CN110964524A - Red, green, yellow and blue fluorescent powder and preparation method thereof - Google Patents

Red, green, yellow and blue fluorescent powder and preparation method thereof Download PDF

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Publication number
CN110964524A
CN110964524A CN201911353899.4A CN201911353899A CN110964524A CN 110964524 A CN110964524 A CN 110964524A CN 201911353899 A CN201911353899 A CN 201911353899A CN 110964524 A CN110964524 A CN 110964524A
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yellow
green
red
fluorescent powder
mesh sieve
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邹军
陈跃
石明明
张子博
徐文博
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Institute of New Materials and Industrial Technology of Wenzhou University
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Institute of New Materials and Industrial Technology of Wenzhou 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
    • C09K11/7759—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing samarium
    • C09K11/776—Chalcogenides
    • C09K11/7761—Chalcogenides with alkaline earth metals
    • 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
    • C09K11/7743—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing terbium
    • C09K11/7752—Phosphates
    • C09K11/7753—Phosphates with alkaline earth metals

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Luminescent Compositions (AREA)

Abstract

A red, green, yellow and blue fluorescent powder and its preparing process, wherein the chemical formula of said fluorescent powder is Ba1‑xMgP2O7：xRE3+(RE＝Dy3+，Tb3+，Sm3+And x is 0 to 0.05). The preparation method comprises the steps of weighing BaCO according to the molar ratio of the raw materials in the chemical formula3，MgO，NH4H2PO4，RE2O3The raw materials are put into a ball mill, ethanol is added for grinding for 1-3 hours, the obtained sample is dried by an oven at 60 ℃, then the sample is put into a mortar for full grinding, the ground sample is put into a porcelain boat for primary calcination after being sieved by a 200-mesh sieve, the obtained powder is ground and ground, the ground powder is further calcined after being sieved by the 200-mesh sieve, the ground powder is ground and sieved by the 200-mesh sieve, and the obtained sample is the red, green, yellow and blue fluorescent powder.

