阅读说明：本技术 一种磷酸盐基荧光粉材料及其制备方法和应用 (Phosphate-based fluorescent powder material and preparation method and application thereof ) 是由 邵起越 徐小雪 姚乐琪 董岩 蒋建清 于 2019-10-30 设计创作，主要内容包括：本发明公开了一种磷酸盐基荧光粉材料及其制备方法和应用,该荧光粉材料的化学表达式为AB<Sub>1-x</Sub>P<Sub>2</Sub>O<Sub>7</Sub>:xCr,其中A为Li、Na、K中至少一种,0.01≤x≤0.1；其制备方法如下：1)按上述磷酸盐基荧光粉材料的化学剂量比精确称取原料；2)将称取的原料充分混合均匀,并将混合物在空气气氛下高温灼烧,得到灼烧产物；3)将灼烧产物研磨成粉末,之后洗涤、烘干,得到所述的磷酸盐基荧光粉材料。本发明所述的荧光粉材料可被蓝光LED芯片有效激发,并发射750～1100nm宽带近红外光,其化学稳定性好,发光性能优异,且制备方法简单、便于操作,成本低,无污染,适用于工业化批量成产。(The invention discloses a phosphate-based fluorescent powder material and a preparation method and application thereof, wherein the chemical expression of the fluorescent powder material is AB 1‑x P 2 O 7 xCr, wherein A is at least one of Li, Na and K, and x is more than or equal to 0.01 and less than or equal to 0.1; the preparation method comprises the following steps: 1) accurately weighing the raw materials according to the chemical dose ratio of the phosphate-based fluorescent powder material; 2) fully and uniformly mixing the weighed raw materials, and firing the mixture at a high temperature in an air atmosphere to obtain a firing product; 3) and grinding the burning product into powder, and then washing and drying to obtain the phosphate-based fluorescent powder material. The fluorescent powder material can be effectively excited by a blue light LED chip and emits 750-1100 nm broadband near-infrared light, and is good in chemical stability, excellent in luminous performance, simple in preparation method, convenient to operate, low in cost, free of pollution and suitable for industrial batch production.)

1. A phosphate-based phosphor material, characterized by: the chemical expression of the fluorescent powder material is AB_1-xP₂O₇xCr, wherein A is at least one of Li, Na and K, and is not less than 0.01x≤0.1。

2. A phosphate-based phosphor material according to claim 1, wherein: the chemical expression of the fluorescent powder material can also be AB_1-x-yP₂O₇xCr, yYb, wherein A is at least one of Li, Na and K, B is at least one of Al, Ga, In and Sc, x is more than or equal to 0.01 and less than or equal to 0.1, and y is more than 0 and less than or equal to 0.05.

3. A phosphate-based phosphor material according to claim 1 or 2, characterized in that: the fluorescent powder material is excited by visible light in the range of 400-520 nm and 550-780 nm and emits broadband near infrared light in the range of 750-1100 nm.

4. A method of preparing a phosphate-based phosphor material according to claim 1 or 2, characterized in that: the method comprises the following steps:

1) accurately weighing carbonate of Li, Na and K, oxide of Al, Ga, In and Sc and NH according to the chemical dose ratio of the phosphate-based fluorescent powder material₄H₂PO₄As a raw material;

2) fully and uniformly mixing the raw materials weighed in the step 1) to obtain a mixture, and firing the mixture at a high temperature in an air atmosphere to obtain a firing product;

3) grinding the burning product obtained in the step 2) into powder, and then washing and drying to obtain the phosphate-based fluorescent powder material.

5. The method of claim 4, wherein the phosphate-based phosphor material is prepared by: the excess percentage of the Li carbonate in the step 1) is 0-15%, and NH₄H₂PO₄The excess percentage is 0-10%.

6. The method of claim 4, wherein the phosphate-based phosphor material is prepared by: the high-temperature burning condition in the step 2) is as follows: the temperature is 800-1100 ℃, the burning time is 2-10 h, and the burning times are at least 1 time.

