN chips with YAG Ce 3+ The yellow fluorescent material is combined. However, blue LEDs are at high excitation power densities (>3W cm -2 ) There is a serious "efficiency drop" problem that limits its application in high power lighting. In contrast, a Laser Diode (LD) can withstand a peak power density of 25kW cm -2 So that the LED lamp has the most development prospect in the field of new generation high-brightness illumination. In general, white light LD (WLD) implementations are substantially similar to the WLED described above, howeverThe realization method can not meet the requirement of a high-quality white light source due to the lack of cyan light and red light components, so that the color rendering index (CRI, ra) is lower than 65, and the relative color temperature (CCT) is higher than 7500K. Only mixing YAG with Ce 3+ Co-encapsulation with cyan and red materials can solve this problem. Strong reabsorption between different types of phosphors can lead to a large reduction in the efficiency of the resultant WLD. In addition, different phosphors have different thermal quenching behaviors, which often cause fluctuation of emission wavelength, seriously affect the CIE coordinates, CRI and CCT of WLD, and reduce the quality of white light source. Therefore, the single-phase broad-spectrum emission fluorescent material attracts attention, and the quality of a white light source synthesized by the single-phase broad-spectrum emission fluorescent material is superior to that of a commercial three-color WLD (white light emitting diode) by combining the broad-band white light fluorescent powder with the near ultraviolet LD chip. However, as a commonly used light emitting ion, eu 2+ The emission bandwidth of the light source is generally in a narrow range of 700110nm, and the adjustment of the emission wavelength of the light source to achieve broadband emission still has great challenges.
In order to solve the problem of low color rendering index of white light source, eu is adopted 2+ As a luminescent ion for preparing a full-spectrum fluorescent material, CN112004644A discloses an ultraviolet excited Eu (II) ion single-doped single-phase full-spectrum fluorescent powder, and preparation and application thereof, wherein Eu is used 2+ Ion as a single activation center, ca 0 MgK(PO 4 ) 7 Is used as a substrate material, and the prepared fluorescent powder and an ultraviolet chip with the wavelength of 375nm are packaged to obtain a light source with the color rendering index of 05. However, the host material is only suitable for ultraviolet chip excitation, which inevitably brings about reduction of luminous efficiency, and limits practical application in white light LED/LD devices.
Disclosure of Invention
One of the purposes of the invention is to provide a high color rendering index full-spectrum fluorescent material which can be simultaneously suitable for ultraviolet light and blue light chip excitation to realize full-spectrum emission and has high color rendering index.
The invention also aims to provide the preparation method of the high-color-rendering-index full-spectrum fluorescent material, which is simple in process and can be industrially produced.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
in a first aspect, the present invention provides a full-spectrum fluorescent material with high color rendering index and molecular formula of Lu 2- x BaAl 4 SiO 12 :xEu 2+ Wherein x is Eu 2+ Doped Lu 3+ The mole percentage of the position, x is more than or equal to 0.02 and less than or equal to 0.1.
The fluorescent material has emission wavelength covering 430nm0850nm and color rendering index being 03006 under the excitation of an ultraviolet LD chip with the wavelength of 355nm, and emission wavelength covering 500nm0820nm and color rendering index being 85088 under the excitation of a blue LD chip with the wavelength of 455 nm.
In a second aspect, the invention provides a method for preparing the above-mentioned high color rendering index full-spectrum fluorescent material, which adopts a solid-phase reaction sintering method, and comprises the following steps:
(1) By Lu 2 O 3 、Eu 2 O 3 、Al 2 O 3 、BaCO 3 、SiO 2 As raw material powder, according to the molecular formula Lu 2-x BaAl 4 SiO 12 :xEu 2 + Weighing the raw materials according to the stoichiometric ratio of the corresponding elements, wherein x is Eu 2+ Doped medium Lu 3+ The mole percentage of the bit, x is more than or equal to 0.02 and less than or equal to 0.1;
(2) Grinding and mixing the raw material powder weighed in the step (1);
(3) Calcining the mixed powder obtained in the step (2) at 7000000 ℃ for 306h to obtain a first sintered product, sieving the first sintered product, and drying and pressing the sieved first sintered product in a steel die to obtain a biscuit;
(4) And (4) placing the biscuit pressed in the step (3) in a reducing atmosphere for constant-temperature sintering for 204h, and cooling to room temperature along with the furnace to obtain the fluorescent material.
