Post-annealing method for realizing emission from Eu < 3 + > high-energy-level excited state 5D1, 2, 3 in silicate oxyapatite, luminescent material and application

Abstract

The invention provides a post-annealing method for realizing emission from Eu < 3 + > high-energy-level excited state 5D1, 2, 3 in silicate oxyapatite, a luminescent material and application, and belongs to the technical field of luminescent materials. The post-annealing method comprises the following steps: heating Eu < 3 + >-doped silicate oxyapatite to T1 through a first heating section in a reducing atmosphere, carrying out first uniform heat treatment, and then cooling to T1 'through a first cooling section; heating to T2 through a second heating section, carrying out second uniform heat treatment, and then cooling to T2 'through a second cooling section; heating to T3 through a third heating section, carrying out third uniform heat treatment, cooling to T3 'through a third cooling section, and naturally cooling along with the furnace to obtain a final product emitted from the Eu < 3 + > high-energy-level excited state 5D1, 2 and 3. According to the invention, efficient and stable luminescence from Eu < 3 + > high-energy-level excited states 5D1, 2 and 3: 5D1 (green light), 5D2 (blue-green light) and 5D3 (blue light) can be realized through post-annealing treatment, meanwhile, red luminescence of 5D0-7FJ (J = 0, 1, 2, 3 and 4) is retained, and the obtained material is high in luminous efficiency and small in luminescence quenching at a high temperature.

Description

Technical Field

[0001] This disclosure belongs to the technical field of luminescent materials, and particularly relates to a post-annealing method, a luminescent material, and an application for realizing emission from high-energy excited states of Eu in silicate oxyapatite. 3+ High-energy excited state 5 D 1,2,3 emission, and applications. Background Art

[0002] The application of rare-earth ion-activated luminescent materials in different technical fields has been widely studied. Among them, europium ion Eu 3+ is the most common red luminescence activator, which has characteristic sharp spectral lines of forbidden transitions from 5 D 0 to 7 F J (J = 0, 1, 2, 3, 4), becoming a red luminescence center with pure chromaticity, high luminescence efficiency, and good thermal stability. For a long time, the research and application of Eu 3+ have only focused on the red luminescence from 5 D 0 → 7 F 0,1,2,3,4 Due to multi-phonon non-radiative transitions and cross-relaxation effects, the luminescence from high-energy excited states 5 D 1,2,3 is extremely easy to be quenched and difficult to be observed, which severely limits the application of Eu 3+ as an activator in the visible light band.

[0003] Therefore, if all-level luminescence transitions of Eu 3+ can be realized in a single matrix, that is, there are simultaneously luminescences from 5 D 1 (green light), 5 D 2 (blue-green light), 5 D 3 (blue light), and 5 D 0 (red light) excited states, the application range of Eu 3+ luminescence can be greatly broadened, a single white luminescence system activated by Eu 3+ can be obtained, and the application in the visible light band can be effectively expanded. However, in the existing literature, there are few materials that can realize the luminescence from 5 D 1,2,3 luminescence, mainly including fluorides, fluorides, and very few oxides. However, the luminescence efficiency of fluoride materials is low, and the synthesis conditions are harsh, requiring the use of a large amount of hydrofluoric acid, which pollutes the environment and is harmful to health. In very few oxide examples, their crystal lattices accommodate Eu 3+The doping concentration is very small, mostly below 1 mol%; and the luminescence efficiency is low. In Eu 3+ doped luminescent materials, the luminescence from high energy levels 5 D 1,2,3 is extremely prone to quenching, severely limiting their applications in the fields of luminescence and display. SUMMARY OF THE INVENTION

[0004] The present disclosure aims to at least solve one of the technical problems of the extremely easy quenching of the emission from the high energy levels of Eu 3+ doped luminescent materials, and provides a post-annealing method, a luminescent material and an application for realizing the emission from the high energy levels of Eu 3+ in silicate oxyapatite. 5 D 1,2,3 emission. 3+ in silicate oxyapatite. 5 D 1,2,3 emission, and a luminescent material and an application thereof.

