CN107033903B - Rare earth ion and transition metal ion doped single-matrix phosphate white fluorescent powder and preparation method thereof - Google Patents

Rare earth ion and transition metal ion doped single-matrix phosphate white fluorescent powder and preparation method thereof Download PDF

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CN107033903B
CN107033903B CN201710433241.9A CN201710433241A CN107033903B CN 107033903 B CN107033903 B CN 107033903B CN 201710433241 A CN201710433241 A CN 201710433241A CN 107033903 B CN107033903 B CN 107033903B
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fluorescent powder
transition metal
rare earth
sintered body
phosphate white
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CN107033903A (en
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王超
李盼来
王志军
杨志平
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Heibei University
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
    • C09K11/7795—Phosphates
    • C09K11/7796—Phosphates with alkaline earth metals

Abstract

The invention discloses a single-matrix phosphate white fluorescent powder doped with rare earth ions and transition metal ions, which has a chemical general formula as follows: ca8.78‑x‑ySrxBayEu0.06Mn0.16Ce(PO4)7Wherein x is more than or equal to 0 and less than or equal to 1.0, y is more than or equal to 0 and less than or equal to 1.0, and x and y are not 0 at the same time. The preparation method comprises the following steps: a) weighing oxides, carbonates or phosphates containing Ca, Sr, Ba, Eu, Mn, Ce and P according to the molar ratio of each element of the chemical general formula of the fluorescent powder, mixing, stirring and grinding to obtain a mixture; b) placing the mixture in a reducing atmosphere, heating, raising the temperature and roasting to obtain a sintered body; c) and cooling the sintered body to room temperature and fully grinding to obtain the sintered body. The white fluorescent powder prepared by the invention has wide excitation wavelength range and high luminous intensity, can be effectively excited by specific ultraviolet wavelength to emit bright white light, and has good thermal stability.

