CN103525419B - Method for preparing nitrogen oxygen silicate luminescent material in normal pressure and at low temperature - Google Patents

Abstract

The invention relates to a method for preparing oxynitride silicate luminescent material under normal pressure and low temperature, which belongs to the technical field of luminescent material. The method solves the technical problems of high temperature required, long time consumption and high cost in the method for preparing the oxynitride silicate luminescent material in the prior art. In the method of the present invention, metal nitrate is used as the source of metal ions, tetraethyl orthosilicate is used as the source of silicon, a complexing agent and a crosslinking agent are added, a sol is first prepared by a sol-gel method, and then the obtained sol is prepared at 60-90 ℃ heating and evaporating to dryness, pre-burning at 400-600℃ for 1-6h, and then sintering at 700-800℃ for 3-5h to obtain the precursor, and finally put the obtained precursor in a container, pass through ammonia gas, and raise the temperature to 1150 Calcining at -1200°C for 4-12 hours under normal pressure, cooling to obtain oxynitride silicate luminescent material. The method of the invention has simple operation steps, low reaction sintering temperature, short sintering time and low cost.

Description

Method for preparing oxynitride silicate luminescent material under normal pressure and low temperature

technical field

The invention relates to a method for preparing an oxynitride silicate luminescent material under normal pressure and low temperature, and belongs to the technical field of luminescent materials.

Background technique

Nitride phosphor has unique excitation spectrum (excitation range covers ultraviolet, near ultraviolet, blue light and even green light) and excellent luminescence characteristics (emission of blue, green, yellow, red light, small thermal quenching, high luminous efficiency) , The material itself has the advantages of non-toxicity and good stability, and is widely used in white light LEDs.

In the prior art, nitrides and nitrogen oxides are mostly formed by sintering oxide or nitride raw materials in a high-temperature, high-pressure nitrogen or ammonia atmosphere by using a high-temperature solid-state method (the effect of the nitrogen or ammonia atmosphere is to ensure that the nitrides The raw material is not oxidized and the nitride or nitrogen oxide products are prevented from being oxidized). The temperatures required by these methods are all above 1500°C, and require repeated sintering for a long time. For example, LiuRu-Shi et al. reported on Chem.Mater. in 2011 that β-SiAlON: Pr ³⁺ phosphor was prepared by high-temperature solid-state method at a pressure of 0.92MPa and a temperature of 1950°C; JingXi- Ping et al. reported on Inorg.Chem. in 2012 that a Sr ₃ Si ₂ O ₄ N ₂ :Eu ²⁺ /Ce ³⁺ luminescent material was prepared by a high-temperature solid-state method at 1550°C. Although the luminescent materials prepared by these methods have good luminescent properties, the high sintering temperature and long sintering time in the preparation process limit the further research and development of LED phosphors, and the use of silicon nitride as a raw material increases the preparation cost.

Contents of the invention

The purpose of the present invention is to solve the technical problems of high temperature, time-consuming and high cost in the method for preparing oxynitride silicate luminescent materials in the prior art, and to provide a method for preparing oxynitride silicate luminescent materials under normal pressure and low temperature. method.

The method for preparing oxynitride silicate luminescent material under normal pressure and low temperature of the present invention comprises the following steps:

(1) Using metal nitrate as a source of metal ions, taking tetraethyl orthosilicate as a silicon source, adding a complexing agent and a crosslinking agent, and preparing a sol by a sol-gel method;

The nitrate of the metal is a nitrate of a matrix metal, or a mixture of a nitrate of a matrix metal and a nitrate of a dopant ion;

(2) Heat and evaporate the sol obtained in step (1) to dryness at 60-90°C, then pre-fire at 400-600°C for 1-6h, and then sinter at 700-800°C for 3-5h to obtain oxynitride silicate luminescent material the precursor of

(3) Put the precursor obtained in step (2) in a container, pass through ammonia gas, heat up to 1150-1200° C., calcinate under normal pressure for 4-12 hours, and cool to obtain the oxynitride silicate luminescent material.

Preferably, step (3) is calcined under pressure for 4-12 hours, more preferably, calcined under pressure of 0.11-1.0 MPa for 4-12 hours.

Preferably, the nitrate of the matrix metal is Y(NO ₃ ) ₃ , and the nitrate of the dopant ion is one of Ce(NO ₃ ) ₃ , Eu(NO ₃ ) ₃ , Tb(NO ₃ ) ₃ species or a mixture of several.

Preferably, the oxynitride silicate luminescent material is Y _4(1-x) Si ₂ N ₂ O ₇ :xA ³⁺ or Y _5(1-x) Si ₃ O ₁₂ N:xA ³⁺ , wherein, A is a mixture of one or more of Ce, Eu, Tb, and x is 0-0.1.

Preferably, the complexing agent is citric acid monohydrate or salicylic acid.

Preferably, the cross-linking agent is polyethylene glycol (PEG), and the molecular weight of polyethylene glycol is 10000-20000.

