Calcium carbonate loaded perovskite quantum dot composite luminescent material as well as preparation method and application thereof
By using calcium carbonate as a carrier on perovskite quantum dots, a KxCs1-xPbBr3/CaCO3 composite luminescent material was prepared, which solved the stability of perovskite quantum dots in water, achieved high stability and strong luminescence in water, and had good illumination display and fluorescent ink application prospects.
Patent Information
- Application Number
- CN202510043712.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-01-10
- Publication Date
- 2025-05-23
AI Technical Summary
Metal halide perovskite quantum dots, especially CsPbBr3, are prone to structural decomposition or agglomeration under the action of oxygen, moisture, heat and light, resulting in fluorescence quenching, seriously hindering its application in the field of lighting display.
The calcium carbonate-loaded perovskite quantum dot composite luminescent material was used to prepare the chemical formula of KxCs1-xPbBr3/CaCO3, 0≤x≤1, and the perovskite quantum dot concentration was 1-30 wt%. The composite material was prepared by impregnation and sintering of DMF solution using calcium carbonate as the carrier and perovskite quantum dots as the surface layer.
The composite luminescent material maintains a high luminescence intensity in water and has high water stability. When the excitation wavelength is 270-400nm, the luminescence intensity is basically unchanged within 120 days, and is suitable for lighting displays and fluorescent inks.
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Figure CN120025819A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of luminescent materials, and in particular relates to a calcium carbonate-loaded perovskite quantum dot composite luminescent material and a preparation method and application thereof. Background Art
[0002] In recent years, metal halide perovskite quantum dots have been widely used as photovoltaic materials due to their low cost and excellent optical properties (such as high quantum yield, wide absorption band, high light absorption coefficient, long carrier lifetime and diffusion length), and have become a research hotspot in the industry. It is a potential candidate for various applications, including solar cells, lasers, photodetectors and light-emitting diodes (LEDs).
[0003] Although metal halide perovskite quantum dots, especially CsPbBr 3 It has many excellent properties and is developing rapidly. 3 When exposed to oxygen, moisture, heat and light, structural decomposition or aggregation easily occurs, resulting in irreversible fluorescence quenching, which seriously hinders its application in the field of lighting and display. Therefore, achieving good stability while maintaining its excellent performance is one of the main challenges in the practical application of perovskites.
[0004] Therefore, researchers have adopted various strategies to improve the 3 Inorganic oxide matrix protects CsPbBr 3 The advantage is that it can solve the high stability required by WLED packaging technology. 3 Encapsulation in inorganic oxides still cannot avoid CsPbBr 3 Aggregation and emission wavelength shift. According to previous studies, although the use of inert shells or their addition to blocking matrices can improve stability, they also have a negative impact on the quality of QDs and even the fluorescence intensity. Summary of the invention
[0005] The purpose of the present invention is to avoid the shortcomings of the prior art and provide a calcium carbonate-loaded perovskite quantum dot composite luminescent material and its preparation method and application. The luminescent material can still maintain a high luminescence intensity in water and has high water stability. The preparation method is simple in process, has low equipment requirements, low energy consumption, is environmentally friendly, and has good industrialization prospects and application prospects.
[0006] In order to achieve the above object, the technical solution of the present invention is as follows:
[0007] On the one hand, the present invention provides a calcium carbonate-loaded perovskite quantum dot composite luminescent material, the chemical formula of the luminescent material is K x Cs 1-xPbBr 3 / CaCO 3 , where 0 ≤ x ≤ 1; in the luminescent material, the concentration of perovskite quantum dots is 1-30 wt%.
[0008] In the above technical solution, further, the composite luminescent material carrier is calcium carbonate, and the surface layer is perovskite quantum dots.
[0009] In the above technical solution, further, the chemical general formula of the luminescent material is K x Cs 1-x PbBr 3 / CaCO 3 , where 0 ≤ x ≤ 0.35, and the concentration of perovskite quantum dots is 5-25 wt%.
[0010] On the other hand, the present invention provides a method for preparing the above composite luminescent material, and the method includes the following steps:
[0011] (1) According to the chemical composition of K x Cs 1-x PbBr 3 , dissolve lead bromide, potassium bromide and cesium bromide in a DMF solution and stir and impregnate to obtain a quantum dot dispersion;
[0012] (2) Add calcium carbonate powder to the quantum dot dispersion obtained in step (1) and stir and impregnate, and dry the obtained product;
[0013] (3) Grind the mixture obtained in step (2) into a powder and then transfer it to a muffle furnace for sintering to obtain the composite luminescent material.