Preferably, lu in step (1) 2 O 3 、Al 2 O 3 、BaCO 3 、SiO 2 Has a particle size of 1 μm02 μm, eu 2 O 3 The particle size of the powder is 100nm 0300nm, and the purity is above 00.00 percent.
Preferably, the grinding time in the step (2) is 20min040min.
Preferably, the sieve mesh in step (3) is 800200 mesh.
Preferably, the constant-temperature sintering temperature in the step (4) is 120001400 ℃.
Compared with the prior art, the invention has the following beneficial effects:
(1) The fluorescent material has emission wavelength covering 430nm0850nm and color rendering index of 03006 under the excitation of an ultraviolet LD chip with the wavelength of 355nm, and emission wavelength covering 500nm0820nm and color rendering index of 85088 under the excitation of a blue light LD chip with the wavelength of 455 nm.
(2) The invention uses Lu 2 BaAl 4 SiO 12 Is a matrix material, has rich ion lattice sites, adopts Eu 2+ As the only light-emitting ion, by Eu 2+ With Eu 3+ The valence state of the light-emitting diode is regulated and controlled, and the charge transfer between valences is induced, so that the wide-spectrum light emission under the excitation of ultraviolet light and blue light is realized simultaneously.
(3) The high-color-rendering-index full-spectrum fluorescent material prepared by the invention is simple in preparation method, short in time consumption, green and environment-friendly, and can be applied to industrial production of LED/LD devices.
Drawings
FIG. 1 is an XRD pattern of a sample prepared in example 1 of the present invention;
FIG. 2 is an emission spectrum of a sample prepared in example 1 of the present invention under excitation of 355nm ultraviolet light;
FIG. 3 is an emission spectrum of a sample prepared in example 1 of the present invention under excitation of 455nm blue light.
Detailed Description
The invention is described in further detail below with reference to the figures and the specific embodiments.
The raw material powders used in the following examples are all commercial products, unless otherwise specified, of which Lu is 2 O 3 、Al 2 O 3 、BaCO 3 、SiO 2 Has a particle diameter of 1 μm02 μm, eu 2 O 3 The particle size of the powder is 100nm 0300nm.
Example 1: preparation of Lu 1.04 Eu 0.06 BaAl 4 SiO 12
According to the chemical formula Lu 1.04 Eu 0.06 BaAl 4 SiO 12 Respectively weighing Lu with the purity of 00.00 percent according to the stoichiometric ratio of the corresponding raw materials 2 O 3 14.08116g、Eu 2 O 3 0.38016g、Al 2 O 3 7.51663g、BaCO 3 3.63320g、SiO 2 2.21480g, mixing, grinding in an agate mortar for 30min, calcining the mixed powder at 800 ℃ for 4h to obtain a first sintered product, sieving the first sintered product with a 100-mesh sieve, drying in a steel die to press the first sintered product into a biscuit, sintering the pressed biscuit at a constant temperature of 1300 ℃ in a reducing atmosphere for 3h, and cooling to room temperature along with a furnace to obtain the fluorescent material.
X-ray diffraction (XRD, model D5005, siemens) is used for researching the crystal structure, the scanning angle 2 theta range is 10-80 degrees, the XRD test pattern of the sample is obtained, the reduced sample is consistent with a standard card (JCPDS 73-1368) as can be seen from figure 1, the doping of Eu ions does not bring obvious influence on the crystal structure, and the obtained fluorescent powder and Lu have the advantages that 2 BaAl 4 SiO 12 Is isomorphic pure phase material.