Preferably, the preparation method of the sol is:

(1) adding metal nitrates to deionized water, stirring evenly to obtain a solution;

(2) Adding a complexing agent to the above solution, stirring evenly, so that the complexing agent and the metal ion are fully coordinated to obtain a coordinated solution;

(3) adding a solution dissolved with ethyl orthosilicate to the above-mentioned coordinated solution, stirring evenly to obtain a mixed solution;

(4) Add a cross-linking agent to the mixed solution, and stir at room temperature above 300 rpm to obtain a sol.

Preferably, the stirring speed of the step (4) is 300-500 rpm.

Preferably, the molar ratio of the metal nitrate to the complexing agent is 1:2, and the concentration of the crosslinking agent in the mixed solution is 0.1-0.12 g/mL.

Beneficial effects of the present invention:

(1) The present invention prepares sol with non-nitride raw materials, removes carbon in the system by calcining in step (2), then provides nitrogen source and reducing atmosphere with ammonia atmosphere, and calcines at lower temperature and normal pressure to obtain nitrogen oxide Silicate luminescent material;

(2) The operation steps of the present invention are simple, the reaction sintering temperature is low, the sintering time is short, the raw material cost used is low, repeatability is strong, can realize batch preparation, reduced workload and energy consumption, avoided existing preparation The high temperature, high pressure, and long-time sintering conditions required by the method can be used to prepare oxynitride silicate luminescent materials for white LEDs;

(3) The method of the present invention can also be implemented under pressure. When the sintering temperature and sintering time are the same, the crystallinity of the product obtained under pressure (0.11-1.0MPa) will be better, and the luminescence performance of the material will be improved. higher.

Description of drawings

Figure 1 is the XRD (X-ray diffraction) spectrum of the precursor prepared in Example 2 of the present invention, the XRD spectrum of Y _3.96 Si ₂ N ₂ O ₇ :0.01Ce ³⁺ and the standard of Y ₄ Si ₂ N ₂ O ₇ XRD spectrum card;

Fig. 2 is the excitation spectrum and emission spectrum of the Y _3.96 Si ₂ N ₂ O ₇ :0.01Ce ³⁺ luminescent material prepared in Example 2 of the present invention.

Detailed ways

The method for preparing oxynitride silicate luminescent material under normal pressure and low temperature comprises the following steps:

(1) Using metal nitrate as a source of metal ions, taking tetraethyl orthosilicate as a silicon source, adding a complexing agent and a crosslinking agent, and preparing a sol by a sol-gel method;

The nitrate of the metal is a nitrate of a matrix metal, or a mixture of a nitrate of a matrix metal and a nitrate of a dopant ion;

The amount of metal nitrate and silicon source is weighed according to the stoichiometric ratio of the chemical formula of the oxynitride silicate luminescent material to be prepared, and the dopant ions can usually replace 0-0.1 of the amount of the substituted cation in the matrix metal;

(2) Heat and evaporate the sol obtained in step (1) to dryness at 60-90°C, then pre-sinter at 400-600°C for 1-6h, and then sinter at 700-800°C for 3-5h to remove carbon, and obtain nitrogen oxysilicic acid Precursors of salt luminescent materials;

(3) Put the precursor obtained in step (2) in a container, pass through ammonia gas, heat up to 1150-1200° C., calcinate under normal pressure for 4-12 hours, and cool to obtain the oxynitride silicate luminescent material.

The present invention can also be implemented under pressure. When the sintering temperature and sintering time are the same, step (3) is calcined under pressure, especially under the condition of 0.11-1.0MPa, the crystallinity of the obtained product will be better, and the material The luminescent performance will be higher; the calcination time is preferably 5-10h.

The method of the present invention is applicable to all oxynitride silicate luminescent materials, especially the chemical formula Y _4(1-x) Si ₂ N ₂ O ₇ :xA ³⁺ or Y _5(1-x) Si ₃ O ₁₂ N:xA ³⁺ oxynitride silicate luminescent material, wherein, A is a mixture of one or more of Ce, Eu, Tb, when it is a mixture of several ions, the mixing ratio is not limited, and x is 0-0.1; When the matrix metal nitrate is Y(NO ₃ ) ₃ , the dopant ion nitrate is one or more of Ce(NO ₃ ) ₃ , Eu(NO ₃ ) ₃ , Tb(NO ₃ ) ₃ mix.

In the present invention, the forms of Y(NO ₃ ) ₃ , Ce(NO ₃ ) ₃ , Eu(NO ₃ ) ₃ and Tb(NO ₃ ) ₃ are not limited, and can also be added in the form of crystal hydrates, such as Y( NO ₃ ) ₃ ·6H ₂ O, Ce(NO ₃ ) ₃ ·6H ₂ O, Tb(NO ₃ ) ₃ ·6H ₂ O, Eu(NO ₃ ) ₃ ·6H ₂ O, etc. These metal nitrates can be It can be purchased or prepared by heating reaction of metal oxide and dilute HNO ₃ .

