Erbium-ytterbium-doped Rb4Ta6O17 up-conversion fluorescent powder and preparation method thereof
By using the aqueous solution ion exchange method in the Rb4Ta6O17 matrix, Er3+/Yb3+ ions were stirred for a long time at 60°C, the problem of Er3+/Yb3+ ion intercalation was solved, and a pure green upconversion fluorescence and a two-dimensional flake-like structure of erbium ytterbium doped Rb4Ta6O17 upconversion phosphor was achieved.
Patent Information
- Application Number
- CN202510548430.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-28
- Publication Date
- 2025-08-12
AI Technical Summary
The prior art is difficult to achieve autonomous intercalation of Er3+/Yb3+ ions in the matrix, making it difficult to obtain pure green upconversion fluorescence and lack of matrix materials with layered hydrate structure.
Using Rb4Ta6O17 as the matrix, the Er3+/Yb3+ ions were allowed to enter the aqueous layer by long-stirring aqueous solution ion exchange method at 60°C to achieve layered distribution, and a two-dimensional sheet-like Rb4Ta6O17:Er3+/Yb3+ upconverted phosphor was prepared.
Under 980nm laser excitation, pure green upconversion fluorescence was obtained, achieving single-atom layered distribution and two-dimensional sheet structure of Er3+/Yb3+.
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Figure CN120464394A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of up-conversion phosphors, and more specifically to an erbium-ytterbium-doped Rb4Ta6O 17 Upconversion phosphor and preparation method thereof. Background Art
[0002] Upconversion phosphors are generally formed by luminescent centers and sensitizing centers replacing certain element sites in the matrix structure. 3+ / Yb 3+ Co-doped phosphors, when excited by 980nm laser, will emit visible green light (~510 to ~574nm) and red light (~643 to ~692nm). This is related to the matrix structure, matrix phonon energy, Er 3+ / Yb 3+ It is related to the distribution of ions in the matrix, energy transfer and cross relaxation.
[0003] However, obtaining pure green fluorescence is a difficult problem. 19 Pure green upconversion luminescent material and its preparation method" discloses a BiTa7O 19 is a matrix, in which Er is doped 3+ 、Yb 3+ and Mo 6+ , the Er-Yb-Mo triple-doped BiTa7O 19 The chemical formula of pure green upconversion luminescent material is Bi a Er b Yb c Ta d Mo e O 19 , where a+b+c=1,d+e=7,in BiTa7O 19 :Er 3+ / Yb 3+ / Mo 4+ Inspired by Er 3+ / Yb 3+ Distributed in one layer and separated by Ta-O layers, pure green upconversion fluorescence is obtained under 980nm laser excitation.
[0004] Therefore, it is necessary to find an up-conversion luminescent material to facilitate Er 3+ / Yb 3+ Ion exchange autonomous intercalation growth, Er after ion exchange 3+ / Yb 3+ A single-atom layer distribution is achieved to obtain pure green upconversion fluorescence, which is different from the previous application of the applicant for BiTa7O 19 Matrix, Er 3+ / Yb 3+ Is to replace Bi 3+ This ion exchange requires a matrix material with a layered hydrate structure and a hydrate layer. In aqueous solution, Er is achieved through ion exchange. 3+ / Yb 3+ Entering the hydration layer, upconversion fluorescence emission is achieved. Summary of the Invention
[0005] The purpose of the present invention is to overcome the above-mentioned defects of the prior art and provide an erbium-ytterbium-doped Rb4Ta6O 17 Up-conversion phosphor and preparation method thereof, using Rb4Ta6O 17 Matrix, Er 3+ / Yb 3+ Ions enter the water-bearing layer and are distributed in layers, which can obtain pure green upconversion fluorescence. At 60℃, after long-term stirring, Er 3+ / Yb 3+ Layered distribution, obtaining two-dimensional sheet Rb4Ta6O 17 :Er 3+ / Yb 3+ The product obtained pure green upconversion fluorescence under 980nm laser excitation.