[0014] In the above technical solution, further, in step (1), the stirring time is 1-3 h.
[0015] In the above technical solution, further, in step (2), the stirring time is 5-8 h, and the drying temperature is 50-100 °C.
[0016] In the above technical solution, further, in step (3), the sintering temperature is 200-400 °C, and the time is 3-5 h.
[0017] The present invention also provides an application of the above composite luminescent material in lighting display and fluorescent ink.
[0018] The beneficial effects of the present invention are:
[0019] 1. When the composite luminescent material of the present invention is excited within the excitation wavelength range of 270-400nm, it emits green light with a peak wavelength of 505-530nm, and its luminous intensity remains basically unchanged in water for 120 days, that is, the luminous intensity does not decay basically; these advantages can meet the actual use requirements and have excellent application prospects in the field of lighting and display.
[0020] 2. The composite luminescent material of the present invention realizes single green light emission under near-ultraviolet light excitation, with a peak at about 525nm, meeting the requirements of fluorescent ink.
[0021] 3. The composite luminescent material of the present invention further improves the fluorescence intensity after being doped with K, and still has strong stability in water, and can also maintain a certain intensity in polar solvents.
[0022] 4. The preparation method of the present invention has simple process, low equipment requirements, low energy consumption, and is environmentally friendly, and has good industrialization and application prospects. BRIEF DESCRIPTION OF THE DRAWINGS
[0023] Figure 1 X-ray diffraction spectra of samples prepared in Example 1, Example 13, Example 14, and Comparative Example 1;
[0024] Figure 2 The emission spectra of the samples prepared in Examples 1-4 under excitation at a wavelength of 365 nm;
[0025] Figure 3 is the X-ray diffraction spectrum of the sample prepared in Example 3;
[0026] Figure 4 The emission spectra of the samples prepared in Example 1, Example 8, Example 9, Example 10 and Example 11 under the excitation of 365nm near-ultraviolet light wavelength;
[0027] Figure 5 The emission spectra of the samples prepared in Example 1, Example 13, Example 14 and Comparative Example 1 under excitation with a near-ultraviolet wavelength of 365 nm;
[0028] Figure 6 The figure shows the change of fluorescence intensity of the sample prepared in Example 2 in water. DETAILED DESCRIPTION
[0029] In order to make the purpose, technical solution and advantages of the embodiments of the present application clearer, the technical solution in the embodiments of the present application will be clearly and completely described below in conjunction with the drawings in the embodiments of the present application. Obviously, the described embodiments are part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of this application.
[0030] Unless otherwise specified, the terms used herein should be understood as commonly used in the art. Therefore, unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art to which this application belongs. In the event of a conflict, this specification takes precedence.
[0031] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in this application can be purchased from the market or prepared by existing methods.
[0032] Example 1
[0033] Table 1
[0034] raw material Weight(g) DMF 5 Cb 0.02 <![CDATA[PbBr 2 ]]> 0.04 <![CDATA[CaCO 3 ]]> 0.5
[0035] Accurately weigh the above amounts of DMF, CsBr and PbBr according to Table 1 2 , put into a beaker, and stir with a magnetic stirrer at room temperature for 2 h to obtain a quantum dot solution; according to the above amount of CaCO 3 Add to the quantum dot solution, stir with a magnetic stirrer at room temperature for 7 hours, and dry the obtained solution at 80°C; grind the dried powder thoroughly, transfer the powder to a glass slide, put it into a muffle furnace and sinter at 400°C for 4 hours, cool it to room temperature, transfer the powder to an agate mortar, grind it thoroughly, and obtain CsPbBr 3 / CaCO 3 Composite luminescent material, including CsPbBr 3 The concentration of quantum dots was 10 wt%.
[0036] Example 2
[0037] Table 2
[0038] raw material Weight(g) DMF 5 Cb 0.02 <![CDATA[PbBr 2 ]]> 0.04 <![CDATA[CaCO 3 ]]> 0.5 KBr 0.002
[0039] Accurately weigh the above amounts of DMF, KBr, CsBr and PbBr according to Table 2 2 , put into a beaker, and stir with a magnetic stirrer at room temperature for 2 h to obtain a quantum dot solution; according to the above amount of CaCO 3Add it to the K-doped quantum dot solution, stir it with a magnetic stirrer at room temperature for 7 hours, and dry the obtained solution at 80°C; grind the dried powder thoroughly, transfer the powder to a glass slide, put it into a muffle furnace and sinter it at 400°C for 4 hours, cool it to room temperature, transfer the powder to an agate mortar, grind it thoroughly, and obtain K 0.15 Cs 0.85 PbB 3 / CaCO 3 Composite luminescent material, in which K 0.15 Cs 0.85 PbB 3 The concentration of quantum dots was 10 wt%.