In the method of the present invention, the pre-calcination time of step (2) is preferably 2-4 hours, and the temperature is preferably 500°C.

In the method of the present invention, the complexing agent is citric acid monohydrate or salicylic acid.

In the method of the present invention, the crosslinking agent is polyethylene glycol (PEG), wherein the molecular weight of PEG is preferably 10000-20000.

Among the present invention, the preparation method of described sol is:

(1) adding the nitrate of matrix metal into deionized water, stirring for 5-30min, to obtain a solution;

Or mix the nitrate of the matrix metal and the nitrate of the doped ion, add deionized water, and stir for 5-30 minutes to obtain a solution;

(2) Add a complexing agent to the above solution, and stir for 10-30min to obtain a complexing agent solution;

(3) Add a solution dissolved in ethyl orthosilicate to the above-mentioned complexing agent solution, and stir for 10-30min to obtain a mixed solution;

(4) Add a cross-linking agent to the mixed solution, stir at 300-500 rpm at room temperature, preferably 400 rpm, for 1-3 hours to obtain a sol.

In the method of the present invention, the solution that is dissolved with ethyl orthosilicate is preferably the dehydrated alcohol solution of ethyl orthosilicate.

In the method of the present invention, the crosslinking agent and the complexing agent are added according to the amount of the nitrogen oxysilicate luminescent material to be prepared, and the excess is also acceptable. The molar ratio of the metal nitrate and the complexing agent is preferably 1:2, and the The concentration of the linking agent in the mixed solution is 0.07-0.2 g/mL, preferably 0.1-0.12 g/mL.

As a preferred solution, the sol preparation process of Y _4(1-x) Si ₂ N ₂ O ₇ :xCe ³⁺ (x=0-0.1) is as follows: heat Y ₂ O ₃ with dilute HNO ₃ to dissolve, add deionized Dilute with water to prepare Y(NO ₃ ) ₃ solution; weigh Ce(NO ₃ ) ₃ and add it to Y(NO ₃ ) ₃ solution, add deionized water, stir for 5-30min, then add lemon monohydrate to the above solution acid, after stirring for 10-30min, add orthosilicate ethyl ester dissolved in an appropriate amount of absolute ethanol to the above mixed solution, stir evenly, add PEG with a molecular weight of 10000-20000 (the concentration of PEG in the solution is 0.1-0.12g /mL), stirred at room temperature for 1-3h to obtain a sol;

The molar ratio of Y, Ce, complexing agent and TEOS is (1-x):x:2:0.5, and the concentration of PEG in the solution is preferably 0.1-0.12 g/mL.

The oxynitride silicate luminescent material prepared by the invention can emit bright blue light under the excitation of near ultraviolet light.

The structural formula of the oxynitride silicate luminescent material prepared by the present invention is tested by XRD, and the test conditions are: use a Bruker D8 focal point diffractometer to measure the XRD pattern of the sample at room temperature, the scanning range is 10-60°, and the scanning speed is 10°/min .

The luminescence performance of the nitrogen oxysilicate luminescent material prepared by the present invention is tested by excitation spectrum and emission spectrum. The test conditions are: Hitachi F-7000 fluorescence spectrometer, 150W xenon lamp as excitation light source, and measurement at normal temperature.

The present invention will be described in further detail below in conjunction with the accompanying drawings and embodiments. The raw materials used in the examples of the present invention are Y ₂ O ₃ with a purity of 99.99%; Ce(NO ₃ ) ₃ 6H ₂ O, Tb(NO ₃ ) ₃ 6H ₂ O, Eu(NO ₃ ) ₃ 6H ₂ O, absolute ethanol, citric acid, TEOS, polyethylene glycol, and _HNO3 were analytically pure, and all of the above raw materials could be obtained commercially.

Example 1

Preparation of Y _4(1-x) Si ₂ N ₂ O ₇ :xCe ³⁺ (x=0.005):

(1) Heat Y ₂ O ₃ with a certain concentration of dilute HNO ₃ to dissolve, add deionized water to dilute, and prepare a Y(NO ₃ ) ₃ solution with a concentration of 0.5mol/L; weigh 0.0022gCe(NO ₃ ) ₃ 6H ₂ O was added to 7.96mL LY(NO ₃ ) ₃ solution, and deionized water was added until the volume of the solution was 10mL. After stirring for 15 minutes, 1.6811g of citric acid monohydrate was added to the above solution; after stirring for 15 minutes, add Add 0.4167g of TEOS dissolved in 10mL of absolute ethanol; after stirring for 30min, add 2g of PEG with a molecular weight of 10000, and stir at 400rpm for 2h at room temperature to make the above solution into a sol;

(2) Transfer the sol to a dish, heat and evaporate to dryness in a water bath at 60°C to obtain a gel; pre-burn the gel in a muffle furnace at 500°C for 2 hours; simply grind the obtained product and transfer it to In a corundum crucible, sinter at 700°C for 3 hours to obtain the precursor of oxynitride silicate;

(3) Put the precursor prepared in step (2) in a tube furnace, pass through ammonia gas, heat up to 1150°C, and calcinate for 4 hours under normal pressure; after the calcination, cool to room temperature, take out the sample to obtain nitrogen oxide Silicate luminescent material.