[0006] To achieve the above object, the technical solution of the present invention is as follows:
[0007] Erbium-ytterbium doped Rb4Ta6O 17 Upconversion phosphor, based on Rb4Ta6O 17 is a matrix, in which Er is doped 3+ and Yb 3+ ; Erbium-ytterbium-doped Rb4Ta6O 17 Upconversion phosphors have a two-dimensional flake structure.
[0008] Optionally, the erbium-ytterbium doped Rb4Ta6O 17 The chemical formula of upconversion phosphor is Rb a Er 3b Yb 3c Ta6O 17 , where a+3b+3c=4.
[0009] Optional, its chemical formula is Rb a Er 3b Yb 3c Ta6O 17 , where a=2.5, b=0.1, c=0.4.
[0010] The present invention also discloses an erbium-ytterbium-doped Rb4Ta6O 17The preparation method of upconversion phosphor comprises the following steps:
[0011] S1: Rb in molar ratio + :Ta 5+ =4:6, weigh the raw materials Rb2CO3 and Ta2O5 and mix them thoroughly, and add 20mol% Rb2CO3 and mix them thoroughly to provide Rb at high temperature. + quality loss;
[0012] S2: After the raw materials are mixed, they are ground to ensure that the raw materials are evenly mixed;
[0013] S3: The ground raw materials are placed in a muffle furnace and kept at 1200℃~1300℃ for 12h~24h and then cooled to room temperature to obtain Rb4Ta6O 17 matrix;
[0014] S4: According to Rb + :Er 3+ :Yb 3+ :Ta 5+ Weigh Er(NO3)3·6H2O and Yb(NO3)3·5H2O in a molar ratio and dissolve them in deionized water to obtain Er 3 + / Yb 3+ aqueous solution;
[0015] S5: The Rb4Ta6O 17 The matrix is dispersed in the Er 3 + / Yb 3+ The erbium-ytterbium doped Rb4Ta6O is obtained by stirring the solution at 60°C to 80°C for 6 to 30 days. After the reaction is completed, the solution is filtered and the washed material is dried to obtain the erbium-ytterbium doped Rb4Ta6O 17 Upconversion phosphors.
[0016] Optionally, in step S4, according to the chemical formula Rb a Er 3b Yb 3c Ta6O 17 The stoichiometric ratio of each element in the formula is: a+3b+3c=4, and the configuration is Er 3+ / Yb 3+ aqueous solution.
[0017] Optionally, in step S2, the grinding time is 30 min to 60 min.
[0018] Optionally, in step S5, the Rb4Ta6O 17 Matrix and the Er 3 + / Yb 3+ The mass volume ratio of the aqueous solution is 0.5g:30mL.
[0019] Optionally, in step S5, the drying temperature is 80° C. to 100° C., and the drying time is 2 h to 6 h.
[0020] Optionally, in steps S1 and S4, the purities of the Rb2CO3, Ta2O5, Er(NO3)3·6H2O, and Yb(NO3)3·5H2O are all 99.0% to 99.9%.
[0021] Optionally, step S3 further includes the following steps: 17 The matrix is dispersed in deionized water and stirred at room temperature, and then the solution is filtered and dried.
[0022] Optionally, in step S5, the stirring speed is 500 r / min to 600 r / min.
[0023] Implementing the embodiments of the present invention will have the following beneficial effects:
[0024] The present invention discloses an erbium- and ytterbium-doped Rb4Ta6O 17 Up-conversion phosphor and its preparation method. The phosphor is composed of Rb4Ta6O with low phonon energy and layered structure. 17 As the matrix, by doping Er in the matrix 3+ and Yb 3+ Ions are grown using ion exchange intercalation technology. This upconversion luminescent material can emit pure green upconversion fluorescence under 980nm laser excitation and has a two-dimensional sheet structure. BRIEF DESCRIPTION OF THE DRAWINGS
[0025] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following is a brief introduction to the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative labor.
[0026] Figure 1 These are the XRD test result diagrams of Examples 1 to 8 of the present invention.
[0027] Figure 2 For the present invention 3+ / Yb 3+ Schematic diagram of ion exchange intercalation growth.
[0028] Figure 3 This is the SEM morphology of Example 1 of the present invention.
[0029] Figure 4This is the SEM morphology of Example 4 of the present invention.