[0005] On the one hand, the present disclosure provides a post-annealing method for realizing the emission from the high energy levels of Eu 3+ in silicate oxyapatite. 5 D 1,2,3 emission, and the post-annealing method includes: heating the Eu 3+ doped silicate oxyapatite to T 1 in a reducing atmosphere for the first homogenization heat treatment, and then cooling it to T 1 ' through the first cooling section; heating the silicate oxyapatite after the first-stage annealing treatment to T 2 for the second homogenization heat treatment, and then cooling it to T 2 ' through the second cooling section; heating the silicate oxyapatite after the second-stage annealing treatment to T 3 for the third homogenization heat treatment, and then cooling it to T 3 ' , and then naturally cooling it in the furnace to obtain the final product with the emission from the high energy levels of Eu 3+ in silicate oxyapatite. 5 D 1,2,3 emission. Optionally, the chemical formula of the Eu 3+ doped silicate oxyapatite is AR 9 (SiO 4 ) 6 O 2 :9 x Eu 3+, A = Li, Na, K; R = La, Gd, Lu, Y, Sc, x is Eu 3+ substitutes for R 3+ in terms of the number of moles, and 0.001 ≤ x ≤ 0.20.

[0006] Optionally, the T 1 = 400 °C to 700 °C, T 1 ' = T 1 – 100 °C.

[0007] Optionally, the T 2 = 700 °C to 900 °C, T 2 ' = T 2 – 100 °C.

[0008] Optionally, the T 3 = 900 °C to 1050 °C, T 3 ' = T 3 – 100 °C.

[0009] Optionally, the stepwise stage annealing treatment is performed on the Eu 3+ doped silicate oxyapatite for at least 3 stages.

[0010] Optionally, the time of the first homogenization heat treatment is 1 to 2 hours; and / or, the time of the second homogenization heat treatment is 1 to 5 hours; and / or, the time of the third homogenization heat treatment is 1 to 10 hours.

[0011] Optionally, the reducing atmosphere is at least one of the first atmosphere, the second atmosphere and the third atmosphere; wherein, the first atmosphere is hydrogen or a mixed gas of hydrogen and nitrogen with a volume ratio of 1:0.2 to 85; the second atmosphere is carbon monoxide gas; the third atmosphere is the gas produced by burning carbon particles or activated carbon in air.

[0012] On the other hand, the present disclosure provides a luminescent material, which is prepared by treating the Eu 3+ doped silicate oxyapatite by the post-annealing method described above.

[0013] On the other hand, the present disclosure provides an application of a luminescent material, using the luminescent material described above in luminescent lighting and display devices.