Example 2

Embodiment 2 is illustrated in conjunction with Fig. 1 and Fig. 2

Preparation of Y _4(1-x) Si ₂ N ₂ O ₇ :xCe ³⁺ (x=0.01):

(1) Heat Y ₂ O ₃ with a certain concentration of dilute HNO ₃ to dissolve, add deionized water to dilute, and prepare a Y(NO ₃ ) ₃ solution with a concentration of 0.5mol/L; weigh 0.0043gCe(NO ₃ ) ₃ 6H ₂ O was added to 7.92mL LY(NO ₃ ) ₃ solution, and deionized water was added until the volume of the solution was 10mL. After stirring for 15 minutes, 1.6811g of citric acid monohydrate was added to the above solution; after stirring for 15 minutes, add Add 0.4167g of TEOS dissolved in 10mL of absolute ethanol; after stirring for 30min, add 2.4g of PEG with a molecular weight of 10000, and stir at 400rpm for 2h at room temperature to make the above solution into a sol;

(2) Transfer the sol to a dish, heat and evaporate to dryness in a water bath at 70°C to obtain a gel; pre-fire the gel in a muffle furnace at 500°C for 3 hours; simply grind the obtained product and transfer it to In a corundum crucible, sinter at 750 ° C for 4 hours to obtain the precursor of oxynitride silicate;

(3) Put the precursor prepared in step (2) in a tube furnace, pass through ammonia gas, heat up to 1150oC, and calcinate for 10 hours under normal pressure; after the calcination, cool to room temperature, take out the sample to obtain silicon oxynitride Salt luminescent material.

In Figure 1, curve a is the XRD spectrum of the precursor, curve b is the XRD spectrum of Y _3.96 Si ₂ N ₂ O ₇ :0.01Ce ³⁺ , and curve c is the standard XRD spectrum of Y ₄ Si ₂ N ₂ O ₇ Figure card; As can be seen from Fig. 1, the XRD collection of spectra of Y _3.96 Si ₂ N ₂ O ₇ :0.01Ce ³⁺ prepared by the method of the present invention and the standard XRD collection of spectra of Y ₄ Si ₂ N ₂ O ₇ material absorption peaks are basically Similarly, it proves that the method of the present invention can prepare oxynitride silicate luminescent materials.

In Figure 2, Curve 1 is the excitation spectrum of Y _3.96 Si ₂ N ₂ O ₇ :0.01Ce ³⁺ , and Curve 2 is the emission spectrum of Y _3.96 Si ₂ N ₂ O ₇ :0.01Ce ³⁺ , as can be seen from Figure 2 , Y _3.96 Si ₂ N ₂ O ₇ :0.01Ce ³⁺ luminescent material has an absorption peak at 365nm in the excitation spectrum, and an absorption peak at 441nm in the emission spectrum, indicating that the prepared oxynitride silicate luminescent material is a blue-light fluorescent material. When excited by near-ultraviolet light, the sample can emit bright blue light.

Example 3

Preparation of Y _4(1-x) Si ₂ N ₂ O ₇ :xCe ³⁺ (x=0.05):

(1) Heat Y ₂ O ₃ with a certain concentration of dilute HNO ₃ to dissolve, add deionized water to dilute, and prepare a Y(NO ₃ ) ₃ solution with a concentration of 0.5mol/L; weigh 0.0217gCe(NO ₃ ) 3.6H ₂ O was added to 7.6mL LY(NO ₃ ) ₃ solution, _and deionized water was added until the volume of the solution was 10mL. After stirring for 30min, 1.6811g of citric acid monohydrate was added to the above solution; after stirring for 15min, add to the above mixed solution Add 0.4167g of TEOS dissolved in 10mL of absolute ethanol; after stirring for 30min, add 2g of PEG with a molecular weight of 20000, and stir at room temperature for 2h at 500rpm to make the above solution into a sol;

(2) Transfer the sol to a dish, heat and evaporate to dryness in a water bath at 80°C to obtain a gel; pre-burn the gel in a muffle furnace at 500°C for 4 hours; simply grind the obtained product and transfer it to In a corundum crucible, sinter at 800°C for 4 hours to obtain the precursor of oxynitride silicate;

(3) Put the precursor prepared in step (2) in a tube furnace, pass through ammonia gas, heat up to 1200°C, and calcinate for 5 hours under normal pressure; after the calcination, cool to room temperature, take out the sample to obtain nitrogen oxide Silicate luminescent material.

