阅读说明：本技术 一种红光上转换发光材料及其制备方法 (Red light up-conversion luminescent material and preparation method thereof ) 是由 杨锦瑜 李慧玲 朱莉萍 李蓝苹 饶啟亮 张玲 于 2019-11-06 设计创作，主要内容包括：本发明公开了一种红光上转换发光材料及其制备方法,所述材料化学通式为Y<Sub>1-<I>x</I>-<I>y</I></Sub>(PO<Sub>3</Sub>)<Sub>3</Sub>:Ho<Sub><I>x</I></Sub>,Yb<Sub><I>y</I></Sub>,所述方法步骤为：一、配制稀土盐溶液及含磷溶液；二、按化学通式Y<Sub>1-<I>x</I>-<I>y</I></Sub>(PO<Sub>3</Sub>)<Sub>3</Sub>:Ho<Sub><I>x</I></Sub>,Yb<Sub><I>y</I></Sub>中物质的量比,移取步骤一中溶液混合均匀；三、将步骤二所得溶液水浴锅中搅拌并将pH调节为1~11；四、将步骤三所得溶液烘干得白色沉淀物；五、将上述所得白色沉淀物研磨后煅烧、再研磨即得到化学通式为Y<Sub>1-<I>x</I>-<I>y</I></Sub>(PO<Sub>3</Sub>)<Sub>3</Sub>:Ho<Sub><I>x</I></Sub>,Yb<Sub><I>y</I></Sub>红光上转换发光材料,本发明所需原材料均可从市场公开购买,使用设备为普通设备无特殊要求,且制备工艺简单,成本低,且上转换发光强度强,易于放大投入批量生产,取得了很好的使用效果。(The invention discloses a red light up-conversion luminescent material and a preparation method thereof, wherein the chemical general formula of the material is Y x y 1‑‑ (PO 3 ) 3 :Ho x ,Yb y The method comprises the following steps: firstly, preparing a rare earth salt solution and a phosphorus-containing solution; II, according to the chemical formula Y x y 1‑‑ (PO 3 ) 3 :Ho x ,Yb y The amount ratio of the substances in the step one, moving the solution obtained in the step two to be uniformly mixed, thirdly, stirring the solution obtained in the step two in a water bath kettle and regulating the pH value to be 1 ~ 11, fourthly, drying the solution obtained in the step three to obtain a white precipitate, fifthly, grinding the white precipitate, calcining and grinding again to obtain the compound with the chemical general formula of Y x y 1‑‑ (PO 3 ) 3 :Ho x ,Yb y The raw materials required by the invention can be purchased from the market, the used equipment is common equipment without special requirements, the preparation process is simple, the cost is low, and the up-conversion luminescent material isThe luminous intensity is strong, the large-scale batch production is easy to put into, and a good use effect is obtained.)

1. A red up-conversion luminescent material, characterized by: the chemical general formula of the material is Y _{x y1--}(PO₃)₃:Ho _x ,Yb _y Wherein:xis the ratio of the number of moles of Ho ions substituted for Y ions,xhas a value range of 0 <x≤0.05，yThe ratio of the number of moles of Yb ions to the number of moles of Y ions,yhas a value range of 0 <y≤0.5。

2. The method of preparing a red light up-conversion luminescent material according to claim 1, wherein: the method comprises the following steps:

respectively preparing a rare earth salt solution and a phosphorus-containing solution;

according to the general formula Y _{x y1--}(PO₃)₃:Ho _x , Yb _y Respectively transferring Y, P, Ho and Yb solution with corresponding amount in the step one according to the mass ratio of Y, P, Ho and Yb elements to be uniformly mixed to obtain mixed solution;

placing the uniformly mixed solution obtained in the step two in a water bath kettle at the temperature of 20 ~ 30 ℃ for water bath stirring, adjusting the pH to 1 ~ 11 by using an acidic pH regulator or an alkaline pH regulator, and stirring for 0.5 ~ 2 h for uniform mixing;

putting the mixed solution obtained in the step three into a drying oven at 70 ~ 120 ℃ for drying for 10 ~ 24 h to obtain a dry white precipitate;

grinding the white precipitate obtained in the fourth step uniformly, transferring the ground white precipitate into a crucible, calcining the crucible in a furnace at 500 ~ 1100 ℃ for 3-24 h, cooling the crucible to room temperature along with the furnace, and grinding to obtain the white precipitate with the chemical general formula of Y _{x y1--}(PO₃)₃:Ho _x , Yb _y A red up-conversion luminescent material.

3. The method of preparing a red light up-conversion luminescent material according to claim 2, wherein: in the first step, the method for preparing the rare earth salt solution comprises the following steps: respectively dissolving yttrium oxide, holmium oxide and ytterbium oxide in concentrated nitric acid or respectively dissolving soluble rare earth salt in deionized water; the method for preparing the phosphorus-containing solution comprises the following steps: the phosphorus salt is dissolved in deionized water or the phosphoric acid is diluted with deionized water.