[0014] The present disclosure provides a post-annealing method, a luminescent material and an application for realizing emission from the high-energy excited state of Eu in silicate oxyapatite. The post-annealing method includes: heating Eu-doped silicate oxyapatite to T in a reducing atmosphere in a first heating section for a first homogenization heat treatment, and then cooling it to T in a first cooling section; heating the silicate oxyapatite after the first-stage annealing treatment to T in a second heating section for a second homogenization heat treatment, and then cooling it to T; heating the silicate oxyapatite after the second-stage annealing treatment to T in a third heating section for a third homogenization heat treatment, and then cooling it to T, and then naturally cooling it in the furnace to obtain the final product with emission from the high-energy excited state of Eu. The present disclosure can achieve efficient and stable luminescence from the high-energy excited state of Eu through a simple post-annealing treatment: (green light), (blue-green light), (blue light), and at the same time retain the red luminescence of ( = 0, 1, 2, 3, 4). This method is simple and easy to operate, the obtained material has high luminescence efficiency, and the luminescence quenching at high temperature is small. 3+ High-energy excited state 5 D 1,2,3 The post-annealing method, the luminescent material and the application for realizing emission from the high-energy excited state of Eu in silicate oxyapatite. The post-annealing method includes: heating Eu-doped silicate oxyapatite to T in a reducing atmosphere in a first heating section for a first homogenization heat treatment, and then cooling it to T in a first cooling section; heating the silicate oxyapatite after the first-stage annealing treatment to T in a second heating section for a second homogenization heat treatment, and then cooling it to T; heating the silicate oxyapatite after the second-stage annealing treatment to T in a third heating section for a third homogenization heat treatment, and then cooling it to T, and then naturally cooling it in the furnace to obtain the final product with emission from the high-energy excited state of Eu. The present disclosure can achieve efficient and stable luminescence from the high-energy excited state of Eu through a simple post-annealing treatment: (green light), (blue-green light), (blue light), and at the same time retain the red luminescence of ( = 0, 1, 2, 3, 4). This method is simple and easy to operate, the obtained material has high luminescence efficiency, and the luminescence quenching at high temperature is small. 3+ Doped silicate oxyapatite is heated to T in a reducing atmosphere in a first heating section for a first homogenization heat treatment, and then cooled to T in a first cooling section; 1 For the first homogenization heat treatment, and then cooled to T in a first cooling section; 1 ' After the first-stage annealing treatment, the silicate oxyapatite is heated to T in a second heating section for a second homogenization heat treatment, and then cooled to T; 2 For the second homogenization heat treatment, and then cooled to T; 2 ' After the second-stage annealing treatment, the silicate oxyapatite is heated to T in a third heating section for a third homogenization heat treatment, and then cooled to T, 3 For the third homogenization heat treatment, and then cooled to T, 3 ' After that, it is naturally cooled in the furnace to obtain the final product with emission from the high-energy excited state of Eu 3+ High-energy excited state 5 D 1,2,3 The present disclosure can achieve efficient and stable luminescence from the high-energy excited state of Eu through a simple post-annealing treatment: 3+ High-energy excited state 5 D 1,2,3 Emission: 5 D 1 (Green light), 5 D 2 (Blue-green light), 5 D 3 (Blue light), and at the same time retain 5 D 0 – 7 F J ( J = 0, 1, 2, 3, 4) of red luminescence, and this method is simple and easy to operate, the obtained material has high luminescence efficiency, and the luminescence quenching at high temperature is small. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 It is a schematic diagram of the implementation route of the post-annealing method in the specific embodiment of the present disclosure; Figure 2 It is the luminescence spectrum of the sample in Example 1 of the present disclosure before and after the post-annealing treatment; Figure 3 It is the luminescence spectrum of the sample in Example 2 of the present disclosure before and after the post-annealing treatment; Figure 4 It is the luminescence spectrum of the sample in Example 3 of the present disclosure before and after the post-annealing treatment; Figure 5 This is the luminescence spectrum of the sample in Example 4 of the present disclosure before and after post-annealing treatment; Figure 6 This is the luminescence spectrum of the sample in Example 5 of the present disclosure before and after post-annealing treatment; Figure 7 This is the luminescence spectrum of the sample in Example 6 of the present disclosure before and after post-annealing treatment. Detailed implementation manners

[0016] To enable those skilled in the art to better understand the technical solutions of the present disclosure, the present disclosure will be further described in detail below with reference to the accompanying drawings and specific implementation manners. It should be understood that the specific embodiments described herein are only used to explain the present disclosure, which are part of the embodiments of the present disclosure, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present disclosure without creative efforts shall fall within the protection scope of the present disclosure.

[0017] As Figure 1 shown, on the one hand, the present disclosure provides a post-annealing method S100 for the emission from the high-energy excited state of Eu 3+ in silicate oxyapatite, which specifically includes the following steps S110 to S130: 5 D 1,2,3 The specific steps are as follows: S110. Put the as-prepared Eu 3+ -doped silicate oxyapatite into an annealing furnace, start the first heating section under a reducing atmosphere, heat it to T 1 at a certain heating rate, then perform the first homogenization treatment at this temperature, and then cool it to T 1 ' through the first cooling section.