Example 4

Preparation of Y _4(1-x) Si ₂ N ₂ O ₇ :xCe ³⁺ (x=0.01):

(1) Heat Y ₂ O ₃ with a certain concentration of dilute HNO ₃ to dissolve, add deionized water to dilute, and prepare a Y(NO ₃ ) ₃ solution with a concentration of 0.5mol/L; weigh 0.0043gCe(NO ₃ ) ₃ 6H ₂ O was added to 7.92mL LY(NO ₃ ) ₃ solution, and deionized water was added until the volume of the solution was 10mL. After stirring for 5 minutes, 1.6811g of citric acid monohydrate was added to the above solution; after stirring for 10 minutes, add Add 0.4167g of TEOS dissolved in 10mL of absolute ethanol; after stirring for 15min, add 2.4g of PEG with a molecular weight of 20000, and stir at 300rpm at room temperature for 3h to make the above solution into a sol;

(2) Transfer the sol to a dish, heat and evaporate to dryness in a water bath at 90°C to obtain a gel; pre-burn the gel in a muffle furnace at 500°C for 6 hours; simply grind the obtained product and transfer it to In a corundum crucible, sinter at 800°C for 5 hours to obtain the precursor of oxynitride silicate;

(3) Put the precursor prepared in step (2) in a tube furnace, pass through ammonia gas, heat up to 1200°C, and calcinate for 10 hours under normal pressure; after the calcination, cool to room temperature, take out the sample to obtain nitrogen oxide Silicate luminescent material.

Example 5

Preparation of Y _4(1-x) Si ₂ N ₂ O ₇ :xTb ³⁺ (x=0.02):

(1) Heat Y ₂ O ₃ with a certain concentration of dilute HNO ₃ to dissolve, add deionized water to dilute, and prepare a Y(NO ₃ ) ₃ solution with a concentration of 0.5mol/L; weigh 0.0091gTb(NO ₃ ) ₃ 6H ₂ O was added to 7.84mL LY(NO ₃ ) ₃ solution, and deionized water was added until the volume of the solution was 10mL. After stirring for 5 minutes, 1.6811g of citric acid monohydrate was added to the above solution; after stirring for 10 minutes, add Add 0.4167g of TEOS dissolved in 10mL of absolute ethanol; after stirring for 15min, add 2.2g of PEG with a molecular weight of 20000, and stir at 400rpm for 2h at room temperature to make the above solution into a sol;

(2) Transfer the sol to a dish, heat and evaporate to dryness in a water bath at 80°C to obtain a gel; pre-burn the gel in a muffle furnace at 500°C for 3 hours; simply grind the obtained product and transfer it to In a corundum crucible, sinter at 800°C for 4 hours to obtain the precursor of oxynitride silicate;

(3) Put the precursor prepared in step (2) in a tube furnace, pass through ammonia gas, heat up to 1200°C, and calcinate for 7 hours under normal pressure; after the calcination, cool to room temperature, take out the sample to obtain nitrogen oxide Silicate luminescent material.

Example 6

Preparation of Y _4(1-x) Si ₂ N ₂ O ₇ :xEu ³⁺ (x=0.05):

(1) Heat Y ₂ O ₃ with a certain concentration of dilute HNO ₃ to dissolve, add deionized water to dilute, and prepare a Y(NO ₃ ) ₃ solution with a concentration of 0.5mol/L; weigh 0.0223gEu(NO ₃ ) ₃ 6H ₂ O was added to 7.6mL LY(NO ₃ ) ₃ solution, and deionized water was added until the volume of the solution was 10mL. After stirring for 5 minutes, 1.6811g of citric acid monohydrate was added to the above solution; after stirring for 10 minutes, add to the above mixed solution Add 0.4167g of TEOS dissolved in 10mL of absolute ethanol; after stirring for 15min, add 2g of PEG with a molecular weight of 20000, and stir at 300rpm for 3h at room temperature to make the above solution into a sol;

(2) Transfer the sol to a dish, heat and evaporate to dryness in a water bath at 75°C to obtain a gel; pre-burn the gel in a muffle furnace at 500°C for 5 hours; simply grind the obtained product and transfer it to In a corundum crucible, sinter at 750°C for 5 hours to obtain the precursor of oxynitride silicate;

(3) Put the precursor prepared in step (2) in a tube furnace, pass through ammonia gas, heat up to 1200°C, and calcinate for 5 hours under normal pressure; after the calcination, cool to room temperature, take out the sample to obtain nitrogen oxide Silicate luminescent material.

Example 7

Preparation of Y ₄ Si ₂ N ₂ O ₇ :

(1) Weigh 7.92mL of LY(NO ₃ ) ₃ (0.5mol/L) solution, add deionized water until the volume of the solution is 10mL, stir for 10min, then add 1.6811g of citric acid monohydrate to the above solution; stir for 10min Then add 0.4167g of TEOS dissolved in 10mL of absolute ethanol to the above mixed solution; after stirring for 10min, add 2.4g of PEG with a molecular weight of 20000, and stir at 400rpm at room temperature for 2h to make the above solution into a sol;

(2) Transfer the sol to a dish, heat and evaporate to dryness in a water bath at 65°C to obtain a gel; pre-burn the gel in a muffle furnace at 500°C for 1.5h; simply grind the obtained product and transfer into a corundum crucible and sintered at 800°C for 5 hours to obtain a precursor of oxynitride silicate.