4. The method of preparing a red light up-conversion luminescent material according to claim 3, wherein: the soluble rare earth salt is one or more of soluble rare earth salts containing nitrate, acetate, hydrochloride or sulfate corresponding to Y, Ho and Yb.

5. The method of preparing a red light up-conversion luminescent material according to claim 3, wherein: the phosphorus-containing solution is one or more of phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate or sodium trimetaphosphate soluble phosphorus-containing compounds.

6. The method for preparing a red light up-conversion luminescent material according to claim 2, wherein the concentration of the rare earth solution and the phosphorus-containing solution in the first step is 0.01 ~ 5.00.00 mol/L.

7. The method of preparing a red light up-conversion luminescent material according to claim 2, wherein: and the total ion concentration of Y, Ho and Yb in the mixed solution in the second step is 0.01-1.50 mol/L.

8. The method of preparing a red light up-conversion luminescent material according to claim 2, wherein: the amount of the rare earth element substance in the mixed solution in the second step (n(Y + Ho + Yb)) and the amount of phosphorus species (C: (Y + Ho + Yb))n(P)) was 1:2.0 ~ 4.0.0.

9. The method of preparing a red light up-conversion luminescent material according to claim 2, wherein: the acidic pH regulator in the third step is one or more of nitric acid, hydrochloric acid and sulfuric acid, and the alkaline pH regulator is one or more of ammonia water, ammonium bicarbonate, sodium bicarbonate and sodium hydroxide.

Technical Field

The invention relates to a luminescent material, in particular to a red light up-conversion luminescent material and a preparation method thereof, belonging to the technical field of rare earth material preparation.

Background

Y (PO) of monoclinic structure₃)₃Having a small ionic radius, Y³⁺YO with ions in slight twist₆Po passing through shared corners in octahedron₄Tetrahedra are mutually isolated, Y³⁺The distance between ions is large, concentration quenching can be reduced, and the fluorescent material has excellent chemical stability and thermal stability, so that the fluorescent material is expected to be a high-quality up-conversion luminescent material matrix. Ho³⁺The ions have red and green emission bands and Yb³⁺Co-doped in BaIn₆Y₂O₁₃Oxyfluoride glass ceramics, ZnO-Al₂O₃-GeO₂-SiO₂Glass-ceramic and Y₇O₆F₉The substrate can emit strong green light; will Ho³⁺Yb as activator³⁺Co-doped as sensitizer into Y (PO)₃)₃Crystal lattice, can be observed in Yb³⁺Ho enhancement by sensitizers³⁺The red light up-conversion luminescence phenomenon. At present, Y (PO)₃)₃The method mainly adopts a high-temperature solid-phase synthesis method and a sol-gel method for preparation, the product prepared by the high-temperature solid-phase method has the defects of large granularity, low product purity, increased particle surface defects due to the fact that the product needs to be subjected to ball milling, difficult control of body lattice defects, difficult uniform doping and the like, so that the performance of the luminescent material is reduced, and the metal alkoxide used in the process of preparing a sample by the sol-gel method has toxicity and certain harm to a human body.

Disclosure of Invention

The technical problem to be solved by the invention is as follows: the powder formed by the method can be sintered at a lower temperature to obtain a uniformly dispersed powder material, and experimental raw materials are nontoxic, so that the existing problems are effectively solved.

The technical scheme of the invention is as follows: a red light up-conversion luminescent material has a chemical general formula of Y _{x y1--}(PO₃)₃:Ho _x , Yb _y Wherein:xis the ratio of the number of moles of Ho ions substituted for Y ions,xhas a value range of 0 <x≤0.05，yThe ratio of the number of moles of Yb ions to the number of moles of Y ions,yhas a value range of 0 <yLess than or equal to 0.5. Wherein, the colon is marked as ": "denotes co-doping of Ho and Yb ions, preferablyxThe value range of (A) is not more than 0.001x≤0.02，yThe value range of (A) is not more than 0.1y≤0.3。

A method of preparing a red light up-conversion luminescent material, the method comprising the steps of:

firstly, respectively preparing a rare earth salt solution and a phosphorus-containing solution;

II, according to the chemical formula Y _{x y1--}(PO₃)₃:Ho _x , Yb _y Respectively transferring Y, P, Ho and Yb solution with corresponding amount in the step one according to the mass ratio of Y, P, Ho and Yb elements to be uniformly mixed to obtain mixed solution;

thirdly, putting the uniformly mixed solution obtained in the second step into a water bath kettle at the temperature of 20 ~ 30 ℃ for water bath stirring, adjusting the pH to 1 ~ 11 by using an acidic pH regulator or an alkaline pH regulator, and stirring for 0.5 ~ 2 h for uniform mixing;

fourthly, placing the mixed solution obtained in the third step in a drying oven at 70 ~ 120 ℃ for drying for 10 ~ 24 h to obtain a dry white precipitate;

fifthly, grinding the white precipitate obtained in the fourth step uniformly, transferring the ground white precipitate into a crucible, calcining the crucible in a furnace at 500 ~ 1100 ℃ for 3-24 h, cooling the crucible to room temperature along with the furnace, and grinding to obtain the white precipitate with the chemical general formula of Y _{x y1--}(PO₃)₃:Ho _x , Yb _y A red up-conversion luminescent material.