Description

Rare earth ion and transition metal ion doped single-matrix phosphate white fluorescent powder and preparation method thereof
Technical Field
The invention relates to a luminescent material and a preparation method thereof, in particular to single-matrix phosphate white fluorescent powder doped with rare earth ions and transition metal ions and a preparation method thereof.
Background
White Light LEDs (Light Emitting diodes) are considered as a fourth generation solid state lighting source that replaces traditional incandescent, fluorescent, and high intensity gas discharge lamps. The LED device has the advantages of energy conservation, high efficiency, environmental protection, small volume, long service life, high reliability, intelligent control and the like, and is widely applied to various illumination and display fields.
Currently, there are four main approaches for realizing white light emission by LEDs: (1) the LED chips respectively emitting red light, green light and blue light are combined together to make red, green and blue lightThe three lights are superposed together to form white light; (2) the near ultraviolet light or purple light LED chip excites three kinds of fluorescent powder which respectively emit red light, green light and blue light, and the red light, the green light and the blue light are mixed into white light; (3) the blue LED chip excites yellow fluorescent powder, and the blue light and the yellow light are mixed into white light; (4) the ultraviolet LED chip excites the white light to emit single-matrix fluorescent powder. In the first implementation mode, the driving voltages required by the red, green and blue LEDs are different, so that the circuit is complex, the cost is high, and the application range is narrow. In the second scheme, the blue phosphor has an absorption effect on red light emitted by the red phosphor, so that the formed white light generates a color shift phenomenon in the actual use process. The most widely used technical scheme at present is the third, the used blue LED is a gallium nitride diode, and the yellow fluorescent powder with mature technology is YAG: Ce3+The blue-light LED can be effectively excited by a 440-480nm blue-light LED chip to be mixed with blue light to form white light, and the white-light LED has the advantages of high luminous brightness, high electro-optic conversion efficiency and strong thermal stability, but has some obvious defects, such as lack of red components in a spectrum, high color temperature, cold luminous color, poor color rendering property and difficulty in controlling the particle size of the fluorescent powder synthesized by reaction. The fourth scheme is more and more concerned in recent years, and the single-matrix three-primary-color fluorescent powder has many advantages, such as the self-absorption phenomenon can be effectively avoided, the color rendering index is high, and the color temperature can be adjusted. Therefore, the continuous development of a wider variety of single-matrix three-primary-color phosphors is a subject actively explored by research and development personnel in the industry at present.
Disclosure of Invention
The invention aims to provide single-matrix phosphate white fluorescent powder doped with rare earth ions and transition metal ions and a preparation method thereof, and provides more choices for market demands for the white fluorescent powder.
The purpose of the invention is realized by the following technical scheme: a single-matrix phosphate white fluorescent powder doped with rare earth ions and transition metal ions is characterized in that the chemical general formula is as follows:
Ca8.78-x-ySrxBayEu0.06Mn0.16Ce(PO4)7wherein 0 is less than or equal to xIs less than or equal to 1.0, y is less than or equal to 1.0 and is less than or equal to 0, and x and y are not 0 at the same time.
Preferably, when x is 0.2 and y is 0.2 in the formula, the thermal stability of the prepared phosphor is best.
The invention also discloses a preparation method of the single-matrix phosphate white fluorescent powder doped with rare earth ions and transition metal ions, which comprises the following steps:
(a) according to the chemical general formula Ca of the fluorescent powder8.78-x-ySrxBayEu0.06Mn0.16Ce(PO4)7Weighing oxides, carbonates or phosphates containing Ca, Sr, Ba, Eu, Mn, Ce and P elements according to the molar ratio of the elements, mixing, stirring and grinding to obtain a mixture, wherein x is more than 0 and less than or equal to 1.0, y is more than 0 and less than or equal to 1.0 in the chemical general formula, and x and y are not 0 at the same time;
(b) placing the mixture in a reducing atmosphere, heating to 1150-1250 ℃, and roasting for 7-8h to obtain a sintered body;
(c) and cooling the obtained sintered body to room temperature, and then fully grinding to obtain the rare earth ion and transition metal ion doped phosphate white fluorescent powder.