[0040] Example 3
[0041] Table 3
[0042] raw material Weight(g) DMF 5 Cb 0.02 <![CDATA[PbBr 2 ]]> 0.04 <![CDATA[CaCO 3 ]]> 0.5 KBr 0.003
[0043] Accurately weigh the above amounts of DMF, KBr, CsBr and PbBr according to Table 3 2 , put into a beaker, and stir with a magnetic stirrer at room temperature for 2 h to obtain a quantum dot solution; according to the above amount of CaCO 3 Add to the quantum dot solution, stir with a magnetic stirrer at room temperature for 7 hours, and dry the obtained solution at 80°C; grind the dried powder thoroughly, transfer the powder to a glass slide, put it into a muffle furnace and sinter at 400°C for 4 hours, cool it to room temperature, transfer the powder to an agate mortar, grind it thoroughly, and obtain K 0.25 Cs 0.75 PbB 3 / CaCO 3 Composite luminescent material, in which K 0.25 Cs 0.75 PbB 3 The concentration of quantum dots was 10 wt%.
[0044] Example 4
[0045] Table 4
[0046] raw material Weight(g) DMF 5 Cb 0.01 <![CDATA[PbBr 2 ]]> 0.04 <![CDATA[CaCO 3 ]]> 0.5 KBr 0.004
[0047] Accurately weigh the above amounts of DMF, KBr, CsBr and PbBr according to Table 4 2 , put into a beaker, and stir with a magnetic stirrer at room temperature for 2 h to obtain a quantum dot solution; according to the above amount of CaCO 3Add to the quantum dot solution, stir with a magnetic stirrer at room temperature for 7 hours, and dry the obtained solution at 80°C; grind the dried powder thoroughly, transfer the powder to a glass slide, put it into a muffle furnace and sinter at 400°C for 4 hours, cool it to room temperature, transfer the powder to an agate mortar, grind it thoroughly, and obtain K 0.35 Cs 0.65 PbB 3 / CaCO 3 Composite luminescent material, in which K 0.35 Cs 0.65 PbB 3 The concentration of quantum dots was 10 wt%.
[0048] Example 5
[0049] Table 5
[0050] raw material Weight(g) DMF 5 Cb 0.01 <![CDATA[PbBr 2 ]]> 0.04 <![CDATA[CaCO 3 ]]> 0.5 KBr 0.06
[0051] Accurately weigh the above amounts of DMF, KBr, CsBr and PbBr according to Table 5 2 , put into a beaker, and stir with a magnetic stirrer at room temperature for 2 h to obtain a quantum dot solution; according to the above amount of CaCO 3 Add to the quantum dot solution, stir with a magnetic stirrer at room temperature for 7 hours, and dry the obtained solution at 80°C; grind the dried powder thoroughly, transfer the powder to a glass slide, put it into a muffle furnace and sinter at 400°C for 4 hours, cool it to room temperature, transfer the powder to an agate mortar, grind it thoroughly, and obtain K 0.5 Cs 0.5 PbB 3 / CaCO 3 Composite luminescent material, in which K 0.5 Cs 0.5 PbB 3 The concentration of quantum dots was 10 wt%.
[0052] Example 6
[0053] Table 6
[0054] raw material Weight(g) DMF 5 <![CDATA[PbBr 2 ]]> 0.04 <![CDATA[CaCO 3 ]]> 0.5 KBr 0.01
[0055] Accurately weigh the above amounts of DMF, KBr and PbBr according to Table 6 2 , put into a beaker, and stir with a magnetic stirrer at room temperature for 2 h to obtain a quantum dot solution; according to the above amount of CaCO 3Add to the quantum dot solution, stir with a magnetic stirrer at room temperature for 7 hours, and dry the obtained solution at 80°C; grind the dried powder thoroughly, transfer the powder to a glass slide, put it into a muffle furnace and sinter it at 400°C for 4 hours, cool it to room temperature with the furnace, transfer the powder to an agate mortar, grind it thoroughly, and obtain KPbBr 3 / CaCO 3 Composite luminescent material, in which KPbBr 3 The concentration of quantum dots was 10 wt%.