The spectral properties of the phosphor were measured using an integrating sphere (R08, everfine, hangzhou, china), and the results showed that the emission wavelength covered 430nm0840nm under the excitation of an ultraviolet LD chip with a wavelength of 355nm, the emission spectrum was shown in fig. 2, the color rendering index was 06, the emission wavelength covered 500nm0820nm under the excitation of a blue LD chip with a wavelength of 455nm, the emission spectrum was shown in fig. 3, and the color rendering index was 88.
Example 2: preparation of Lu 1.08 Eu 0.02 BaAl 4 SiO 12
According to the chemical formula Lu 1.08 Eu 0.02 BaAl 4 SiO 12 Respectively weighing Lu with the purity of 00.00 percent according to the stoichiometric ratio of the corresponding raw materials 2 O 3 14.50480g、Eu 2 O 3 0.11662g、Al 2 O 3 7.50814g、BaCO 3 3.62018g、SiO 2 2.21230g, blending, grinding in an agate mortar for 30min, calcining the mixed powder at 800 ℃ for 4h to obtain a first sintered product, sieving the first sintered product with a 100-mesh sieve, drying in a steel die to press the first sintered product into a biscuit, sintering the pressed biscuit at the constant temperature of 1300 ℃ for 3h,and cooling to room temperature along with the furnace to obtain the fluorescent material.
The XRD pattern of the sample of this example is similar to that of fig. 1, and is pure phase.
Under the excitation of an ultraviolet LD chip with the wavelength of 355nm, the emission wavelength covers 430nm0800nm, and the color rendering index is 03, and under the excitation of a blue LD chip with the wavelength of 455nm, the emission wavelength covers 500nm0780nm, and the color rendering index is 85.
Example 3: preparation of Lu 1.06 Eu 0.04 BaAl 4 SiO 12
According to the chemical formula Lu 1.04 Eu 0.06 BaAl 4 SiO 12 Respectively weighing Lu with the purity of 00.00 percent according to the stoichiometric ratio of the corresponding raw materials 2 O 3 14.35007g、Eu 2 O 3 0.25281g、Al 2 O 3 7.51230g、BaCO 3 3.63123g、SiO 2 2.21364g, mixing, grinding in an agate mortar for 30min, calcining the mixed powder at 800 ℃ for 4h to obtain a first sintered product, sieving the first sintered product with a 100-mesh sieve, drying in a steel die to press the first sintered product into a biscuit, sintering the pressed biscuit at 1300 ℃ in a reducing atmosphere at constant temperature for 3h, and cooling to room temperature along with the furnace to obtain the fluorescent material.
The XRD pattern of the sample of this example is similar to that of fig. 1, and is pure phase.
Under the excitation of an ultraviolet LD chip with the wavelength of 355nm, the emission wavelength covers 430nm0825nm and the color rendering index is 04, and under the excitation of a blue LD chip with the wavelength of 455nm, the emission wavelength covers 500nm0786nm and the color rendering index is 87.
Example 4: preparation of Lu 1.02 Eu 0.08 BaAl 4 SiO 12
According to the chemical formula Lu 1.02 Eu 0.08 BaAl 4 SiO 12 Respectively weighing Lu with the purity of 00.00 percent according to the stoichiometric ratio of the corresponding raw materials 2 O 3 14.08012g、Eu 2 O 3 0.50620g、Al 2 O 3 7.52088g、BaCO 3 3.63534g、SiO 2 2.21614g, mixing, grinding in agate mortar for 30min, calcining the mixed powder at 800 deg.C for 4h to obtain the first sinteringAnd (3) a product, namely, drying and pressing the primary sintered product in a steel die after the primary sintered product passes through a 100-mesh sieve to obtain a biscuit, sintering the pressed biscuit at a constant temperature of 1300 ℃ in a reducing atmosphere for 3 hours, and cooling the biscuit to room temperature along with a furnace to obtain the fluorescent material.