(3) Put the precursor prepared in step (2) in a tube furnace, pass through ammonia gas, heat up to 1200°C, and calcinate for 9 hours under normal pressure; after the calcination, cool to room temperature, take out the sample to obtain inorganic nitrogen oxide material.

Example 8

Preparation of Y _4(1-x) Si ₂ N ₂ O ₇ :x(0.3Eu ³⁺ :0.7Tb ³⁺ )(x=0.1):

(1) Heat Y ₂ O ₃ with a certain concentration of dilute HNO ₃ to dissolve, add deionized water to dilute, and prepare a Y(NO ₃ ) ₃ solution with a concentration of 0.5mol/L; weigh 0.01338gEu(NO ₃ ) ₃ 6H ₂ O and add 0.0315g Tb(NO ₃ ) ₃ 6H ₂ O to 7.2mL LY(NO ₃ ) ₃ solution, add deionized water until the volume of the solution is 10mL, stir for 5min, then add 1.6811g- Hydrate citric acid; after stirring for 10 minutes, add 0.4167 g of TEOS dissolved in 10 mL of absolute ethanol to the above mixed solution; after stirring for 30 minutes, add 2 g of PEG with a molecular weight of 20,000, and stir at room temperature for 3 hours at 300 rpm to make the above solution into a sol;

(2) Transfer the sol to a dish, heat and evaporate to dryness in a water bath at 75°C to obtain a gel; pre-burn the gel in a muffle furnace at 500°C for 2 hours; simply grind the obtained product and transfer it to In a corundum crucible, sinter at 750°C for 2 hours to obtain the precursor of oxynitride silicate;

(3) Put the precursor prepared in step (2) in a tube furnace, pass through ammonia gas, heat up to 1200°C, and calcinate for 5 hours under normal pressure; after the calcination, cool to room temperature, take out the sample to obtain nitrogen oxide Silicate luminescent material.

Example 9

Preparation of Y _5(1-x) Si ₃ O ₁₂ N:xCe ³⁺ (x=0.01):

(1) Heat Y ₂ O ₃ with a certain concentration of dilute HNO ₃ to dissolve, add deionized water to dilute, and prepare a Y(NO ₃ ) ₃ solution with a concentration of 0.5mol/L; weigh 0.0043gCe(NO ₃ ) 3.6H ₂ O was added to 9.9mL LY(NO ₃ ) ₃ solution, _and deionized water was added until the volume of the solution was 10mL. After stirring for 15 minutes, 2.1014g of citric acid monohydrate was added to the above solution; after stirring for 15 minutes, add to the above mixed solution Add 0.625 g of TEOS dissolved in 10 mL of absolute ethanol; after stirring for 30 min, add 2.4 g of PEG with a molecular weight of 10,000, and stir at 300 rpm for 2 h at room temperature to make the above solution into a sol;

(2) Transfer the sol to a dish, heat and evaporate to dryness in a water bath at 70°C to obtain a gel; pre-fire the gel in a muffle furnace at 500°C for 3 hours; simply grind the obtained product and transfer it to In a corundum crucible, sinter at 750 ° C for 4 hours to obtain the precursor of oxynitride silicate;

(3) Put the precursor prepared in step (2) in a tube furnace, pass through ammonia gas, heat up to 1200°C, and calcinate for 10 hours under normal pressure; after the calcination, cool to room temperature, take out the sample to obtain nitrogen oxide Silicate luminescent material.

Example 10

Preparation of Y _5(1-x) Si ₃ O ₁₂ N:xCe ³⁺ (x=0.05):

(1) Heat Y ₂ O ₃ with a certain concentration of dilute HNO ₃ to dissolve, add deionized water to dilute, and prepare a Y(NO ₃ ) ₃ solution with a concentration of 0.5mol/L; weigh 0.0217gCe(NO ₃ ) ₃ 6H ₂ O was added to 9.5mL LY(NO ₃ ) ₃ solution, and deionized water was added until the volume of the solution was 10mL. After stirring for 30min, 2.1014g of citric acid monohydrate was added to the above solution; after stirring for 15min, add to the above mixed solution Add 0.625 g of TEOS dissolved in 10 mL of absolute ethanol; after stirring for 30 min, add 2.2 g of PEG with a molecular weight of 10,000, and stir at 400 rpm for 2 h at room temperature to make the above solution into a sol;

(2) Transfer the sol to a dish, heat and evaporate to dryness in a water bath at 80°C to obtain a gel; pre-burn the gel in a muffle furnace at 500°C for 4 hours; simply grind the obtained product and transfer it to In a corundum crucible, sinter at 800°C for 4 hours to obtain the precursor of oxynitride silicate;

(3) Put the precursor prepared in step (2) in a tube furnace, pass through ammonia gas, heat up to 1150°C, and calcinate for 8 hours under normal pressure; after the calcination, cool to room temperature, take out the sample to obtain nitrogen oxide Silicate luminescent material.