[0056] Example 7
[0057] Table 7
[0058] raw material Weight(g) DMF 5 Cb 0.002 <![CDATA[PbBr 2 ]]> 0.002 <![CDATA[CaCO 3 ]]> 0.5
[0059] Accurately weigh the above amounts of DMF, CsBr and PbBr according to Table 7 2 , put into a beaker, and stir with a magnetic stirrer at room temperature for 2 h to obtain a quantum dot solution; according to the above amount of CaCO 3 Add to the quantum dot solution, stir with a magnetic stirrer at room temperature for 7 hours, and dry the obtained solution at 80°C; grind the dried powder thoroughly, transfer the powder to a glass slide, put it into a muffle furnace and sinter at 400°C for 4 hours, cool it to room temperature, transfer the powder to an agate mortar, grind it thoroughly, and obtain CsPbBr 3 / CaCO 3 Composite luminescent material, including CsPbBr 3 The quantum dot concentration was 1 wt%.
[0060] Example 8
[0061] Table 8
[0062] raw material Weight(g) DMF 5 Cb 0.01 <![CDATA[PbBr 2 ]]> 0.02 <![CDATA[CaCO 3 ]]> 0.5
[0063] Accurately weigh the above amounts of DMF, CsBr and PbBr according to Table 8 2 , put into a beaker, and stir with a magnetic stirrer at room temperature for 2 h to obtain a quantum dot solution; according to the above amount of CaCO 3 Add to the quantum dot solution, stir with a magnetic stirrer at room temperature for 7 hours, and dry the obtained solution at 80°C; grind the dried powder thoroughly, transfer the powder to a glass slide, put it into a muffle furnace and sinter at 400°C for 4 hours, cool it to room temperature, transfer the powder to an agate mortar, grind it thoroughly, and obtain CsPbBr 3 / CaCO 3 Composite luminescent material, including CsPbBr 3 The quantum dot concentration was 5 wt%.
[0064] Example 9
[0065] Table 9
[0066] raw material Weight(g) DMF 5 Cb 0.03 <![CDATA[PbBr 2 ]]> 0.06 <![CDATA[CaCO 3 ]]> 0.5
[0067] Accurately weigh the above amounts of DMF, CsBr and PbBr according to Table 9 2 , put into a beaker, and stir with a magnetic stirrer at room temperature for 2 h to obtain a quantum dot solution; according to the above amount of CaCO 3 Add to the quantum dot solution, stir with a magnetic stirrer at room temperature for 7 hours, and dry the obtained solution at 80°C; grind the dried powder thoroughly, transfer the powder to a glass slide, put it into a muffle furnace and sinter at 400°C for 4 hours, cool it to room temperature, transfer the powder to an agate mortar, grind it thoroughly, and obtain CsPbBr 3 / CaCO 3 Composite luminescent material, including CsPbBr 3 The quantum dot concentration was 15 wt%.
[0068] Example 10
[0069] Table 10
[0070] raw material Weight(g) DMF 5 Cb 0.05 <![CDATA[PbBr 2 ]]> 0.08 <![CDATA[CaCO 3 ]]> 0.5
[0071] Accurately weigh the above amounts of DMF, CsBr and PbBr according to Table 10 2 , put into a beaker, and stir with a magnetic stirrer at room temperature for 2 h to obtain a quantum dot solution; according to the above amount of CaCO 3 Add to the quantum dot solution, stir with a magnetic stirrer at room temperature for 7 hours, and dry the obtained solution at 80°C; grind the dried powder thoroughly, transfer the powder to a glass slide, put it into a muffle furnace and sinter at 400°C for 4 hours, cool it to room temperature, transfer the powder to an agate mortar, grind it thoroughly, and obtain CsPbBr 3 / CaCO 3 Composite luminescent material, including CsPbBr 3 The concentration of quantum dots was 20 wt%.
[0072] Embodiment 11
[0073] Table 11
[0074] raw material Weight(g) DMF 5 Cb 0.06 <![CDATA[PbBr 2 ]]> 0.11 <![CDATA[CaCO 3 ]]> 0.5
[0075] Accurately weigh the above amounts of DMF, CsBr and PbBr according to Table 11 2 , put into a beaker, and stir with a magnetic stirrer at room temperature for 2 h to obtain a quantum dot solution; according to the above amount of CaCO 3Add to the quantum dot solution, stir with a magnetic stirrer at room temperature for 7 hours, and dry the obtained solution at 80°C; grind the dried powder thoroughly, transfer the powder to a glass slide, put it into a muffle furnace and sinter at 400°C for 4 hours, cool it to room temperature, transfer the powder to an agate mortar, grind it thoroughly, and obtain CsPbBr 3 / CaCO 3 Composite luminescent material, including CsPbBr 3 The concentration of quantum dots was 25 wt%.