7. The method of claim 4, wherein the phosphate-based phosphor material is prepared by: grinding the burning product into powder in the step 3), and then washing and drying, namely grinding the burning product into powder, sieving the powder with a 200-mesh sieve, washing for 1-3 times, centrifuging and drying the precipitate at the temperature of 60-80 ℃.

8. Use of a phosphate-based phosphor material according to claim 1 or 2, characterized in that: the phosphate-based fluorescent powder material can be used for constructing a broadband near-infrared fluorescence conversion type LED device.

Technical Field

The invention relates to a phosphate-based fluorescent powder material and a preparation method and application thereof, belonging to the technical field of solid luminescent materials.

Background

The near-infrared light source has wide application in the fields of food detection, minimally invasive diagnosis, biological imaging, solar cell, spectrum test and the like. The current commercial near-infrared light sources mainly comprise tungsten filament incandescent lamps, near-infrared lasers and near-infrared LEDs. The tungsten filament incandescent lamp can provide an ultra-wide continuous light source from visible light to near infrared light, but has short service life, large volume, high working temperature and low luminous efficiency of the near infrared light part; the near-infrared laser and the near-infrared LED have high luminous intensity, but have the intrinsic characteristic of narrow coverage of an emission band. For applications requiring miniaturized and broadband-emitting near-infrared light sources, these light sources are not ideal, and there is a strong need to construct a long-life, small-volume, high-efficiency, wide-spectrum near-infrared light source from a new approach.

The LED device excited by the blue light chip is rapidly developed in the field of illumination, and becomes a latest generation of illumination light source, which provides a new way and thought for the research and development of broadband near-infrared light sources. The novel fluorescence conversion type broadband near-infrared LED light source can be built by compounding the near-infrared fluorescent powder and the blue light LED chip. Due to the mature preparation process and excellent performance of the blue light LED chip, the novel broadband near-infrared light source has the advantages of low cost, good thermal stability, high power, energy conservation and environmental protection. On the other hand, the corresponding fluorescent powder material is prepared by selecting a proper matrix material and luminous ion combination, and can provide continuously adjustable broadband near-infrared light emission under the excitation of a blue light chip.

At present, the research on the fluorescent powder material is mainly focused on a visible light region, the research on the fluorescent powder material which can be effectively excited by a blue light chip and can emit broadband near infrared light is less, and no corresponding mature product is provided in each field. Therefore, further intensive research on near-infrared fluorescent powder materials is needed, and a broadband near-infrared light source with high performance and multiple purposes is constructed in a new way.

Disclosure of Invention

The technical problem is as follows: the invention aims to provide a phosphate-based fluorescent powder material, a preparation method and application thereof, wherein the material is stable in chemical property and excellent in luminous performance, can be effectively excited by visible light in the ranges of 400-520 nm and 550-780 nm, and emits broadband near-infrared light in the range of 750-1100 nm; the preparation method of the material is simple, convenient to operate, low in cost, free of pollution and suitable for industrial batch production.

The technical scheme is as follows: the invention provides a phosphate-based fluorescent powder material, and the chemical expression of the fluorescent powder material is AB_1-xP₂O₇xCr, wherein A is at least one of Li, Na and K, and x is more than or equal to 0.01 and less than or equal to 0.1.

Wherein:

the chemical expression of the fluorescent powder material can also be AB_1-x-yP₂O₇xCr, yYb, wherein A is at least one of Li, Na and K, B is at least one of Al, Ga, In and Sc, x is more than or equal to 0.01 and less than or equal to 0.1, and y is more than 0 and less than or equal to 0.05.

The fluorescent powder material can be excited by visible light in the range of 400-520 nm and 550-780 nm and emits broadband near infrared light in the range of 750-1100 nm.

The invention also provides a preparation method of the phosphate-based fluorescent powder material, which adopts a high-temperature solid phase method for preparation, and the method comprises the following steps:

1) accurately weighing carbonate of Li, Na and K, oxide of Al, Ga, In and Sc and NH according to the chemical dose ratio of the phosphate-based fluorescent powder material₄H₂PO₄As a raw material;

2) fully and uniformly mixing the raw materials weighed in the step 1) to obtain a mixture, and firing the mixture at a high temperature in an air atmosphere to obtain a firing product;

3) grinding the burning product obtained in the step 2) into powder, and then washing and drying to obtain the phosphate-based fluorescent powder material.