Example 11

Preparation of Y _5(1-x) Si ₃ O ₁₂ N:xTb ³⁺ (x=0.02):

(1) Heat Y ₂ O ₃ with a certain concentration of dilute HNO ₃ to dissolve, add deionized water to dilute, and prepare a Y(NO ₃ ) ₃ solution with a concentration of 0.5mol/L; weigh 0.0091gTb(NO ₃ ) 3.6H ₂ O was added to 9.8mL LY(NO ₃ ) ₃ solution, _and deionized water was added until the volume of the solution was 10mL. After stirring for 5 minutes, 2.1014g of citric acid monohydrate was added to the above solution; after stirring for 10 minutes, add Add 0.625 g of TEOS dissolved in 10 mL of absolute ethanol; after stirring for 15 min, add 2.4 g of PEG with a molecular weight of 20,000, and stir at room temperature for 1 h at 500 rpm to make the above solution into a sol;

(2) Transfer the sol to a dish, heat and evaporate to dryness in a water bath at 65°C to obtain a gel; pre-burn the gel in a muffle furnace at 450°C for 5 hours; simply grind the obtained product and transfer it to In a corundum crucible, sinter at 800°C for 5 hours to obtain the precursor of oxynitride silicate;

(3) Put the precursor prepared in step (2) in a tube furnace, pass through ammonia gas, heat up to 1150°C, and calcinate for 9 hours under normal pressure; after the calcination, cool to room temperature, take out the sample to obtain nitrogen oxide Silicate luminescent material.

Example 12

Preparation of Y _5(1-x) Si ₃ O ₁₂ N:xEu ³⁺ (x=0.05):

(1) Heat Y ₂ O ₃ with a certain concentration of dilute HNO ₃ to dissolve, add deionized water to dilute, and prepare a Y(NO ₃ ) ₃ solution with a concentration of 0.5mol/L; weigh 0.0223gEu(NO ₃ ) ₃ 6H ₂ O was added to 9.5mL LY(NO ₃ ) ₃ solution, and deionized water was added until the volume of the solution was 10mL. After stirring for 5 minutes, 2.1014g of citric acid monohydrate was added to the above solution; after stirring for 10 minutes, add Add 0.625 g of TEOS dissolved in 10 mL of absolute ethanol; after stirring for 15 min, add 2 g of PEG with a molecular weight of 10,000, and stir at room temperature for 3 h at 400 rpm to make the above solution into a sol;

(2) Transfer the sol to a dish, heat and evaporate to dryness in a water bath at 80°C to obtain a gel; pre-burn the gel in a muffle furnace at 600°C for 2 hours; simply grind the obtained product and transfer it to In a corundum crucible, sinter at 700°C for 5 hours to obtain the precursor of oxynitride silicate;

(3) Put the precursor prepared in step (2) in a tube furnace, feed ammonia gas, heat up to 1200°C, and calcine for 8 hours under normal pressure; after calcination, cool to room temperature, take out the sample to obtain nitrogen oxide Silicate luminescent material.

Example 13

Preparation of Y ₅ Si ₃ O ₁₂ N:

(1) Weigh 10mL of LY(NO ₃ ) ₃ (0.5mol/L) solution, stir for 30min, add 2.1014g of citric acid monohydrate to the above solution; stir for 15min, add 0.625g of 10 mL of TEOS in absolute ethanol; after stirring for 30 min, add 2 g of PEG with a molecular weight of 20,000, and stir at 500 rpm for 2 h at room temperature to make the above solution into a sol;

(2) Transfer the sol to a dish, place it in a water bath at 75° C. and evaporate it to dryness to obtain a gel; pre-burn the gel in a muffle furnace at 500° C. for 3 hours; simply grind the obtained product and transfer it to In a corundum crucible, sinter at 750 ° C for 4 hours to obtain the precursor of oxynitride silicate;

(3) Put the precursor prepared in step (2) in a tube furnace, pass through ammonia gas, heat up to 1200°C, and calcinate for 7 hours under normal pressure; after the calcination, cool to room temperature, take out the sample to obtain inorganic nitrogen oxide material.