[0030] Figure 5 This is an enlarged SEM morphology image of Example 4 of the present invention.
[0031] Figure 6 This is the SEM morphology of Example 6 of the present invention.
[0032] Figure 7 This is an enlarged SEM morphology image of Example 6 of the present invention.
[0033] Figure 8 This is the SEM morphology of Example 8 of the present invention.
[0034] Figure 9 This is an enlarged SEM morphology image of Example 8 of the present invention.
[0035] Figure 10 These are up-conversion fluorescence spectra of Examples 1 and 3 to 8 of the present invention under 980 nm laser excitation. DETAILED DESCRIPTION
[0036] The present invention will be further described below with reference to specific examples, but the present invention is not limited thereto in any way.
[0037] Example 1 (Preparation of Rb4Ta6O 17 Matrix):
[0038] A Rb4Ta6O 17 The preparation method of layered oxide adopts solid phase method, which mainly includes the following steps:
[0039] S1: Weigh 0.7665g of Rb2CO3 and 2g of Ta2O5 according to the stoichiometric ratio and mix them thoroughly. The molar ratio of each raw material is based on Rb + :Ta 5+ =4:6, and add an excess of 20 mol% Rb2CO3 to provide Rb at high temperature + quality loss;
[0040] S2: After mixing the raw materials, put them into an agate mortar and grind them for 30 minutes to make the raw materials evenly mixed;
[0041] S3: After grinding, the raw materials were placed in a muffle furnace, kept at 1200 ° C for 12 hours and then cooled to room temperature to obtain Rb4Ta6O 17 matrix.
[0042] Example 2 (Washing Rb4Ta6O 17 Matrix):
[0043] A hydrous Rb4Ta6O 17The preparation method of layered oxide mainly comprises the following steps:
[0044] S1: Weigh 0.7665g of Rb2CO3 and 2g of Ta2O5 according to the stoichiometric ratio and mix them thoroughly. The molar ratio of each raw material is based on Rb + :Ta 5+ =4:6, and an excess of 20 mol% Rb2CO3 is added to provide mass loss at high temperature;
[0045] S2: After mixing the raw materials, put them into an agate mortar and grind them for 30 minutes to make the raw materials evenly mixed;
[0046] S3: After grinding, the raw materials were placed in a muffle furnace, kept at 1200 ° C for 12 hours and then cooled to room temperature to obtain Rb4Ta6O 17 matrix;
[0047] S4: 0.5g of Rb4Ta6O 17 The powder was dispersed in 30 mL of deionized water and stirred at 500 rpm for 1 day at room temperature;
[0048] S5: After the reaction is completed, the solution is filtered and the washed material is dried at 80°C for 2 h to obtain the final material.
[0049] Example 3 (0.1Er 3+ / 0.1Yb 3+ Ion exchange Rb4Ta6O 17 Matrix):
[0050] An erbium-ytterbium intercalation layer Rb4Ta6O 17 The preparation method of upconversion phosphor adopts aqueous solution ion exchange method, which mainly includes the following steps:
[0051] S1: Weigh 10 mol% of Er(NO3)3·6H2O (0.0136 g) and 10 mol% of Yb(NO3)3·5H2O (0.0132 g) and dissolve them in 30 mL of deionized water to prepare Er 3 + / Yb 3+ aqueous solution;
[0052] S2: 0.5 g of Rb4Ta6O prepared in Example 1 17 The powder was dispersed in 30 mL of prepared Er 3+ / Yb 3+ In aqueous solution, the reaction was stirred at 500 r / min at 60 ° C for 6 days, and the molar ratio was Er(NO3)3·6H2O ： Rb4Ta6O 17 =1:10; Yb(NO3)3·6H2O ：Rb4Ta6O 17 =1:10;
[0053] S3: After the reaction is completed, the solution is filtered and the washed material is dried at 80°C for 2 h to obtain the final material.