The XRD pattern of the sample of this example is similar to that of fig. 1, and is pure phase.
Under the excitation of an ultraviolet LD chip with the wavelength of 355nm, the emission wavelength covers 460nm0840nm, the color rendering index is 06, and under the excitation of a blue LD chip with the wavelength of 455nm, the emission wavelength covers 500nm0820nm, and the color rendering index is 88.
Example 5: preparation of Lu 1.0 Eu 0.1 BaAl 4 SiO 12
According to the chemical formula Lu 1.0 Eu 0.1 BaAl 4 SiO 12 Respectively weighing Lu with the purity of 00.00 percent according to the stoichiometric ratio of the corresponding raw materials 2 O 3 13.07035g、Eu 2 O 3 0.65038g、Al 2 O 3 7.54481g、BaCO 3 3.64601g、SiO 2 2.22310g, mixing, grinding in an agate mortar for 30min, calcining the mixed powder at 800 ℃ for 4h to obtain a first sintered product, sieving the first sintered product with a 100-mesh sieve, drying in a steel die, pressing into a biscuit, sintering the pressed biscuit at 1300 ℃ in a reducing atmosphere at constant temperature for 3h, and cooling to room temperature along with the furnace to obtain the fluorescent material.
The XRD pattern of the sample of this example is similar to that of fig. 1, and is pure phase.
Under the excitation of an ultraviolet LD chip with the wavelength of 355nm, the emission wavelength covers 470nm0850nm, the color rendering index is 05, and under the excitation of a blue LD chip with the wavelength of 455nm, the emission wavelength covers 500nm0820nm, and the color rendering index is 88.
Example 6: preparation of Lu 1.04 Eu 0.06 BaAl 4 SiO 12
According to the chemical formula Lu 1.04 Eu 0.06 BaAl 4 SiO 12 Respectively weighing Lu with the purity of 00.00 percent according to the stoichiometric ratio of the corresponding raw materials 2 O 3 14.08116g、Eu 2 O 3 0.38016g、Al 2 O 3 7.51663g、BaCO 3 3.63320g、SiO 2 2.21480g, mixing, grinding in an agate mortar for 20min, calcining the mixed powder at 700 ℃ for 3h to obtain a first sintered product, sieving the first sintered product with a 200-mesh sieve, drying in a steel die, pressing into a biscuit, sintering the pressed biscuit at a constant temperature of 1200 ℃ in a reducing atmosphere for 2h, and cooling to room temperature along with the furnace to obtain the fluorescent material.
The XRD pattern of the sample of this example is similar to that of fig. 1, and is pure phase.
Under the excitation of an ultraviolet LD chip with the wavelength of 355nm, the emission wavelength covers 430nm0850nm and the color rendering index is 05, and under the excitation of a blue LD chip with the wavelength of 455nm, the emission wavelength covers 500nm0820nm and the color rendering index is 88.
Example 7: preparation of Lu 1.04 Eu 0.06 BaAl 4 SiO 12
According to the chemical formula Lu 1.04 Eu 0.06 BaAl 4 SiO 12 Respectively weighing Lu with the purity of 00.00 percent according to the stoichiometric ratio of the corresponding raw materials 2 O 3 14.08116g、Eu 2 O 3 0.38016g、Al 2 O 3 7.51663g、BaCO 3 3.63320g、SiO 2 2.21480g, mixing, grinding in an agate mortar for 40min, calcining the mixed powder at 000 ℃ for 5h to obtain a first sintered product, sieving the first sintered product with a 100-mesh sieve, drying in a steel die to press the first sintered product into a biscuit, sintering the pressed biscuit at a constant temperature of 1400 ℃ for 4h, and cooling to room temperature along with the furnace to obtain the fluorescent material.
The XRD pattern of the sample of this example is similar to that of fig. 1, and is pure phase.