The grinding time of the step (a) is 20-30 min.
The chemical formula of the fluorescent powder in the step (a) is Ca8.38Sr0.2Ba0.2Eu0.06Mn0.16Ce(PO4)7The thermal stability of the phosphor is best.
The temperature rise rate in the step (b) is 2-5 ℃/min.
The reducing atmosphere in the step (b) refers to embedding of carbon powder with large particle size or H2And N2The mixed gas forms a reducing atmosphere.
The heating in the step (b) is carried out for 8h at the temperature of 1150-1250 ℃, and preferably for 8h at the temperature of 1200 ℃.
In the prior art, most of fluorescent powder of single-matrix doping elements cannot simultaneously generate a luminous center for emitting red light, green light and blue light, so that the obtained white light has insufficient spectral content and poor display performance, and the application of the white light fluorescent powder is limited. The fluorescent powder provided by the invention is prepared bySpecific proportion of rare earth ion Eu2+And transition metal ion Mn2+The phosphor is doped into a single host to be used as an activator and a sensitizer to form a luminescence center, is derived from a host sensitization luminescence mechanism, successfully overcomes the technical obstacles, and obtains the bright single phosphate host white phosphor with strong thermal stability by doping Sr and Ba and a specific Sr/Ba doping ratio. The fluorescent powder prepared by the invention has strong broadband absorption at the wavelength of 280 plus 350nm, the emission wavelength range is 360 plus 750nm, full spectrum emission can be realized in the wavelength range, and the excitation requirement of a near ultraviolet LED chip is met. The white fluorescent powder prepared by the invention has wide range of excitation wavelength and high luminous intensity, can be effectively excited by specific ultraviolet wavelength to emit bright white light, and particularly, the luminous intensity of the existing single-matrix doped fluorescent powder is weakened at high temperature, and the stability is poor. The white fluorescent powder provided by the invention adopts a high-temperature solid phase method, has the advantages of simple preparation process, easiness in operation and control, high safety, short preparation time and high production efficiency, and is suitable for industrial large-scale production and application.
Drawings
Fig. 1 is a graph comparing an XRD pattern with a standard pattern of phosphors prepared in examples 1 and 6.
FIG. 2 shows excitation and emission spectra of the phosphor prepared in example 3.
FIG. 3 is a graph showing color coordinates of phosphors prepared in examples 1, 5, 6, 10 and 12 of the present invention.
FIG. 4 shows temperature-variable spectra of phosphors prepared in examples 1, 6 and 12 of the present invention and comparative example 1.
Detailed Description
The following examples serve to illustrate the invention in further detail, but without restricting it in any way.
Example 1
(1) Weighing the following raw materials in parts by weight: 1.139g of CaCO30.039g of SrCO30.014g of Eu2O30.024g of MnCO3、1.068g of NH4H2PO40.228g of CeO2Mixing, stirring, and grinding for 20min to obtain mixture;
(2) placing the ground mixture powder in a small crucible and placing in H2And N2(H2And N2The volume ratio of (1) to (9), heating to 1200 ℃ at a heating rate of 2 ℃/min, sintering for 8 hours at the temperature, and naturally cooling to room temperature to obtain a sintered body;
(3) cooling the obtained sintered body to room temperature, and fully grinding to obtain the rare earth ion and transition metal ion doped single-matrix phosphate white fluorescent powder Ca8.58Sr0.2Eu0.06Mn0.16Ce(PO4)7。
Examples 2 to 5
The preparation method of the embodiment 2-5 is the same as the embodiment 1, only the raw material proportion is different, and the proportion and the chemical formula of the prepared fluorescent powder are as follows:
item The prepared fluorescent powder CaCO3/g SrCO3/g Eu2O3/g MnCO3/g NH4H2PO4/g CeO2/g
Example 2 Ca8.38Sr0.4Eu0.06Mn0.16Ce(PO4)7 1.112 0.078 0.014 0.024 1.068 0.228
Example 3 Ca8.18Sr0.6Eu0.06Mn0.16Ce(PO4)7 1.086 0.117 0.014 0.024 1.068 0.228
Example 4 Ca7.98Sr0.8Eu0.06Mn0.16Ce(PO4)7 1.059 0.157 0.014 0.024 1.068 0.228
Example 5 Ca7.78Sr1.0Eu0.06Mn0.16Ce(PO4)7 1.033 0.196 0.014 0.024 1.068 0.228
Example 6
(1) Weighing the following raw materials in parts by weight: 1.139g of CaCO30.052g of BaCO30.014g of Eu2O30.024g of MnCO31.068g of NH4H2PO4、0.228g CeO2Mixing, stirring, and grinding for 20min to obtain mixture;
(2) placing the ground mixture powder in a small crucible and placing in H2And N2(H2And N2The volume ratio of (1) to (9), heating to 1200 ℃ at a heating rate of 2 ℃/min, sintering for 8 hours at the temperature, and naturally cooling to room temperature to obtain a sintered body;