Example 14

Preparation of Y _5(1-x) Si ₃ O ₁₂ N:x(0.5Tb ³⁺ :0.5Ce ³⁺ )(x=0.1):

(1) Heat Y ₂ O ₃ with a certain concentration of dilute HNO ₃ to dissolve, add deionized water to dilute, and prepare a Y(NO ₃ ) ₃ solution with a concentration of 0.5mol/L; weigh 0.02265gTb(NO ₃ ) ₃ 6H ₂ O and 0.0217g Ce(NO ₃ ) ₃ 6H ₂ O were added to 9mL LY(NO ₃ ) ₃ solution, and deionized water was added until the volume of the solution was 10mL. After stirring for 5min, 2.1014g monohydrate Citric acid; after stirring for 10 min, add 0.625 g of TEOS dissolved in 10 mL of absolute ethanol to the above mixed solution; after stirring for 15 min, add 2.4 g of PEG with a molecular weight of 20,000, and stir at room temperature for 1 h at 500 rpm to make the above solution into a sol;

(2) Transfer the sol to a dish, heat and evaporate to dryness in a water bath at 90°C to obtain a gel; pre-fire the gel in a muffle furnace at 450°C for 6 hours; simply grind the obtained product and transfer it to In a corundum crucible, sinter at 800°C for 5 hours to obtain the precursor of oxynitride silicate;

(3) Put the precursor prepared in step (2) in a tube furnace, pass through ammonia gas, heat up to 1150°C, and calcinate under normal pressure for 12 hours; after the calcination, cool to room temperature, take out the sample to obtain nitrogen oxide Silicate luminescent material.

Apparently, the descriptions of the above embodiments are only used to help understand the method and core idea of the present invention. It should be pointed out that for those of ordinary skill in the technical field, without departing from the principle of the present invention, some improvements and modifications can also be made to the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention .

Claims (10)

1. prepare the method for nitrogen-oxygen-silicon salt luminescent material under atmospheric low-temperature, it is characterized in that, comprise the following steps:

(1) originate as metal ion using the nitrate of metal, be silicon source with tetraethoxy, add coordination agent and linking agent, prepare colloidal sol by sol-gel method;

The nitrate of described metal is the nitrate of matrix metal, or is the mixture of the nitrate of matrix metal and the nitrate of dopant ion;

(2) colloidal sol step (1) obtained, at 60-90 DEG C of heating evaporate to dryness, then at 400-600 DEG C of pre-burning 1-6h, then at 700-800 DEG C of sintering 3-5h, obtains the presoma of nitrogen-oxygen-silicon salt luminescent material;

(3) presoma obtained in step (2) is placed in container, passes into ammonia, be warming up to 1150-1200 DEG C, calcine 4-12h under normal pressure, cooling, namely obtains nitrogen-oxygen-silicon salt luminescent material.

2. prepare the method for nitrogen-oxygen-silicon salt luminescent material according to claim 1 under atmospheric low-temperature, it is characterized in that, described step (3) calcines 4-12h under an increased pressure.

3. prepare the method for nitrogen-oxygen-silicon salt luminescent material according to claim 2 under atmospheric low-temperature, it is characterized in that, described step (3) calcines 4-12h under 0.11-1.0MPa.

4. prepare the method for nitrogen-oxygen-silicon salt luminescent material according to claim 1 under atmospheric low-temperature, it is characterized in that, the nitrate of described matrix metal is Y (NO ₃) ₃, the nitrate of described dopant ion is Ce (NO ₃) ₃, Eu (NO ₃) ₃, Tb (NO ₃) ₃in the mixing of one or more.

5. prepare the method for nitrogen-oxygen-silicon salt luminescent material according to claim 1 under atmospheric low-temperature, it is characterized in that, described nitrogen-oxygen-silicon salt luminescent material is Y _{4 (1-x)}si ₂n ₂o ₇: xA ³⁺or Y _{5 (1-x)}si ₃o ₁₂n:xA ³⁺, wherein, A is the mixing of one or more in Ce, Eu, Tb, and x is 0-0.1.

6. prepare the method for nitrogen-oxygen-silicon salt luminescent material according to claim 1 under atmospheric low-temperature, it is characterized in that, described coordination agent is monohydrate potassium or Whitfield's ointment.

7. prepare the method for nitrogen-oxygen-silicon salt luminescent material according to claim 1 under atmospheric low-temperature, it is characterized in that, described linking agent is polyoxyethylene glycol, and molecular weight polyethylene glycol is 10000-20000.

8. prepare the method for nitrogen-oxygen-silicon salt luminescent material according to claim 1 under atmospheric low-temperature, it is characterized in that, the preparation method of described colloidal sol is:

(1) nitrate of metal is added deionized water, stir, obtain solution;

(2) in above-mentioned solution, add coordination agent, stir, make coordination agent and the complete coordination of metal ion, obtain solution after coordination;

(3) in solution after above-mentioned coordination, add the solution being dissolved with tetraethoxy, stir, obtain mixing solutions;

(4) in mixing solutions, add linking agent again, under room temperature, more than 300rpm stirs, and obtains colloidal sol.

9. prepare the method for nitrogen-oxygen-silicon salt luminescent material according to claim 8 under atmospheric low-temperature, it is characterized in that, the mixing speed of described step (4) is 300-500rpm.

10. prepare the method for nitrogen-oxygen-silicon salt luminescent material according to claim 8 under atmospheric low-temperature, it is characterized in that, the nitrate of described metal and the mol ratio of coordination agent are 1: 2, and the concentration of linking agent in mixing solutions is 0.07-0.2g/mL.