[0054] Example 4 (0.1Er 3+ / 0.2Yb 3+ Ion exchange Rb4Ta6O 17 Matrix):
[0055] An erbium-ytterbium intercalation layer Rb4Ta6O 17 The preparation method of upconversion phosphor adopts aqueous solution ion exchange method, which mainly includes the following steps:
[0056] S1: Weigh 10 mol% of Er(NO3)3·6H2O (0.0136 g) and 20 mol% of Yb(NO3)3·5H2O (0.0264 g) and dissolve them in 30 mL of deionized water to prepare Er 3 + / Yb 3+ aqueous solution;
[0057] S2: 0.5 g of Rb4Ta6O prepared in Example 1 17 The powder was dispersed in 30 mL of prepared Er 3+ / Yb 3+ In aqueous solution, the reaction was stirred at 500 r / min at 60 ° C for 6 days, and the molar ratio was Er(NO3)3·6H2O ： Rb4Ta6O 17 =1:10; Yb(NO3)3·6H2O ： Rb4Ta6O 17 =1:5;
[0058] S3: After the reaction is completed, the solution is filtered and the washed material is dried at 80°C for 2 h to obtain the final material.
[0059] Example 5 (0.1Er 3+ / 0.25Yb 3+ Ion exchange Rb4Ta6O 17 Matrix):
[0060] An erbium-ytterbium intercalation layer Rb4Ta6O 17 The preparation method of upconversion phosphor adopts aqueous solution ion exchange method, which mainly includes the following steps:
[0061] S1: Weigh 10 mol% Er(NO3)3·6H2O (0.0136 g) and 30 mol% Yb(NO3)3·5H2O (0.0396 g) and dissolve them in 30 mL of deionized water to prepare Er 3 + / Yb 3+ aqueous solution;
[0062] S2: 0.5 g of Rb4Ta6O prepared in Example 1 17 The powder was dispersed in 30 mL of prepared Er 3+ / Yb 3+ In aqueous solution, the reaction was stirred at 500 r / min at 60 ° C for 6 days, and the molar ratio was Er(NO3)3·6H2O ： Rb4Ta6O 17 =1:10; Yb(NO3)3·6H2O ： Rb4Ta6O 17 =1:4;
[0063] S3: After the reaction is completed, the solution is filtered and the washed material is dried at 80°C for 2 h to obtain the final material.
[0064] Example 6 (0.1Er 3+ / 0.3Yb 3+ Ion exchange Rb4Ta6O 17 Matrix):
[0065] An erbium-ytterbium intercalation layer Rb4Ta6O 17 The preparation method of upconversion phosphor adopts aqueous solution ion exchange method, which mainly includes the following steps:
[0066] S1: Weigh 10 mol% of Er(NO3)3·6H2O (0.0136 g) and 40 mol% of Yb(NO3)3·5H2O (0.0528 g) and dissolve them in 30 mL of deionized water to prepare Er 3 + / Yb 3+ aqueous solution;
[0067] S2: 0.5 g of Rb4Ta6O prepared in Example 1 17 The powder was dispersed in 30 mL of prepared Er 3+ / Yb 3+ In aqueous solution, the reaction was stirred at 500 r / min at 60 ° C for 6 days, and the molar ratio was Er(NO3)3·6H2O ： Rb4Ta6O 17 =1:10; Yb(NO3)3·6H2O ： Rb4Ta6O 17 =3:10;
[0068] S3: After the reaction is completed, the solution is filtered and the washed material is dried at 80°C for 2 h to obtain the final material.
[0069] Example 7 (0.1Er 3+ / 0.35Yb 3+ Ion exchange Rb4Ta6O 17 Matrix):
[0070] An erbium-ytterbium intercalation layer Rb4Ta6O 17 The preparation method of upconversion phosphor adopts aqueous solution ion exchange method, which mainly includes the following steps:
[0071] S1: Weigh 10 mol% Er(NO3)3·6H2O (0.0136 g) and 50 mol% Yb(NO3)3·5H2O (0.0660 g) and dissolve them in 30 mL of deionized water to prepare Er 3 + / Yb 3+ aqueous solution;
[0072] S2: 0.5 g of Rb4Ta6O prepared in Example 1 17 The powder was dispersed in 30 mL of prepared Er 3+ / Yb 3+ In aqueous solution, the reaction was stirred at 500 r / min at 60 ° C for 6 days, and the molar ratio was Er(NO3)3·6H2O ： Rb4Ta6O 17 =1:10; Yb(NO3)3·6H2O ： Rb4Ta6O 17 =7:20;
[0073] S3: After the reaction is completed, the solution is filtered and the washed material is dried at 80°C for 2 h to obtain the final material.