(3) cooling the obtained sintered body to room temperature, and fully grinding to obtain the rare earth ion and transition metal ion doped single-matrix phosphate white fluorescent powder Ca8.58Ba0.2Eu0.06Mn0.16Ce(PO4)7。
Examples 7 to 10
The preparation methods of the examples 7-10 are the same as the example 6, only the raw material proportions are different, and the proportions and the chemical formulas of the prepared fluorescent powder are as follows:
item Prepared phosphate fluorescent powder CaCO3/g BaCO3/g Eu2O3/g MnCO3/g NH4H2PO4/g CeO2/g
Example 7 Ca8.38Ba0.4Eu0.06Mn0.16Ce(PO4)7 1.112 0.105 0.014 0.024 1.068 0.228
Example 8 Ca8.18Ba0.6Eu0.06Mn0.16Ce(PO4)7 1.086 0.157 0.014 0.024 1.068 0.228
Example 9 Ca7.98Ba0.8Eu0.06Mn0.16Ce(PO4)7 1.059 0.209 0.014 0.024 1.068 0.228
Example 10 Ca7.78Ba1.0Eu0.06Mn0.16Ce(PO4)7 1.033 0.262 0.014 0.024 1.068 0.228
Example 11
(1) Weighing the following raw materials in parts by weight: 1.123g of CaCO30.039g of SrCO30.026g of BaCO30.014g of Eu2O30.024g of MnCO31.065g of NH4H2PO40.228g of CeO2Mixing, stirring, and grinding for 20min to obtain mixture;
(2) placing the ground mixture powder in a small crucible and placing in H2And N2(H2And N2The volume ratio of (1) to (9), heating to 1200 ℃ at a heating rate of 2 ℃/min, sintering for 8 hours at the temperature, and naturally cooling to room temperature to obtain a sintered body;
(3) cooling the obtained sintered body to room temperature, and fully grinding to obtain rare earth ion and transition metal ion doped single-matrix phosphateWhite phosphor Ca8.48Sr0.2Ba0.1Eu0.06Mn0.16Ce(PO4)7。
Examples 12 to 14
The preparation methods of examples 12-14 are the same as example 11, except that the raw material ratios are different, and the ratios and the chemical formulas of the prepared fluorescent powder are as follows:
item Prepared phosphate fluorescent powder CaCO3/g SrCO3/g BaCO3/g Eu2O3/g MnCO3/g NH4H2PO4/g CeO2/g
Example 12 Ca8.38Sr0.2Ba0.2Eu0.06Mn0.16Ce(PO4)7 1.110 0.039 0.052 0.014 0.024 1.065 0.228
Example 13 Ca8.28Sr0.4Ba0.1Eu0.06Mn0.16Ce(PO4)7 1.097 0.078 0.026 0.014 0.024 1.065 0.228
Example 14 Ca8.18Sr0.4Ba0.2Eu0.06Mn0.16Ce(PO4)7 1.083 0.078 0.052 0.014 0.024 1.065 0.228
Comparative example 1
(1) Weighing the following raw materials in parts by weight: 1.165g of CaCO30.014g of Eu2O30.024g of MnCO31.068g of NH4H2PO40.228g of CeO2Mixing, stirring, and grinding for 20min to obtain mixture;
(2) placing the ground mixture powder in a small crucible and placing in H2And N2(H2And N2The volume ratio of (1) to (9), heating to 1200 ℃ at a heating rate of 2 ℃/min, sintering for 8 hours at the temperature, and naturally cooling to room temperature to obtain a sintered body;
(3) cooling the obtained sintered body to room temperature, and fully grinding to obtain the rare earth ion and transition metal ion doped single-matrix phosphate white fluorescent powder Ca8.78Eu0.06Mn0.16Ce(PO4)7。
Example 15 the optical and other properties of the phosphors prepared in examples and comparative examples were examined.
The experimental method comprises the following steps:
detection of Ca prepared in examples 1 and 68.58Sr0.2Eu0.06Mn0.16Ce(PO4)7And Ca8.58Ba0.2Eu0.06Mn0.16Ce(PO4)7The X-ray diffraction pattern of the obtained fluorescent powder is shown in figure 1.
Detection of Ca prepared in example 38.18Sr0.6Eu0.06Mn0.16Ce(PO4)7The excitation and emission spectra are obtained, as shown in FIG. 2, where the excitation wavelength λ isexThe emission band is from 360nm to 750nm at 320nm, so that composite white light emission is obtained, and the white light emitting fluorescent powder excited by the near ultraviolet LED is successfully prepared.
Detection of the phosphors Ca prepared in example 1, example 5, example 6, example 10 and example 12, respectively8.58Sr0.2Eu0.06Mn0.16Ce(PO4)7、Ca7.78Sr1.0Eu0.06Mn0.16Ce(PO4)7、Ca8.58Ba0.2Eu0.06Mn0.16Ce(PO4)7、Ca7.78Ba1.0Eu0.06Mn0.16Ce(PO4)7And Ca8.38Sr0.2Ba0.2Eu0.06Mn0.16Ce(PO4)7As shown in fig. 3; the synthesized fluorescent powder realizes adjustable color and controllable color temperature on the basis of white light emission.
Ca prepared in example 1, example 6, example 12 and comparative example 1 was examined8.58Sr0.2Eu0.06Mn0.16Ce(PO4)7、Ca8.58Ba0.2Eu0.06Mn0.16Ce(PO4)7、Ca8.38Sr0.2Ba0.2Eu0.06Mn0.16Ce(PO4)7、Ca8.78Eu0.06Mn0.16Ce(PO4)7The variable temperature spectrum of the material has improved stability of the luminescence temperature after independently doping Sr or Ba. When Sr and Ba are doped simultaneously, the luminescence temperature stability of the material is further improved, as shown in (a), (b), (c) and (d) of FIG. 4.
The preparation methods described in the specification of the present invention can prepare the phosphors to be protected in the present invention, and the phosphors prepared under the disclosed process parameters all have substantially similar experimental effects to the portion of the phosphors detected in example 15.