Wherein:

the excess percentage of the Li carbonate in the step 1) is 0-15%, and NH₄H₂PO₄The excess percentage is 0-10%.

The high-temperature burning condition in the step 2) is as follows: the temperature is 800-1100 ℃, the burning time is 2-10 h, and the burning times are at least 1 time.

Grinding the burning product into powder in the step 3), and then washing and drying, namely grinding the burning product into powder, sieving the powder with a 200-mesh sieve, washing for 1-3 times, centrifuging and drying the precipitate at the temperature of 60-80 ℃.

The invention also provides an application of the phosphate-based fluorescent powder material, and the phosphate-based fluorescent powder material is applied to construction of a broadband near-infrared fluorescence conversion type LED device.

Has the advantages that: compared with the prior art, the invention has the following advantages:

1. the invention provides a novel fluorescent powder material type, which is wide in excitation range, can be excited by visible light in the ranges of 400-520 nm and 550-780 nm, can emit broadband near infrared light in the range of 750-1100 nm, has the emission wavelength completely in a near infrared band, and is large in half-peak width, high in luminous efficiency and good in luminous heat stability; the fluorescent powder material can be packaged with a blue light or red light LED chip to construct a broadband near-infrared fluorescence conversion type LED device, can be used as a novel near-infrared light source, and has the technical advantages of high energy efficiency, small size, wide spectrum and the like.

2. The fluorescent powder material prepared by the invention has stable property, and the luminous intensity is basically unchanged through the processes of heating, water soaking and the like.

3. The invention also provides a preparation method of the fluorescent powder material, the fluorescent powder material is synthesized by adopting a solid-phase reaction method, and the method is simple, convenient to operate, low in cost, free of pollution and suitable for industrial batch production.

Drawings

FIG. 1 is a graph showing excitation and emission spectra of a phosphate-based phosphor material of example 1 of the present invention, with a monitoring wavelength of 835nm and an excitation wavelength of 450 nm;

FIG. 2 is a graph showing excitation and emission spectra of a phosphate-based phosphor material in example 2 of the present invention, with a monitoring wavelength of 790nm and an excitation wavelength of 450 nm;

FIG. 3 is an excitation and emission spectra of a phosphate-based phosphor material of example 3 of the present invention, with a monitoring wavelength of 870nm and an excitation wavelength of 450 nm;

FIG. 4 is a graph showing excitation and emission spectra of a phosphate-based phosphor material of example 4 of the present invention, with a monitor wavelength of 875nm and an excitation wavelength of 450 nm;

FIG. 5 is a graph showing excitation and emission spectra of a phosphate-based phosphor material of example 6, with a monitor wavelength of 875nm and an excitation wavelength of 450 nm;

FIG. 6 shows the excitation and emission spectra of the phosphor-based phosphor material of example 7 of the present invention, with a monitor wavelength of 875nm and an excitation wavelength of 450 nm.

Detailed Description

The invention provides a phosphate-based fluorescent powder material and a preparation method and application thereof, wherein the phosphate-based fluorescent powder material has a chemical expression as follows: AB_1-x-yP₂O₇xCr, yYb, wherein A is at least one of Li, Na and K, B is at least one of Al, Ga, In and Sc, x is more than or equal to 0.01 and less than or equal to 0.1, y is more than or equal to 0 and less than or equal to 0.05, and Cr is used as a luminescent ion and is an essential component; yb plays a role in further broadening the emission wavelength of the phosphor, and is an unnecessary component, which may be selectively added or not added; no proportion requirement exists between the two; the fluorescent powder material can be effectively excited by a blue light LED chip and emits 750-1100 nm broadband near-infrared light, and is good in chemical stability, excellent in luminous performance, simple in preparation method, convenient to operate, low in cost, free of pollution and suitable for industrial batch production.