Description

Red, green, yellow and blue fluorescent powder and preparation method thereof
Technical Field
The invention relates to the technical field of luminescent materials, in particular to red, green, yellow and blue fluorescent powder and a preparation method thereof.
Background
In recent years, the problems of energy shortage and environmental pollution are becoming more serious, and the development and application of new energy-saving and environment-friendly technologies are becoming urgent needs for human survival and development. WLED is a new type of solid-state illumination source, which is the focus of attention. At present, a common mode for realizing the white light LED is realized by adding yellow fluorescent powder on a blue light chip, and half of the common mode depends on the blue light chip, but the problem of blue light harm is increasingly prominent at present, so that the finding of a substrate which is excited by ultraviolet light and can emit white light in a mixed mode is very important.
In recent years, phosphate compounds have become an important class of luminescent materials due to their advantages of low preparation temperature, high brightness, wide band gap, strong absorption in the ultraviolet region, high ultraviolet transmittance, stable physicochemical properties, easy particle size control, and the like. Alkali metal pyrophosphate and alkaline earth pyrophosphate have characteristics required as inorganic phosphorus materials. However, phosphors based on other types (e.g., sulfate, nitride, aluminate, borate, etc.) have been reported, but there are some drawbacks associated with these phosphors. For example, sulfide phosphors are thermally unstable and sensitive to moisture. The preparation of nitride phosphors often requires complex environmental conditions, such as high temperature and high nitrogen pressure. In addition, aluminate and borate phosphors generally exhibit lower quantum efficiencies. Phosphor materials based on the phosphate family can be prepared at moderate temperatures. They have better thermal and chemical stability than aluminate and borate phosphors.
Therefore, a novel phosphate phosphor is in the spotlight.
Disclosure of Invention
The present invention is directed to solving the above problems by providing a multi-colored phosphate phosphor which can emit blue, yellow, green and red lights of four different colors, and provides a solution for ultraviolet excited white LEDs.
The invention also aims to provide a preparation method of the fluorescent powder.
The technical scheme of the invention.
The red, green, yellow and blue fluorescent powder is characterized in that the chemical formula of the red, green, yellow and blue fluorescent powder is BaMgP2O7：RE3+(RE＝Dy3+，Tb3+，Sm3+)。
The preparation method of the red, green, yellow and blue fluorescent powder specifically comprises the following steps:
(1) calculated in mole percent, i.e. BaCO3：MgO：NH4H2PO4：RE2O325 percent to 50 percent (23.75-25 percent): 0-1.25% of BaCO, weighing chemical pure BaCO3，MgO，NH4H2PO4，RE2O3Raw materials;
(2) putting the raw materials into a ball mill, adding ethanol, grinding for 1-3 hours, drying the obtained sample at 60 ℃ in an oven, then fully grinding the sample in a mortar, and sieving the ground sample by a 200-mesh sieve to obtain mixed powder;
(3) and (3) placing the mixed powder which is obtained in the step (2) and passes through the 200-mesh sieve into a porcelain boat for primary calcination, controlling the temperature to be 400-mesh and 600 ℃ for heat preservation for 4h, naturally cooling to room temperature, crushing, grinding and passing through the 200-mesh sieve, placing the obtained sinter into the porcelain boat for secondary calcination, controlling the temperature to be 900-mesh and 1050 ℃ in air atmosphere for secondary calcination for 4h, crushing the obtained sinter obtained in the secondary calcination, grinding by using a mortar, and passing through the 200-mesh sieve to obtain the red, green, yellow and blue fluorescent powder.
The four-color fluorescent powder can be applied to the field of LEDs because of emitting blue, red, yellow and green colors.
The invention has the advantages of
(1) The invention provides a preparation method of multi-color fluorescent powder of phosphate matrix, which is simple, low in synthesis temperature and beneficial to industrial production.
(2) The four kinds of fluorescent powder with different colors provided by the invention can emit light in the same substrate, so that the four kinds of fluorescent powder can be applied by combining and synthesizing a white light LED.
(3) The phosphor powder of the phosphate matrix has stable physicochemical properties, so that the reliability of the white light LED prepared by the method is greatly improved.
Drawings
FIG. 1 is the XRD spectrum obtained in example 1.
FIG. 2 is an emission spectrum of example 1.
FIG. 3 is an emission spectrum of example 2.
FIG. 4 is an emission spectrum of example 3.
FIG. 5 is an emission spectrum of example 4.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Specific implementations of the present invention are described in detail below with reference to specific embodiments.
Example 1
A blue fluorescent powder with chemical formula of BaMgP2O7。
The preparation method of the blue fluorescent powder specifically comprises the following steps:
(1) calculated in mole percent, i.e. BaCO3：MgO：NH4H2PO4：Tb2O325 percent to 50 percent (23.75-25 percent): 0-1.25% of BaCO, weighing chemical pure BaCO3，MgO，NH4H2PO4，Tb2O3Raw materials;
(2) putting the raw materials into a ball mill, adding ethanol, grinding for 1-3 hours, drying the obtained sample at 60 ℃ in an oven, then fully grinding the sample in a mortar, and sieving the ground sample by a 200-mesh sieve to obtain mixed powder;
(3) and (3) placing the mixed powder which is obtained in the step (2) and passes through the 200-mesh sieve into a porcelain boat for primary calcination, controlling the temperature to be 400-mesh and 600 ℃ for heat preservation for 4h, naturally cooling to room temperature, crushing, grinding and passing through the 200-mesh sieve, placing the obtained sinter into the porcelain boat for secondary calcination, controlling the temperature to be 900-mesh and 1050 ℃ in air atmosphere for secondary calcination for 4h, crushing the obtained sinter obtained in the secondary calcination, grinding by using a mortar, and passing through the 200-mesh sieve to obtain the blue fluorescent powder.