Claims (5)

1. A single-matrix phosphate white fluorescent powder doped with rare earth ions and transition metal ions is characterized in that the chemical general formula is as follows: ca8.78-x-ySrxBayEu0.06Mn0.16Ce(PO4)7Wherein x =0.2 and y = 0.2.
2. A preparation method of single-matrix phosphate white fluorescent powder doped with rare earth ions and transition metal ions is characterized by comprising the following steps: (a) according to the chemical general formula Ca of the fluorescent powder8.78-x-ySrxBayEu0.06Mn0.16Ce(PO4)7Weighing oxides, carbonates or phosphates containing Ca, Sr, Ba, Eu, Mn, Ce and P elements according to the molar ratio of the elements, mixing, stirring and grinding to obtain a mixture, wherein x =0.2 and y =0.2 in the chemical general formula; (b) mixing the abovePlacing the compound in a reducing atmosphere, heating to 1150-1250 ℃, and roasting for 7-8h to obtain a sintered body; and (c) cooling the sintered body to room temperature, and fully grinding to obtain the single-matrix phosphate white fluorescent powder doped with rare earth ions and transition metal ions.
3. The method for preparing rare earth ion and transition metal ion doped single matrix phosphate white phosphor according to claim 2, wherein the grinding time in step (a) is 20-30 min.
4. The method for preparing rare earth ion and transition metal ion doped single matrix phosphate white phosphor according to claim 2, wherein the temperature rise rate in step (b) is 2-5 ℃/min.
5. The method for preparing rare earth ion and transition metal ion doped single matrix phosphate white phosphor according to claim 2, wherein the reducing atmosphere in step (b) is large particle size carbon powder embedding or H2And N2The mixed gas forms a reducing atmosphere.
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CN108217621B (en) * 2018-03-02 2021-11-30 西北大学 Phosphate and synthesis and application of fluorescent powder using phosphate as matrix
CN109679653A (en) * 2019-01-14 2019-04-26 惠州学院 A kind of single-substrate white LED white fluorescent powder

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CN103589424A (en) * 2013-09-24 2014-02-19 厦门通士达新材料有限公司 Yellow orange-orange red fluorescent material and preparation method thereof

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CN103589424A (en) * 2013-09-24 2014-02-19 厦门通士达新材料有限公司 Yellow orange-orange red fluorescent material and preparation method thereof

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Title
Crystal structure, luminescence properties, energy transfer and thermal properties of a novel color-tunable, white light-emitting phosphor Ca9-x-yCe(PO4)7:xEu2+,yMn2+;Chao Wang et al.;《Phys. Chem. Chem. Phys.》;20160920;第18卷;第28661-28673页 *

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