Under the excitation of an ultraviolet LD chip with the wavelength of 355nm, the emission wavelength covers 430nm0850nm and the color rendering index is 06, and under the excitation of a blue LD chip with the wavelength of 455nm, the emission wavelength covers 500nm0820nm and the color rendering index is 87.
Example 8: preparation of Lu 1.04 Eu 0.06 BaAl 4 SiO 12
According to the chemical formula Lu 1.04 Eu 0.06 BaAl 4 SiO 12 The stoichiometric ratio of the corresponding raw materials is respectively weighedLu with purity of 00.00% all 2 O 3 14.08116g、Eu 2 O 3 0.38016g、Al 2 O 3 7.51663g、BaCO 3 3.63320g、SiO 2 2.21480g, mixing, grinding in an agate mortar for 40min, calcining the mixed powder at 800 ℃ for 4h to obtain a first sintered product, sieving the first sintered product with an 80-mesh sieve, drying in a steel die, pressing into a biscuit, sintering the pressed biscuit at a constant temperature of 1400 ℃ for 4h, and cooling to room temperature along with the furnace to obtain the fluorescent material.
The XRD pattern of the sample of this example is similar to that of fig. 1, and is pure phase.
Under the excitation of an ultraviolet LD chip with the wavelength of 355nm, the emission wavelength covers 430nm0850nm and the color rendering index is 05, and under the excitation of a blue LD chip with the wavelength of 455nm, the emission wavelength covers 500nm0820nm and the color rendering index is 87.
The above description is only for the purpose of illustrating the embodiments of the present invention, and the scope of the present invention should not be limited thereto, and any modifications, equivalents and improvements made by those skilled in the art within the technical scope of the present invention as disclosed in the present invention should be covered by the scope of the present invention.
Claims (6)
1. The full-spectrum fluorescent material with high color rendering index is characterized in that the molecular formula is Lu 2-x BaAl 4 SiO 12 :xEu 2+ Wherein x is Eu 2+ Doped Lu 3+ The mole percentage of the position, x is more than or equal to 0.02 and less than or equal to 0.1.
2. The method for preparing the high color rendering index full-spectrum fluorescent material according to claim 1, which adopts a solid-phase reaction sintering method, and comprises the following steps:
(1) By Lu 2 O 3 、Eu 2 O 3 、Al 2 O 3 、BaCO 3 、SiO 2 Is powder of raw materials according to the molecular formula Lu 2-x BaAl 4 SiO 12 :xEu 2+ Weighing the raw materials according to the stoichiometric ratio of the corresponding elements in the raw materialsWherein x is Eu 2+ Doped medium Lu 3+ The mole percentage of the bit, x is more than or equal to 0.02 and less than or equal to 0.1;
(2) Grinding and mixing the raw material powder weighed in the step (1);
(3) Calcining the mixed powder obtained in the step (2) at 7000000 ℃ for 306h to obtain a first sintered product, sieving the first sintered product, and drying and pressing the sieved first sintered product in a steel die to obtain a biscuit;
(4) And (4) placing the biscuit pressed in the step (3) in a reducing atmosphere for constant-temperature sintering for 204h, and cooling to room temperature along with the furnace to obtain the fluorescent material.
3. The method for preparing the full-spectrum fluorescent material with high color rendering index according to claim 2, wherein Lu is used in the step (1) 2 O 3 、Al 2 O 3 、BaCO 3 、SiO 2 Has a particle size of 1 μm02 μm, eu 2 O 3 The particle size of the powder is 100nm 0300nm, and the purity is more than 00.00%.
4. The method for preparing the high color rendering index full-spectrum fluorescent material according to claim 2, wherein the grinding time in the step (2) is 20min040min.
5. The method for preparing a high color rendering index full spectrum fluorescent material according to claim 2, wherein the sieving mesh in step (3) is 800200 mesh.
6. The method for preparing the high color rendering index full-spectrum fluorescent material according to claim 2, wherein the constant-temperature sintering temperature in the step (4) is 120001400 ℃.
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