[0018] In step S110, the Eu 3+ -doped silicate oxyapatite is used as the starting material, and the chemistry of this starting material is AR 9 (SiO 4 ) 6 O 2 :9 x Eu 3+ , A = Li, Na, K; R = La, Gd, Lu, Y, Sc, x is the molar number of Eu 3+ substituting R 3+ , and 0.001 ≤ x ≤ 0.20.

[0019] In some preferred embodiments, T 1 = 400 °C to 700 °C, T 1 '=T 1 –100 °C, that is, T 1 can preferably be 400 °C, 500 °C, 600 °C, 700 °C, etc., T 1 ' can preferably be 300 °C to 600 °C, for example, 300 °C, 400 °C, 500 °C, 600 °C, etc. Of course, this T 1 ' should be adjusted adaptively according to T 1 For example, when T 1 is 500 °C, T 1 ' should be 400 °C.

[0020] In some other preferred embodiments, the holding time of the first homogenizing heat treatment can preferably be 1 to 2 hours, for example, 1 hour, 1.5 hours, 2 hours, etc.

[0021] S120. The silicate oxyapatite after the first-stage annealing treatment enters the second heating section, from T 1 ' and is heated to T 2 at a certain heating rate for the second homogenizing heat treatment, and then cooled to T 2 ' .

[0022] In some preferred embodiments, T 2 = 700 °C to 900 °C, T 2 ' = T 2 –100 °C. Similarly, T 2 can preferably be 700 °C, 800 °C, 900 °C, etc., T 2 ' can preferably be 600 °C to 800 °C, for example, 600 °C, 700 °C, 800 °C, etc. Of course, this T 2 ' should be adjusted adaptively according to T 2 For example, when T 2 is 700 °C, T 2 ' should be 600 °C.

[0023] In some other preferred embodiments, the holding time of the second homogenizing heat treatment can preferably be 1 to 5 hours, for example, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, etc.

[0024] S130. The silicate oxyapatite after the second-stage annealing treatment enters the third heating section, from T 2 ' and is heated to T 3Perform the third homogenizing heat treatment, and then cool it to T through the third cooling stage 3 ' , and then cool it naturally in the furnace to obtain the final product emitted from Eu 3+ High-energy excited state 5 D 1,2,3 . In some preferred embodiments, T 3 = 900 °C to 1050 °C, T 3 ' = T 3 –100 °C. Similarly, T 3 can be preferably 900 °C, 1000 °C, 1050 °C, etc., and T 3 ' can be preferably 800 °C to 950 °C. For example, 800 °C, 850 °C, 900 °C, 950 °C, etc. Of course, this T 3 ' should be adjusted adaptively according to T 3 . For example, when T 3 is 950 °C, T 1 ' should be 850 °C.

[0025] In some other preferred embodiments, the holding time of the third homogenizing heat treatment can be preferably 1 to 10 hours. For example, 1 hour, 3 hours, 5 hours, 7 hours, 10 hours, etc.

[0026] It should be noted that in the stepwise stage annealing, the temperature of the homogenizing heat treatment in each stage gradually increases, that is, T 1 < T 2 < T 3 .

[0027] It should be further noted that the stepwise stage annealing is at least 3 stages. That is to say, in some other preferred embodiments, the material can be subjected to a fourth-stage annealing treatment after step S130. Of course, after the third-stage annealing treatment reaches the highest temperature, the fourth-stage annealing treatment requires a cooling treatment.

[0028] It should still be noted that the reducing atmosphere of this embodiment is at least one of the first atmosphere, the second atmosphere, and the third atmosphere; wherein, the first atmosphere is hydrogen or a mixed gas of hydrogen and nitrogen with a volume ratio of 1:0.2 to 85; the second atmosphere is carbon monoxide gas; the third atmosphere is the gas produced by burning carbon particles or activated carbon in air.