[0076] Example 12
[0077] Table 12
[0078] raw material Weight(g) DMF 5 Cb 0.07 <![CDATA[PbBr 2 ]]> 0.1 <![CDATA[CaCO 3 ]]> 0.5
[0079] Accurately weigh the above amounts of DMF, CsBr and PbBr according to Table 12 2 , put into a beaker, and stir with a magnetic stirrer at room temperature for 2 h to obtain a quantum dot solution; according to the above amount of CaCO 3 Add to the quantum dot solution, stir with a magnetic stirrer at room temperature for 7 hours, and dry the obtained solution at 80°C; grind the dried powder thoroughly, transfer the powder to a glass slide, put it into a muffle furnace and sinter at 400°C for 4 hours, cool it to room temperature, transfer the powder to an agate mortar, grind it thoroughly, and obtain CsPbBr 3 / CaCO 3 Composite luminescent material, including CsPbBr 3 The quantum dot concentration was 30 wt%.
[0080] Example 13
[0081] Table 13
[0082] raw material Weight(g) DMF 5 Cb 0.02 <![CDATA[PbBr 2 ]]> 0.04 <![CDATA[CaCO 3 ]]> 0.5
[0083] Accurately weigh the above amounts of DMF, CsBr and PbBr according to Table 13 2 , put into a beaker, and stir with a magnetic stirrer at room temperature for 2 h to obtain a quantum dot solution; according to the above amount of CaCO 3 Add to the quantum dot solution, stir with a magnetic stirrer at room temperature for 7 hours, and dry the obtained solution at 80°C; grind the dried powder thoroughly, transfer the powder to a glass slide, put it into a muffle furnace and sinter at 300°C for 4 hours, cool it to room temperature, transfer the powder to an agate mortar, grind it thoroughly, and obtain CsPbBr 3 / CaCO 3 Composite luminescent material, including CsPbBr 3 The concentration of quantum dots was 10 wt%.
[0084] Embodiment 14
[0085] Table 14
[0086] raw material Weight(g) DMF 5 Cb 0.02 <![CDATA[PbBr 2 ]]> 0.04 <![CDATA[CaCO 3 ]]> 0.5
[0087] Accurately weigh the above amounts of DMF, CsBr and PbBr according to Table 14 2 , put into a beaker, and stir with a magnetic stirrer at room temperature for 2 h to obtain a quantum dot solution; according to the above amount of CaCO 3 Add to the quantum dot solution, stir with a magnetic stirrer at room temperature for 7 hours, and dry the obtained solution at 80°C; grind the dried powder thoroughly, transfer the powder to a glass slide, put it into a muffle furnace and sinter at 200°C for 4 hours, cool it to room temperature with the furnace, transfer the powder to an agate mortar, grind it thoroughly, and obtain CsPbBr 3 / CaCO 3 Composite luminescent material, including CsPbBr 3 The concentration of quantum dots was 10 wt%.
[0088] Embodiment 15
[0089] Table 15
[0090] raw material Weight(g) DMF 5 Cb 0.02 <![CDATA[PbBr 2 ]]> 0.04 <![CDATA[CaCO 3 ]]> 0.5 KBr 0.003
[0091] Accurately weigh the above amounts of DMF, KBr, CsBr and PbBr according to Table 15 2 , put into a beaker, and stir with a magnetic stirrer at room temperature for 1 h to obtain a quantum dot solution; according to the above amount of CaCO 3 Add to the quantum dot solution, stir with a magnetic stirrer at room temperature for 7 hours, and dry the obtained solution at 80°C; grind the dried powder thoroughly, transfer the powder to a glass slide, put it in a muffle furnace and sinter at 400°C for 4 hours, cool it to room temperature, transfer the powder to an agate mortar, grind it thoroughly, and obtain K 0.25 Cs 0.75 PbB 3 / CaCO 3 Composite luminescent material, in which K 0.25 Cs 0.75 PbB 3 The concentration of quantum dots was 10 wt%.
[0092] Example 16
[0093] Table 16
[0094] raw material Weight(g) DMF 5 Cb 0.02 <![CDATA[PbBr 2 ]]> 0.04 <![CDATA[CaCO 3 ]]> 0.5 KBr 0.003
[0095] According to Table 16, accurately weigh the above amounts of DMF, KBr, CsBr and PbBr 2 , put into a beaker, and stir with a magnetic stirrer at room temperature for 3 h to obtain a quantum dot solution; according to the above amount of CaCO 3 Add to the quantum dot solution, stir with a magnetic stirrer at room temperature for 7 hours, and dry the obtained solution at 80°C; grind the dried powder thoroughly, transfer the powder to a glass slide, put it into a muffle furnace and sinter at 400°C for 4 hours, cool it to room temperature, transfer the powder to an agate mortar, grind it thoroughly, and obtain K 0.25 Cs 0.75 PbB 3 / CaCO 3 Composite luminescent material, in which K 0.25 Cs 0.75 PbB 3 The concentration of quantum dots was 10 wt%.