[0074] Example 8 (0.1Er 3+ / 0.4Yb 3+ Ion exchange Rb4Ta6O 17 Matrix):
[0075] An erbium-ytterbium intercalation layer Rb4Ta6O 17 The preparation method of upconversion phosphor adopts aqueous solution ion exchange method, which mainly includes the following steps:
[0076] S1: Weigh 10 mol% Er(NO3)3·6H2O (0.0136 g) and 50 mol% Yb(NO3)3·5H2O (0.0660 g) and dissolve them in 30 mL of deionized water to prepare Er 3 + / Yb 3+ aqueous solution;
[0077] S2: 0.5 g of Rb4Ta6O prepared in Example 1 17 The powder was dispersed in 30 mL of prepared Er 3+ / Yb 3+ In aqueous solution, the reaction was stirred at 500 r / min at 60 ° C for 6 days, and the molar ratio was Er(NO3)3·6H2O ： Rb4Ta6O 17 =1:10; Yb(NO3)3·6H2O ： Rb4Ta6O 17 =2:5;
[0078] S3: After the reaction is completed, the solution is filtered and the washed material is dried at 80°C for 2 h to obtain the final material.
[0079] Structural performance testing
[0080] 1. The structure of the up-conversion fluorescent materials of Examples 1 to 8 was tested. The test results are shown in Figure 1 :The test uses Cu target, the equipment model is RigakuD / MAXRE, the incident wavelength Since there is no Rb4Ta6O 17 ·3H2O standard card, similar Rb4Ta6O was selected 17 ·3H2O standard card. Rb4Ta6O of Example 1 sintered at high temperature solid phase 17 The sample and the washed sample of Example 2 are both hydrates. The interlayer distances of the water-bearing layer (040) are and It shows that after washing, hydration increases and the interlayer distance expands. 3+ concentration, increasing Yb 3+ The XRD results of the concentration of Er 3+ / Yb 3+ After ion exchange hydration layer, Yb 3+ As the concentration increases, the interlayer spacing decreases first and then increases. The minimum interlayer spacing is (Example 6). This shows that Er 3+ / Yb 3+ After the ion exchange hydration layer, hydrolysis occurs, causing water to be discharged and the interlayer spacing to decrease. 3+ After entering the hydration layer, the interlayer distance increases from 8.39A to According to the XRD results, the specific ion exchange intercalation growth mechanism is as follows Figure 2 shown.
[0081] 2. The materials provided in Examples 1, 4, 6 and 8 were subjected to SEM morphology testing. The test results are as follows: Figures 3 to 9 shown. Figure 3 The solid-phase sintered Rb4Ta6O 17 ·3H2O sample shows irregular solid-phase sintering morphology. Figures 4 to 9 Yes Er 3+ / Yb 3+ Different Yb after ion exchange 3+ The SEM morphology of the samples of Example 4, Example 6 and Example 8 with different concentrations, with different magnifications. The results show that after ion exchange, the morphology becomes flaky. Figure 9 In the figure, transparent flake-like structures can be seen, which indicates that the sample is thin enough to be considered as a two-dimensional layered material. 3+ The change of concentration did not change the morphology of the samples.
[0082] 3. The up-conversion fluorescence spectrum of the above-mentioned Examples 1, 3 to 8 was tested under 980nm laser excitation. Figure 10 As shown, the results show that the matrix Rb4Ta6O 17 No fluorescence, Er 3+ / Yb 3+ After ion exchange, it shows pure green upconversion fluorescence. 3+ With the increase of concentration, the green upconversion fluorescence intensity first increases and then decreases. 17 :0.1Er 3+ / 0.3Yb 3+ The upconversion fluorescence intensity is the highest when .