[0029] The present disclosure reforms the microdefects of the material through stepwise continuous annealing, and realizes Eu in a single matrix in silicate oxyapatite 3+For the all-round radiative transition, the luminescent material has a high luminescence efficiency. Moreover, this annealing method is simple and easy to operate, with very good repeatability, and no other reagents need to be added, which is an effective means for further post-treatment of oxygen-containing materials.

[0030] On the other hand, the present disclosure provides a luminescent material, which is prepared by treating Eu 3+ doped silicate oxyapatite with the post-annealing method described above. That is, the raw material can be annealed stepwise to obtain the final product emitting from the high-energy excited state 3+ of Eu 5 D 1,2,3 .

[0031] On the other hand, the present disclosure provides an application of a luminescent material, which applies the luminescent material described above to luminescent lighting and display devices.

[0032] The luminescent material of this embodiment can not only display the red luminescence characteristic line spectrum from 5 D 0 – 7 F J ( J =0, 1, 2, 3, 4), but also realizes the emission from the high-energy level 5 D 1,2,3 in the blue-green region: 5 D 1 (green light), 5 D 2 (blue-green light), 5 D 3 (blue light). Therefore, as a luminescent material for realizing white light emission in a single matrix, it can be applied to luminescent lighting and display devices.

[0033] Next, the post-annealing method for the emission from the high-energy excited state 3+ of Eu 5 D 1,2,3 in silicate oxyapatite will be further described with specific examples: Example 1 The original sample of this Example 1 is LiLa 9 (SiO 4 ) 6 O 2 :0.009Eu 3+ . According to Figure 1 , it is annealed stepwise, and the steps are as follows: Stage S1: Put the original sample of Example 1 into the annealing furnace and enter the first heating section under a reducing atmosphere: heat from room temperature to T1 = 400 °C; then enter the first soaking stage: at T 1 = 400 °C, hold for 2 hours; then enter the first cooling stage: cool the furnace temperature to T 1 ' = 300 °C. Then enter the heating stage of stage S2: from T 1 ' = 300 °C heat to T 2 = 700 °C; then enter the second soaking stage: at T 2 = 700 °C, hold for 5 hours; then enter the second cooling stage: cool to T 2 ' = 600 °C. Then enter the heating stage of stage S3: from T 2 ' = 600 °C heat to T 3 = 1050 °C; then enter the third soaking stage: at T 3 = 1050 °C, hold for 1 hour; then enter the third cooling stage: cool to T 3 ' = 950 °C. Then cool naturally with the furnace to room temperature to obtain the final product that has undergone post-annealing treatment and realizes emission from the Eu 3+ high-energy excited state 5 D 1,2,3 emission.

[0034] As Figure 2 shown, all the luminescence of the original sample of Example 1 before annealing was from 5 D 0, → 7 F 0,1,2,3,4 red luminescence. After the post-annealing treatment, emissions from 5 D 1,2,3 were added: 5 D 1 (green light), 5 D 2 (blue-green light), 5 D 3 (blue light), making it a luminescent material that realizes white light emission in a single matrix.

[0035] Example 2 The original sample of this Example 2 was LiGd 9 (SiO 4 ) 6 O 2 :0.09Eu 3+ , and a stepwise stage annealing was carried out using the Figure 1 route. The steps are as follows: In stage S1, the original sample of Example 2 is placed in an annealing furnace and the first heating stage is carried out under a reducing atmosphere: first, it is heated to T 1 = 700 °C; then it enters the first soaking stage: it is held at T 1 = 700 °C for 1 hour; subsequently, it enters the first cooling stage: the furnace temperature is cooled to T 1 ' = 600 °C, and it enters the heating stage of stage S2: it is heated from T 1 ' = 600 °C to T 2 = 900 °C; then it enters the second soaking stage: it is held at T 2 = 900 °C for 1 hour; subsequently, it enters the second cooling stage: it is cooled to T 2 ' = 800 °C; then it enters the heating stage of stage S3: it is heated from T 2 ' = 800 °C to T 3 = 900 °C; then it enters the third soaking stage: it is held at T 3 = 950 °C for 10 hours; subsequently, it enters the third cooling stage: it is cooled to T 3 ' = 850 °C; then it is naturally cooled to room temperature in the furnace, and the final product that realizes emission from the high-energy excited state of Eu 3+ high-energy excited state 5 D 1,2,3 is obtained.