The blue phosphor obtained above was white in appearance.
Subjecting the obtained molecular formula to BaMgP by X-ray diffractometer2O7The XRD pattern of the blue fluorescent powder is shown in figure 1, which shows that the molecular formula is BaMgP2O7The blue fluorescent powder is BaMgP2O7Pure phase.
The blue fluorescent powder obtained by the above method is measured by a fluorescence spectrometer, and the emission spectrum is shown in fig. 2, and it can be seen from fig. 2 that the emission wavelength is 450nm under 352nm excitation.
Example 2
A green phosphor powder with a chemical formula of Ba1-xMgP2O7：xTb3+。
The preparation method of the blue fluorescent powder specifically comprises the following steps:
(1) calculated in mole percent, i.e. BaCO3：MgO：NH4H2PO4：Tb2O3Weighing chemically pure BaCO according to the proportion of 25 percent to 50 percent3，MgO，NH4H2PO4，Tb2O3Raw materials;
(2) putting the raw materials into a ball mill, adding ethanol, grinding for 1-3 hours, drying the obtained sample at 60 ℃ in an oven, then fully grinding the sample in a mortar, and sieving the ground sample by a 200-mesh sieve to obtain mixed powder;
(3) and (3) placing the mixed powder which is obtained in the step (2) and passes through the 200-mesh sieve into a porcelain boat for primary calcination, controlling the temperature to be 400-mesh and 600 ℃ for heat preservation for 4h, naturally cooling to room temperature, crushing, grinding and passing through the 200-mesh sieve, placing the obtained sinter into the porcelain boat for secondary calcination, controlling the temperature to be 900-mesh and 1050 ℃ in air atmosphere for secondary calcination for 4h, crushing the obtained sinter obtained in the secondary calcination, grinding by using a mortar, and passing through the 200-mesh sieve to obtain the blue fluorescent powder.
The green phosphor obtained above was white in appearance.
Subjecting the obtained molecular formula to Ba by X-ray diffractometer1-xMgP2O7：xTb3+The XRD pattern of the green phosphor is the same as that of FIG. 1, which shows that the molecular formula is Ba1-xMgP2O7：xTb3+The green phosphor is BaMgP2O7Pure phase.
The blue phosphor obtained above was measured by a fluorescence spectrometer, and the emission spectrum obtained is shown in fig. 3, and it can be seen from fig. 3 that the emission wavelength is in green under 352nm excitation.
Example 3
A yellow fluorescent powder with chemical formula of Ba1-xMgP2O7：xDy3+。
The preparation method of the blue fluorescent powder specifically comprises the following steps:
(1) calculated in mole percent, i.e. BaCO3：MgO：NH4H2PO4：Tb2O3Weighing chemically pure BaCO according to the proportion of 25 percent to 50 percent3，MgO，NH4H2PO4，Dy2O3Raw materials;
(2) putting the raw materials into a ball mill, adding ethanol, grinding for 1-3 hours, drying the obtained sample at 60 ℃ by an oven, then putting the dried sample into a mortar for full grinding, and sieving the ground sample by a 200-mesh sieve to obtain mixed powder;
(3) and (3) placing the mixed powder which is obtained in the step (2) and passes through the 200-mesh sieve into a porcelain boat for primary calcination, controlling the temperature to be 400-mesh and 600 ℃ for heat preservation for 4h, naturally cooling to room temperature, crushing, grinding and passing through the 200-mesh sieve, placing the obtained sinter into the porcelain boat for secondary calcination, controlling the temperature to be 900-mesh and 1050 ℃ in air atmosphere for secondary calcination for 4h, crushing the obtained sinter obtained in the secondary calcination, grinding by using a mortar, and passing through the 200-mesh sieve to obtain the blue fluorescent powder.
The yellow phosphor obtained above is white in appearance.
Subjecting the obtained molecular formula to X-ray diffractometer to obtain the compound with the molecular formula Ba1-xMgP2O7：xDy3+The XRD pattern of the yellow phosphor is the same as that of FIG. 1, which shows that the molecular formula is Ba1-xMgP2O7：xDy3+The yellow fluorescent powder is BaMgP2O7Pure phase.
The blue phosphor obtained above was measured by a fluorescence spectrometer, and the emission spectrum obtained is shown in fig. 4, and it can be seen from fig. 4 that the emission wavelength is in yellow light under 352nm excitation.
Example 4
A red phosphor powder with chemical formula of Ba1-xMgP2O7：xSm3+。
The preparation method of the blue fluorescent powder specifically comprises the following steps:
(1) calculated in mole percent, i.e. BaCO3：MgO：NH4H2PO4：Sm2O3Weighing chemically pure BaCO according to the proportion of 25 percent to 50 percent3，MgO，NH4H2PO4，Sm2O3Raw materials;
(2) putting the raw materials into a ball mill, adding ethanol, grinding for 1-3 hours, drying the obtained sample at 60 ℃ by an oven, then putting the dried sample into a mortar for full grinding, and sieving the ground sample by a 200-mesh sieve to obtain mixed powder;
(3) and (3) placing the mixed powder which is obtained in the step (2) and passes through the 200-mesh sieve into a porcelain boat for primary calcination, controlling the temperature to be 400-mesh and 600 ℃ for heat preservation for 4h, naturally cooling to room temperature, crushing, grinding and passing through the 200-mesh sieve, placing the obtained sinter into the porcelain boat for secondary calcination, controlling the temperature to be 900-mesh and 1050 ℃ in air atmosphere for secondary calcination for 4h, crushing the obtained sinter obtained in the secondary calcination, grinding by using a mortar, and passing through the 200-mesh sieve to obtain the blue fluorescent powder.
The red phosphor obtained above was white in appearance.
Subjecting the obtained molecular formula to Ba by X-ray diffractometer1-xMgP2O7：xSm3+With red phosphorThe XRD pattern of the sample was determined as shown in FIG. 1, indicating that the molecular formula is Ba1-xMgP2O7：xSm3+The red phosphor is BaMgP2O7Pure phase.
The blue fluorescent powder obtained by the above method is measured by a fluorescence spectrometer, and the emission spectrum is shown in fig. 5. as can be seen from fig. 5, under 352nm excitation, the emission wavelength is in red.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (6)