[0083] In summary, the prior art shows that Er 3+ / Yb 3+ Ions of other valence states can be grown on Rb4Ta6O by ion exchange intercalation. 17 In. 3+ / Yb 3+ It exhibits a 2D layer distribution, isolated by Ta-O layers. It exhibits pure green upconversion fluorescence under 980nm laser excitation. After long periods of ion exchange and stirring, a two-dimensional sheet material can be prepared.
[0084] The above-described embodiments merely represent several implementation methods of the present invention. While the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the patent application. It should be noted that a person skilled in the art would be able to make various modifications and improvements without departing from the spirit of the present invention, all of which fall within the scope of protection of the present invention. Therefore, the scope of protection of the patent for this invention shall be determined by the appended claims.
Claims
1. Erbium-ytterbium doped Rb4Ta6O 17 An upconversion phosphor, characterized in that Rb4Ta6O 17 is a matrix, in which Er is doped 3+ and Yb 3+ ; Erbium-ytterbium-doped Rb4Ta6O 17 Upconversion phosphors have a two-dimensional flake structure.
2. Erbium-ytterbium-doped Rb4Ta6O according to claim 1 17 An upconversion phosphor, characterized in that The Er-Yb doped Rb4Ta6O 17 The chemical formula of upconversion phosphor is Rb a Er 3b Yb 3c Ta6O 17 , where a+3b+3c=4.
3. The erbium-ytterbium-doped Rb4Ta6O according to claim 2 17 An upconversion phosphor, characterized in that Its chemical formula is Rb a Er 3b Yb 3c Ta6O 17 , where a=2.5, b=0.1, c=0.
4.
4. An erbium-ytterbium-doped Rb4Ta6O according to any one of claims 1 to 3 17 The method for preparing upconversion phosphor is characterized in that: The following steps are involved: S1: Rb in molar ratio + :Ta 5+ =4:6, weigh the raw materials Rb2CO3 and Ta2O5 and mix them thoroughly, and add 20mol% Rb2CO3 and mix them thoroughly to provide Rb at high temperature. + quality loss; S2: After the raw materials are mixed, they are ground to ensure that the raw materials are evenly mixed; S3: The ground raw materials are placed in a muffle furnace and kept at 1200℃~1300℃ for 12h~24h and then cooled to room temperature to obtain Rb4Ta6O 17 matrix; S4: According to Rb + :Er 3+ :Yb 3+ :Ta 5+ Weigh Er(NO3)3·6H2O and Yb(NO3)3·5H2O in a molar ratio and dissolve them in deionized water to obtain Er 3 + / Yb 3+ aqueous solution; S5: The Rb4Ta6O 17 The matrix is dispersed in the Er 3 + / Yb 3+ The erbium-ytterbium doped Rb4Ta6O is obtained by stirring the solution at 60°C to 80°C for 6 to 30 days. After the reaction is completed, the solution is filtered and the washed material is dried to obtain the erbium-ytterbium doped Rb4Ta6O 17 Upconversion phosphors.
5. The preparation method according to claim 4, characterized in that Step S4, according to the chemical formula Rb a Er 3b Yb 3c Ta6O 17 The stoichiometric ratio of each element in the formula is: a+3b+3c=4, and the configuration is Er 3+ / Yb 3+ aqueous solution.
6. The preparation method according to claim 4, characterized in that Step S2: The grinding time is 30 min to 60 min.
7. The preparation method according to claim 4, characterized in that Step S5, the Rb4Ta6O 17 Matrix and the Er 3 + / Yb 3+ The mass volume ratio of the aqueous solution is 0.5g:30mL; The drying temperature is 80° C. to 100° C., and the drying time is 2 hours to 6 hours.
8. The preparation method according to claim 4, characterized in that Step S3 also includes the following steps: 17 The matrix is dispersed in deionized water and stirred at room temperature, and then the solution is filtered and dried.
9. The preparation method according to claim 4, characterized in that In steps S1 and S4, the purities of the Rb2CO3, Ta2O5, Er(NO3)3·6H2O, and Yb(NO3)3·5H2O are all 99.0% to 99.9%.
10. The preparation method according to claim 4, characterized in that In step S5, the stirring speed is 500 r / min to 600 r / min.