[0036] As Figure 3 shown, all the luminescence of the original sample of Example 2 before annealing comes from 5 D 0, → 7 F 0,1,2,3,4 red luminescence. After the post-annealing treatment, emissions from 5 D 1,2,3 are added: 5 D 1 (green light), 5 D 2 (blue-green light), 5 D 3 (blue light), making it a luminescent material that realizes white light emission in a single matrix.

[0037] Example 3 The original sample of this Example 3 is NaGd 9 (SiO 4 ) 6 O 2 :0.45Eu 3+ , using Figure 1Perform stepwise stage annealing along the route, and the method includes the following steps: Stage S1, put the original sample of Example 3 into the annealing furnace, and perform the first heating section under a reducing atmosphere: first heat to T 1 = 600 °C; then enter the first soaking section: hold at T 1 = 600 °C for 1 hour; then enter the first cooling section: cool the furnace temperature to T 1 ' = 500 °C, and then enter Stage S2: heating section: heat from T 1 ' = 500 °C to T 2 = 850 °C; then enter the second soaking section: hold at T 2 = 850 °C for 3 hours; then enter the second cooling section: cool to T 2 ' = 750 °C; then enter Stage S3, heating section: heat from T 2 ' = 750 °C to T 3 = 1000 °C; then enter the third soaking section: hold at T 3 = 1000 °C for 6 hours; then enter the third cooling section: cool to T 3 ' = 900 °C; then cool naturally with the furnace to room temperature to obtain the final product after post-annealing treatment that realizes emission from the high-energy excited state of Eu 3+ High-energy excited state 5 D 1,2,3 Emission.

[0038] As Figure 4 shown, all the luminescence of the original sample of Example 3 before annealing comes from 5 D 0, → 7 F 0,1,2,3,4 Red luminescence. After the post-annealing treatment, new emissions from 5 D 1,2,3 are added: 5 D 1 (green light), 5 D 2 (blue-green light), 5 D 3 (blue light), making it a luminescent material that realizes white light emission in a single matrix.

[0039] Example 4 For the original sample NaLa 9 (SiO 4 ) 6 O 2 :0.9Eu 3+, using Figure 1 the following route for stepwise stage annealing, the method comprising the following steps: Stage S1, placing the original sample of Example 4 into an annealing furnace, and performing a first heating section under a reducing atmosphere: first heating to T 1 = 600 °C; then entering a first soaking section: soaking at T 1 = 600 °C for 1 hour; then entering a first cooling section: cooling the furnace temperature to T 1 ' = 500 °C, and then entering Stage S2: heating section: heating from T 1 ' = 500 °C to T 2 = 850 °C; then entering a second soaking section: soaking at T 2 = 850 °C for 3 hours; then entering a second cooling section: cooling to T 2 ' = 750 °C; then entering Stage S3, heating section: heating from T 2 ' = 750 °C to T 3 = 1000 °C; then entering a third soaking section: soaking at T 3 = 1000 °C for 6 hours; then entering a third cooling section: cooling to T 3 ' = 900 °C; then naturally cooling to room temperature with the furnace to obtain the final product after post-annealing treatment, which realizes emission from the high-energy excited state of Eu 3+ high-energy excited state 5 D 1,2,3 emission.

[0040] As Figure 5 shown, all the luminescence of the original sample of Example 4 before annealing is from 5 D 0, → 7 F 0,1,2,3,4 red luminescence. After post-annealing treatment, emissions from 5 D 1,2,3 are newly added: 5 D 1 (green light), 5 D 2 (blue-green light), 5 D 3 (blue light), making it a luminescent material that realizes white light emission in a single matrix.

[0041] Example 5 For the original sample of Example 5, NaY 9 (SiO 4 ) 6 O2 : 0.99Eu 3+ Using Figure 1 the following route for stepwise stage annealing, the method comprising the following steps: Stage S1, placing the original sample of Example 4 into an annealing furnace and performing the first heating section under a reducing atmosphere: first heating to T 1 = 700 °C; then entering the first soaking section: holding at T 1 = 700 °C for 2 hours; subsequently entering the first cooling section: cooling the furnace temperature to T 1 ' = 600 °C, and then entering Stage S2: heating section: heating from T 1 ' = 600 °C to T 2 = 850 °C; then entering the second soaking section: holding at T 2 = 850 °C for 3 hours; subsequently entering the second cooling section: cooling to T 2 ' = 750 °C; then entering Stage S3, heating section: heating from T 2 ' = 750 °C to T 3 = 1000 °C; then entering the third soaking section: holding at T 3 = 1000 °C for 6 hours; subsequently entering the third cooling section: cooling to T 3 ' = 900 °C; then naturally cooling to room temperature with the furnace to obtain the final product after post-annealing treatment, which realizes emission from the high-energy excited state of Eu 3+ high-energy excited state 5 D 1,2,3 emission.

[0042] As Figure 6 shown, all the luminescence of the original sample of Example 5 before annealing was from the red luminescence of 5 D 0, → 7 F 0,1,2,3,4 After post-annealing treatment, new emissions from 5 D 1,2,3 appeared: 5 D 1 (green light), 5 D 2 (blue-green light), 5 D 3 (blue light), making it a luminescent material that realizes white light emission in a single matrix.

[0043] Example 6 For the original sample KY 9 (SiO4 ) 6 O 2 :1.35Eu 3+ , using the Figure 1 route for stepwise stage annealing, the method comprising the following steps: Stage S1, placing the original sample of Example 6 into an annealing furnace and performing the first heating section under a reducing atmosphere: first heating to T 1 = 700 °C; then entering the first soaking section: soaking at T 1 = 700 °C for 2 hours; subsequently entering the first cooling section: cooling the furnace temperature to T 1 ' = 600 °C, and then entering Stage S2: heating section: heating from T 1 ' = 600 °C to T 2 = 850 °C; then entering the second soaking section: soaking at T 2 = 850 °C for 3 hours; subsequently entering the second cooling section: cooling to T 2 ' = 750 °C; then entering Stage S3, heating section: heating from T 2 ' = 750 °C to T 3 = 1000 °C; then entering the third soaking section: soaking at T 3 = 1000 °C for 6 hours; subsequently entering the third cooling section: cooling to T 3 ' = 900 °C; then naturally cooling to room temperature with the furnace to obtain the final product after post-annealing treatment, achieving emission from the high-energy excited state of Eu 3+ high-energy excited state 5 D 1,2,3 emission.

[0044] As Figure 7 shown, all the luminescence of the original sample of Example 6 before annealing is from the 5 D 0, → 7 F 0,1,2,3,4 red luminescence. After the post-annealing treatment, new emissions from 5 D 1,2,3 are added: 5 D 1 (green light), 5 D 2 (blue-green light), 5 D 3 (blue light), making it a luminescent material that realizes white light emission in a single matrix.

[0045] The present disclosure proposes a method for realizing from Eu in silicate oxyapatite3+ High-energy-level excited state 5 D 1,2,3 The post-annealing method, luminescent material and application of emission have the following beneficial effects compared with the prior art: First, in the currently Eu 2+ In the ion-doped luminescent material, even when prepared in a reducing atmosphere, it is very difficult to achieve luminescence from the high-energy-level excited state. Compared with the existing technology, the post-annealing method of the present disclosure can easily obtain luminescence from the high-energy-level excited state in the silicate oxyapatite matrix 5 D 1,2,3 Moreover, the doping concentration is high, and the luminescence efficiency and stability are very good.

[0046] Second, the post-annealing method of the present disclosure realizes white-light emission display in a single silicate oxyapatite matrix, greatly broadening the Eu 3+ Luminescence application range.

[0047] Third, the luminescent material prepared by the present disclosure has small quenching of luminescence at high temperatures, and the main peak of luminescence at high temperatures is stable, maintaining the stability of chromaticity, which is beneficial to the preparation of high-power luminescent and display devices.

[0048] Fourth, the post-annealing method of the present disclosure can induce and stabilize defects in the oxygen matrix material, transforming to achieve rich luminescence physical properties. This method is simple to operate, and has excellent stability and repeatability.

[0049] It can be understood that the above embodiments are only exemplary embodiments adopted to illustrate the principle of the present disclosure. However, the present disclosure is not limited thereto. For those of ordinary skill in the art, various modifications and improvements can be made without departing from the spirit and essence of the present disclosure, and these modifications and improvements are also regarded as the protection scope of the present disclosure.

Claims

1. A method for realizing the process of obtaining Eu from silicate oxyapatite 3+ High-energy excited state 5 D 1,2,3 A post-emitter annealing method, characterized in that The post annealing method comprises: Will Eu 3+ The doped silicate oxyapatite is heated to T1 in a reducing atmosphere through a first heating stage for a first uniform heat treatment, and then cooled to T1 through a first cooling stage. ' ; After the first stage annealing treatment, the silicate oxyapatite is heated to T2 in the second heating section for the second uniform heat treatment, and then cooled to T2 in the second cooling section. ' ; After the second stage annealing treatment, the silicate oxyapatite is heated to T3 in the third heating section for the third uniform heat treatment, and then cooled to T3 in the third cooling section. ' , and then the furnace naturally cools down to obtain Eu 3+ High-energy excited state 5 D 1,2,3 The final product of the launch.

2. The post-annealing method according to claim 1, characterized in that: The Eu 3+ The chemistry of the doped silicate oxyapatite is AR9(SiO4)6O2:9 x Eu 3+ , A=Li, Na, K; R=La, Gd, Lu, Y, Sc, x For Eu 3+ Replace R 3+ The number of moles, and 0.001≤ x ≤0.

20.

3. The post-annealing method according to claim 1, characterized in that: The T1=400℃~700℃, T1 ' =T1–100°C.

4. The post-annealing method according to claim 1, characterized in that: The T2 = 700 ℃ ~ 900 ℃, T2 ' =T2–100°C.

5. The post-annealing method according to claim 1, characterized in that: The T3 = 900 ℃ ~ 1050 ℃, T3 ' =T3–100°C.

6. The post-annealing method according to any one of claims 1 to 5, characterized in that: For the Eu 3+ The doped silicate oxyapatite is subjected to at least three steps of step-wise annealing.

7. The post-annealing method according to any one of claims 1 to 5, characterized in that: The first uniform heat treatment lasts for 1 to 2 hours; and / or, The second uniform heat treatment lasts for 1 to 5 hours; and / or, The third uniform heat treatment lasts for 1 to 10 hours.

8. The post-annealing method according to any one of claims 1 to 5, characterized in that: The reducing atmosphere is at least one of the first atmosphere, the second atmosphere and the third atmosphere; wherein, The first atmosphere is hydrogen or a mixed gas with a volume ratio of hydrogen to nitrogen of 1:0.2-85; The second atmosphere is carbon monoxide gas; The third atmosphere is a gas produced by burning carbon particles or activated carbon in air.

9. A luminescent material, characterized in that: The luminescent material is Eu prepared by the post-annealing method according to any one of claims 1 to 8. 3+ Prepared by processing doped silicate oxyapatite.

10. An application of a luminescent material, characterized in that: The luminescent material according to claim 9 is used in luminescent lighting and display devices.

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