[0096] Embodiment 17
[0097] Table 17
[0098] raw material Weight(g) DMF 5 Cb 0.02 <![CDATA[PbBr 2 ]]> 0.04 <![CDATA[CaCO 3 ]]> 0.5 KBr 0.003
[0099] According to Table 17, accurately weigh the above amounts of DMF, KBr, CsBr and PbBr 2 , put into a beaker, and stir with a magnetic stirrer at room temperature for 2 h to obtain a quantum dot solution; according to the above amount of CaCO 3 Add to the quantum dot solution, stir with a magnetic stirrer at room temperature for 5 hours, and dry the obtained solution at 80°C; grind the dried powder thoroughly, transfer the powder to a glass slide, put it into a muffle furnace and sinter at 400°C for 4 hours, cool it to room temperature, transfer the powder to an agate mortar, grind it thoroughly, and obtain K 0.25 Cs 0.75 PbB 3 / CaCO 3 Composite luminescent material, in which K 0.25 Cs 0.75 PbB 3 The concentration of quantum dots was 10 wt%.
[0100] Embodiment 18
[0101] Table 18
[0102] raw material Weight(g) DMF 5 Cb 0.02 <![CDATA[PbBr 2 ]]> 0.04 <![CDATA[CaCO 3 ]]> 0.5 KBr 0.003
[0103] According to Table 18, accurately weigh the above amounts of DMF, KBr, CsBr and PbBr 2, put into a beaker, and stir with a magnetic stirrer at room temperature for 2 h to obtain a quantum dot solution; according to the above amount of CaCO 3 Add to the quantum dot solution, stir with a magnetic stirrer at room temperature for 8 hours, and dry the obtained solution at 80°C; grind the dried powder thoroughly, transfer the powder to a glass slide, put it into a muffle furnace and sinter at 400°C for 4 hours, cool it to room temperature, transfer the powder to an agate mortar, grind it thoroughly, and obtain K 0.25 Cs 0.75 PbB 3 / CaCO 3 Composite luminescent material, in which K 0.25 Cs 0.75 PbB 3 The concentration of quantum dots was 10 wt%.
[0104] Embodiment 19
[0105] Table 19
[0106] raw material Weight(g) DMF 5 Cb 0.02 <![CDATA[PbBr 2 ]]> 0.04 <![CDATA[CaCO 3 ]]> 0.5 KBr 0.003
[0107] According to Table 19, accurately weigh the above amounts of DMF, KBr, CsBr and PbBr 2 , put into a beaker, and stir with a magnetic stirrer at room temperature for 2 h to obtain a quantum dot solution; according to the above amount of CaCO 3 Add to the quantum dot solution, stir with a magnetic stirrer at room temperature for 7 hours, and dry the obtained solution at 50°C; grind the dried powder thoroughly, transfer the powder to a glass slide, put it into a muffle furnace and sinter at 400°C for 4 hours, cool it to room temperature, transfer the powder to an agate mortar, grind it thoroughly, and obtain K 0.25 Cs 0.75 PbB 3 / CaCO 3 Composite luminescent material, in which K 0.25 Cs 0.75 PbB 3 The concentration of quantum dots was 10 wt%.
[0108] Embodiment 20
[0109] Table 20
[0110]
[0111]
[0112] Accurately weigh the above amounts of DMF, KBr, CsBr and PbBr according to Table 20 2 , put into a beaker, and stir with a magnetic stirrer at room temperature for 2 h to obtain a quantum dot solution; according to the above amount of CaCO3 Add to the quantum dot solution, stir with a magnetic stirrer at room temperature for 7 hours, and dry the obtained solution at 100°C; grind the dried powder thoroughly, transfer the powder to a glass slide, put it in a muffle furnace and sinter it at 400°C for 4 hours, cool it to room temperature, transfer the powder to an agate mortar, grind it thoroughly, and obtain K 0.25 Cs 0.75 PbB 3 / CaCO 3 Composite luminescent material, in which K 0.25 Cs 0.75 PbB 3 The concentration of quantum dots was 10 wt%.
[0113] Embodiment 21
[0114] Table 21
[0115] raw material Weight(g) DMF 5 Cb 0.02 <![CDATA[PbBr 2 ]]> 0.04 <![CDATA[CaCO 3 ]]> 0.5 KBr 0.003
[0116] Accurately weigh the above amounts of DMF, KBr, CsBr and PbBr according to Table 21 2 , put into a beaker, and stir with a magnetic stirrer at room temperature for 2 h to obtain a quantum dot solution; according to the above amount of CaCO 3 Add to the quantum dot solution, stir with a magnetic stirrer at room temperature for 7 hours, and dry the obtained solution at 80°C; grind the dried powder thoroughly, transfer the powder to a glass slide, put it into a muffle furnace and sinter at 400°C for 3 hours, cool it to room temperature, transfer the powder to an agate mortar, grind it thoroughly, and obtain K 0.25 Cs 0.75 PbB 3 / CaCO 3 Composite luminescent material, in which K 0.25 Cs 0.75 PbB 3 The concentration of quantum dots was 10 wt%.
[0117] Embodiment 22
[0118] Table 22
[0119]
[0120]
[0121] Accurately weigh the above amounts of DMF, KBr, CsBr and PbBr according to Table 22 2 , put into a beaker, and stir with a magnetic stirrer at room temperature for 2 h to obtain a quantum dot solution; according to the above amount of CaCO 3Add to the quantum dot solution, stir with a magnetic stirrer at room temperature for 7 hours, and dry the obtained solution at 80°C; grind the dried powder thoroughly, transfer the powder to a glass slide, put it into a muffle furnace and sinter at 400°C for 5 hours, cool it to room temperature, transfer the powder to an agate mortar, grind it thoroughly, and obtain K 0.25 Cs 0.75 PbB 3 / CaCO 3 Composite luminescent material, in which K 0.25 Cs 0.75 PbB 3 The concentration of quantum dots was 10 wt%.
[0122] Embodiment 23
[0123] Table 23
[0124] raw material Weight(g) DMF 5 Cb 0.02 <![CDATA[PbBr 2 ]]> 0.04 <![CDATA[CaCO 3 ]]> 0.5 KBr 0.003
[0125] Accurately weigh the above amounts of DMF, KBr, CsBr and PbBr according to Table 23 2 , put into a beaker, and stir with a magnetic stirrer at room temperature for 2 h to obtain a quantum dot solution; according to the above amount of CaCO 3 Add to the quantum dot solution, stir with a magnetic stirrer at room temperature for 7 hours, and dry the obtained solution at 80°C; grind the dried powder thoroughly, transfer the powder to a glass slide, put it into a muffle furnace and sinter at 300°C for 4 hours, cool it to room temperature, transfer the powder to an agate mortar, grind it thoroughly, and obtain K 0.25 Cs 0.75 PbB 3 / CaCO 3 Composite luminescent material, in which K 0.25 Cs 0.75 PbB 3 The concentration of quantum dots was 10 wt%.
[0126] Embodiment 24
[0127] Table 24
[0128] raw material Weight(g) DMF 5 Cb 0.02 <![CDATA[PbBr 2 ]]> 0.04 <![CDATA[CaCO 3 ]]> 0.5 KBr 0.003
[0129] Accurately weigh the above amounts of DMF, KBr, CsBr and PbBr according to Table 24 2 , put into a beaker, and stir with a magnetic stirrer at room temperature for 2 h to obtain a quantum dot solution; according to the above amount of CaCO 3Add to the quantum dot solution, stir with a magnetic stirrer at room temperature for 7 hours, and dry the obtained solution at 80°C; grind the dried powder thoroughly, transfer the powder to a glass slide, put it into a muffle furnace and sinter at 200°C for 4 hours, cool it to room temperature, transfer the powder to an agate mortar, grind it thoroughly, and obtain K 0.25 Cs 0.75 PbB 3 / CaCO 3 Composite luminescent material, in which K 0.25 Cs 0.75 PbB 3 The concentration of quantum dots was 10 wt%.
[0130] Comparative Example 1
[0131] Table 25
[0132] raw material Weight(g) DMF 5 Cb 0.02 <![CDATA[PbBr 2 ]]> 0.04 <![CDATA[CaCO 3 ]]> 0.5
[0133] Accurately weigh the above amounts of DMF, CsBr and PbBr according to Table 25 2 , put into a beaker, and stir with a magnetic stirrer at room temperature for 2 h to obtain a quantum dot solution; according to the above amount of CaCO 3 Add to the quantum dot solution, stir with a magnetic stirrer at room temperature for 7 hours, dry the obtained solution at 80°C, and grind the dried powder thoroughly to obtain CsPbBr 3 / CaCO 3 Composite luminescent material, including CsPbBr 3 The concentration of quantum dots was 10 wt%.
[0134] Figure 1 The X-ray diffraction spectra of the samples prepared in Example 1, Example 13, Example 14 and Comparative Example 1 show that the diffraction peaks of the perovskite quantum dot composite luminescent materials sintered at high temperatures of 400°C, 300°C and 200°C and at room temperature correspond to CsPbBr 3 and CaCO 3 .
[0135] Figure 2 The emission spectra of the samples prepared in Example 1-4 under 365 nm wavelength excitation are shown in the figure. It can be seen from the figure that the K x Cs 1-x PbB 3 / CaCO 3 When the sample is excited by 365nm near-ultraviolet light, the peak value is around 525nm, and the luminescence intensity is highest when x is 0.25.
[0136] Figure 3The X-ray diffraction spectrum of the sample prepared in Example 3 shows that the K 0.25 Cs 0.75 PbB 3 / CaCO 3 Perovskite quantum dot composite luminescent material, whose diffraction peak corresponds to K 0.25 Cs 0.75 PbB 3 and CaCO 3 .
[0137] Figure 4 These are the emission spectra of the samples prepared in Example 1, Example 8, Example 9, Example 10, and Example 11 under excitation with a near-ultraviolet wavelength of 365 nm. It can be seen from the figure that the samples with different quantum dot concentrations have a peak value at around 525 nm under excitation with a near-ultraviolet wavelength of 365 nm.
[0138] Figure 5 The emission spectra of the samples prepared in Example 1, Example 13, Example 14 and Comparative Example 1 under the excitation of 365nm near-ultraviolet light wavelength can be seen from the figure. 3 / CaCO 3 The sample was excited by 365nm near-ultraviolet light, and the peak was around 527nm. After heat treatment at 400℃, the CsPbBr 3 / CaCO 3 The luminescence intensity is higher, and its half-peak width is 20-35nm; while the luminescence intensity of the unsintered samples and the samples sintered at 200℃ and 300℃ is significantly reduced.
[0139] Figure 6 Take 2g of the sample prepared in Example 2, put it into 10ml of aqueous solution, stir it thoroughly and let it stand for 120 days. Figure 6 It can be seen that the fluorescence intensity in water remains basically unchanged within 120 days.
[0140] The above embodiments are only preferred embodiments of the present invention and are not intended to limit the implementation methods. The protection scope of the present invention shall be subject to the scope defined in the claims. Other different forms of changes or modifications may be made based on the above description. Obvious changes or modifications derived therefrom are still within the protection scope of the present invention.
Claims
1. A calcium carbonate-loaded perovskite quantum dot composite luminescent material, characterized in that: The chemical formula of the luminescent material is K x Cs 1-x PbBr3 / CaCO3, wherein 0≤x≤1; in the luminescent material, the concentration of perovskite quantum dots is 1-30wt%.
2. The composite luminescent material according to claim 1, characterized in that: The composite luminescent material carrier is calcium carbonate, and the surface layer is perovskite quantum dots.
3. The composite luminescent material according to claim 1, characterized in that: The chemical formula of the luminescent material is K x Cs 1- x PbBr3 / CaCO3, where 0≤x≤0.35, and the concentration of perovskite quantum dots is 5-25wt%.
4. A method for preparing the composite luminescent material according to any one of claims 1 to 3, characterized in that: The method comprises the following steps: (1) According to K x Cs 1-x The chemical composition of PbBr3 is obtained by dissolving lead bromide, potassium bromide and cesium bromide in DMF solution and stirring and impregnating to obtain a quantum dot dispersion; (2) adding calcium carbonate powder to the quantum dot dispersion obtained in step (1), stirring and impregnating the mixture, and drying the obtained product; (3) Grinding the mixture obtained in step (2) into powder and then transferring it into a muffle furnace for sintering to obtain the composite luminescent material.
5. The preparation method according to claim 4, characterized in that: In the step (1), the stirring time is 1-3 hours.
6. The preparation method according to claim 4, characterized in that: In the step (2), the stirring time is 5-8 hours and the drying temperature is 50-100°C.
7. The preparation method according to claim 4, characterized in that: In the step (3), the sintering temperature is 200-400° C. and the sintering time is 3-5 hours.
8. Use of the composite luminescent material according to any one of claims 1 to 3 or the composite luminescent material prepared by the preparation method according to any one of claims 4 to 7 in lighting display and fluorescent ink.