1. The red, green, yellow and blue fluorescent powder is characterized in that the chemical formula of the red, green, yellow and blue fluorescent powder is BaMgP2O7：RE3+(RE＝Dy3+，Tb3+，Sm3+)。
2. The red, green, yellow and blue phosphor of claim 1, wherein the blue phosphor has a chemical formula of BaMgP2O7。
3. The red, green, yellow and blue phosphor of claim 1, wherein the red phosphor has a chemical formula of BaMgP2O7：Sm3+。
4. The red, green, yellow and blue phosphor of claim 1, wherein the green phosphor has a chemical formula of BaMgP2O7：Tb3+。
5. The red, green, yellow and blue phosphor of claim 1, wherein the yellow phosphor has a chemical formula of BaMgP2O7：Dy3+。
6. The method for preparing red, green, yellow and blue fluorescent powder according to claim 1, which comprises the following steps:
(1) calculated in mole percent, i.e. BaCO3：MgO：NH4H2PO4：RE2O325 percent to 50 percent (23.75-25 percent): 0-1.25% of BaCO, weighing chemical pure BaCO3，MgO，NH4H2PO4，RE2O3Raw materials;
(2) putting the raw materials into a ball mill, adding ethanol, grinding for 1-3 hours, drying the obtained sample at 60 ℃ in an oven, then fully grinding the sample in a mortar, and sieving the ground sample by a 200-mesh sieve to obtain mixed powder;
(3) and (3) placing the mixed powder which is obtained in the step (2) and passes through the 200-mesh sieve into a porcelain boat for primary calcination, controlling the temperature to be 400-plus-one, keeping the temperature for 4h at 600 ℃, naturally cooling to room temperature, crushing, grinding and passing through the 200-mesh sieve, then placing the obtained sinter into the porcelain boat for secondary calcination, controlling the temperature to be 900-plus-one, 1050-plus-one, in air atmosphere, for secondary calcination for 4h, crushing the obtained sinter obtained in the secondary calcination, grinding by using a mortar, and passing through the 200-mesh sieve to obtain the red, green, yellow and blue fluorescent powder.
CN201911353899.4A 2019-12-25 2019-12-25 Red, green, yellow and blue fluorescent powder and preparation method thereof Pending CN110964524A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113713944A (en) * 2021-08-02 2021-11-30 东莞市唯美陶瓷工业园有限公司 Raw material treatment method for digital ceramic glaze ink

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104498030A (en) * 2014-12-29 2015-04-08 上海应用技术学院 Multicolor fluorescent powder and synthesis method thereof
CN104877678A (en) * 2015-05-11 2015-09-02 上海应用技术学院 Yellow long-afterglow luminescent material and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104498030A (en) * 2014-12-29 2015-04-08 上海应用技术学院 Multicolor fluorescent powder and synthesis method thereof
CN104877678A (en) * 2015-05-11 2015-09-02 上海应用技术学院 Yellow long-afterglow luminescent material and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
J. A. WANI ET AL.,: ""Dy3+‐, Sm3+‐, Ce3+‐ and Tb3+‐activated optical properties of microcrystalline BaMgP2O7 phosphors"", 《LUMINESCNECE》, vol. 32, no. 2, 6 July 2016 (2016-07-06), pages 240 - 252 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113713944A (en) * 2021-08-02 2021-11-30 东莞市唯美陶瓷工业园有限公司 Raw material treatment method for digital ceramic glaze ink
CN113713944B (en) * 2021-08-02 2023-08-22 东莞市唯美陶瓷工业园有限公司 Raw material treatment method for digital ceramic glaze ink

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