In the first step, the method for preparing the rare earth salt solution comprises the following steps: respectively dissolving yttrium oxide, holmium oxide and ytterbium oxide in concentrated nitric acid or respectively dissolving soluble rare earth salt in deionized water; the method for preparing the phosphorus-containing solution comprises the following steps: the phosphorus salt is dissolved in deionized water or the phosphoric acid is diluted with deionized water.

The soluble rare earth salt is one or more of soluble rare earth salts containing nitrate, acetate, hydrochloride or sulfate corresponding to Y, Ho and Yb, and preferably nitrate.

The phosphorus-containing solution is one or more of soluble phosphorus-containing compounds of phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate or sodium trimetaphosphate, preferably one or two of phosphoric acid and ammonium dihydrogen phosphate.

In the first step, the concentration of the rare earth solution and the phosphorus-containing solution is 0.01 ~ 5.00.00 mol/L, preferably the concentration of the rare earth solution is 0.01 ~ 1.00.00 mol/L, and the concentration of the phosphorus-containing solution is 0.01 ~ 3.00.00 mol/L.

The total ion concentration of Y, Ho and Yb in the mixed metal ion solution in the second step is 0.01-1.50 mol/L, and the total ion concentration of Y, Ho and Yb in the mixed metal ion solution is preferably 0.10-1.00 mol/L.

The amount of the rare earth element substance in the mixed solution in the second step (n(Y + Ho + Yb)) and the amount of phosphorus species (C: (Y + Ho + Yb))n(P)) is 1:2.0 ~ 4.0.0, preferably 1:2.5 ~ 3.

The stirring time of the water bath in the third step is 0.5 ~ 2 h, and the preferable stirring time of the water bath is 1 ~ 1.5.5 h.

The acidic pH regulator in the third step is one or more of nitric acid, hydrochloric acid and sulfuric acid, and the alkaline pH regulator is one or more of ammonia water, ammonium bicarbonate, sodium bicarbonate and sodium hydroxide.

The drying temperature in the fourth step is 70 ~ 120 ℃, preferably 80 ~ 100 ℃, and the drying time is 10 ~ 24 h, preferably 18 ~ 20 h.

The calcination temperature in the fifth step is 500 ~ 1100 ℃, and the preferred calcination temperature is 700 ~ 900 ℃.

The invention has the beneficial effects that: compared with the prior art, the technical scheme of the invention is adopted, the coprecipitation method generates the powder material with small average particle size, uniform dispersion and less agglomeration, the method is simple to operate and has simple requirements on raw materials, the raw materials are inorganic saline solution, the preparation of the coprecipitation method can be prepared under acidic, neutral and alkaline conditions, and the white powder precursor formed by the method can be sintered at lower temperature to obtain the uniformly dispersed powder material.

The white powder precursor is calcined at 500 ℃ to prepare Ho³⁺、Yb³⁺Codoped Y (PO)₃)₃Crystal and strong up-conversion luminescence intensity. The raw materials required by the invention can be purchased from the market, the used equipment is common equipment without special requirements, the preparation process is simple, the cost is low, the large-scale batch production is easy to realize, and the good use effect is obtained.

Drawings

FIG. 1 is Y prepared according to example 1 of the present invention_0.6975(PO₃)₃:Ho_0.0025, Yb_0.3An X-ray powder diffraction pattern of a red light up-conversion luminescent material;

FIG. 2 is Y prepared according to example 2 of the present invention _x0.8-(PO₃)₃:Ho _x , Yb_0.2(x= 0.0025, 0.005, 0.01,0.02, 0.05) at 980 nm;

FIG. 3 is Y prepared in example 3 of the present invention_0.59(PO₃)₃:Ho_0.01, Yb_0.4An X-ray powder diffraction pattern of a red light up-conversion luminescent material;

FIG. 4 is Y prepared in example 4 of the present invention_0.795(PO₃)₃:Ho_0.005, Yb_0.2A room-temperature emission spectrum of the red light up-conversion luminescent material under the excitation of 980nm light;

FIG. 5 is Y prepared in example 5 of the present invention_0.949(PO₃)₃:Ho_0.001, Yb_0.05A room-temperature emission spectrum of the red light up-conversion luminescent material under the excitation of 980nm light;

FIG. 6 is Y prepared in example 6 of the present invention_0.495(PO₃)₃:Ho_0.005, Yb_0.5Room temperature emission spectrum of red light up-conversion luminescent material under excitation of 980nm lightFigure (a).

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings.