Method for preparing Sb-doped Cs2NaInCl6 self-trapping exciton light-emitting nanoparticles
Sb-doped Cs2NaInCl6 nanoparticles were prepared by hot injection, introducing SCN- ions to passivate defects and enhance electron-phonon coupling, thus solving the problems of low luminescence intensity and quantum yield and achieving a significant improvement in luminescence performance.
Patent Information
- Application Number
- CN202510969466.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-11
- Publication Date
- 2025-11-21
AI Technical Summary
The existing Sb-doped Cs2NaInCl6 luminescent materials have low luminescence intensity and quantum yield, which makes it difficult to meet the application requirements of new optoelectronic materials.
Sb-doped Cs2NaInCl6 self-trapped exciton luminescent nanoparticles were prepared by a hot-injection method. By introducing SCN- ions to passivate material defects, the electron-phonon coupling strength was enhanced, promoting the formation of self-trapped excitons.
It significantly improved the luminescence quantum yield of Sb-doped Cs2NaInCl6, and increased the luminescence intensity by about 2-4 times.
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Abstract
Description
TECHNICAL FIELD
[0001] The application relates to the technical field of luminescent materials, and discloses a method for preparing Sb-doped Cs2NaInCl6 self-trapped exciton luminescent nanoparticles. BACKGROUND
[0002] In the non-lead perovskite system, the double perovskite structure is widely concerned due to its unique crystal structure and electronic characteristics. Among them, Cs2NaInCl6 as a new type of non-lead double perovskite has the advantages of wide band gap, high stability and low toxicity, but its intrinsic luminescent efficiency is low, which is mainly caused by the limited radiation recombination process of self-trapped excitons. Self-trapped exciton luminescence is usually caused by carrier localization due to lattice distortion, and its luminescent characteristics are strongly dependent on the electronic-phonon coupling strength and defect state distribution of the material. In Cs2NaInCl6, the introduction of Sb 3+ can form [InCl6] 3- luminescent centers and realize high-efficiency broadband luminescence through exciton self-trapping effect. However, how to optimize and control the luminescent properties of Sb-doped Cs2NaInCl6, especially the improvement of luminescent intensity and quantum yield, is a key technical problem for the application of this type of material in the new photoelectric material industry. SUMMARY
[0003] In view of the above defects of the prior art, the technical problem to be solved by the application is to provide a method for improving the performance of Sb-doped perovskite self-trapped exciton luminescent material.
[0004] To achieve the above-mentioned purpose, the application provides a method for preparing Sb-doped Cs2NaInCl6 self-trapped exciton luminescent nanoparticles, which is prepared by a hot injection method; the method is characterized in that, in the preparation process, SCN-ions are introduced, the introduced SCN-ions can passivate the surface and internal defects of the Cs2NaInCl6 material, inhibit the non-radiative recombination caused by defect trap centers, enhance the electronic-phonon coupling strength, promote the formation of self-trapped excitons, and thus increase the self-trapped exciton luminescent performance of Sb-doped non-lead-based perovskite Cs2NaInCl6.
[0005] As an optimization, NaSCN is used as an additive to achieve the purpose of introducing SCN-ions.
[0006] As an optimization, in the preparation process, the following steps are included:
[0007] Step 1, in a container, 1 mmol of Cs2CO3, 1 mL of oleic acid and 2 mL of 1-octadecene are added, then the reaction temperature is increased to 100-130 DEG C until a transparent Cs oleate precursor solution A is formed;
[0008] Step 2: Place 0.01-0.1 mmol of SbCl3, 0.01-0.5 mmol of NaSCN, 0.5-1 mmol of NaCl, and 0.9-1 mmol of InCl3 into a container and mix with 10 mL of 1-octadecene, 1.5 mL of oleic acid, and 1.5 mL of oleylamine; then heat the mixture to 100-130 °C and degas it under vacuum for 1 hour, and then heat it to 150-170 °C under a nitrogen atmosphere until the reaction is complete and a transparent metal halide precursor solution B is formed.
[0009] Step 3: Quickly inject Cs oleic acid precursor solution A into metal halide precursor solution B, and then quickly place the mixed solution in an ice-water bath to cool it to room temperature; after cooling, centrifuge the solution to remove unreacted substances in the supernatant, and then wash the precipitate several times in hexane to obtain SCN- ion-treated nanocrystals.
[0010] As an optimization, a three-necked flask is used as the container in step 1; and a stable environment is provided in the three-necked flask by continuously introducing nitrogen gas.
[0011] In summary, the beneficial effects of introducing SCN-ions in the above methods are that SCN-ions passivate the surface and internal defects of Cs2NaInCl6 materials, suppress nonradiative recombination caused by defect trap centers, enhance the electron-phonon coupling strength of the material, promote the formation of self-trapped excitons, and ultimately improve the luminescence quantum yield of Sb-doped Cs2NaInCl6 double perovskite luminescent materials. Attached Figure Description
[0012] Figure 1 The X-ray diffraction patterns of the Sb-doped Cs2NaInCl6 double perovskite luminescent materials obtained in Example 1 and Comparative Example 1 are shown.
[0013] Figure 2 The emission spectra of Example 1 and Comparative Example 1 under 315 nm excitation are shown.
[0014] Figure 3 The emission spectra of Example 2 and Comparative Example 2 under 315 nm excitation are shown.
[0015] Figure 4 The emission spectra of Example 3 and Comparative Example 3 under 315 nm excitation are shown. Detailed Implementation
[0016] The present invention will be further described below with reference to the embodiments.
[0017] Example 1;
[0018] Sb-doped Cs₂NaInCl₆ self-trapped exciton luminescent nanoparticles were prepared using the following steps;
[0019] (1) In a three-necked flask, add 1 mmol of Cs2CO3, 1 mL of oleic acid and 2 mL of 1-octadecene, then raise the reaction temperature to 100°C and provide a stable environment by continuously purging nitrogen gas until the reaction is complete and a transparent Cs oleic acid precursor solution A is formed.
[0020] (2) Place 0.01 mmol of SbCl3, 0.1 mmol of NaSCN, 0.9 mmol of NaCl, and 1 mmol of InCl3 into a three-necked flask, and mix with 10 mL of 1-octadecene, 1.5 mL of oleic acid, and 1.5 mL of oleylamine. Then heat the mixture to 100 °C and degas it under vacuum for 1 hour. Then heat it to 150 °C under a nitrogen atmosphere until the reaction is complete and a transparent metal halide precursor solution B is formed.
[0021] (3) Quickly inject Cs oleic acid precursor solution A into metal halide precursor solution B, and then quickly place the mixed solution in an ice-water bath to cool it to room temperature. After cooling, centrifuge the solution to remove unreacted substances from the supernatant, and then wash the precipitate several times in hexane to obtain thiocyanate-treated nanocrystals.
[0022] This invention provides Comparative Example 1, which compares the effects with Example 1, and the synthesis method is as follows:
[0023] (1) In a three-necked flask, add 1 mmol of Cs2CO3, 1 mL of oleic acid and 2 mL of 1-octadecene, then raise the reaction temperature to 100°C and provide a stable environment by continuously purging nitrogen gas until the reaction is complete and a transparent Cs oleic acid precursor solution A is formed.
[0024] (2) Place 0.01 mmol of SbCl3, 1 mmol of NaCl, and 1 mmol of InCl3 into a three-necked flask and mix with 10 mL of 1-octadecene, 1.5 mL of oleic acid, and 1.5 mL of oleylamine. Then heat the mixture to 100 °C and degas it under vacuum for 1 hour. Then heat it to 150 °C under a nitrogen atmosphere until the reaction is complete and a transparent metal halide precursor solution B is formed.
[0025] (3) Quickly inject Cs oleic acid precursor solution A into metal halide precursor solution B, and then quickly place the mixed solution in an ice-water bath to cool it to room temperature. After cooling, centrifuge the solution to remove unreacted substances from the supernatant, and then wash the precipitate several times in hexane to obtain thiocyanate-treated nanocrystals.
[0026] Comparative Example 1 uses the same experimental method as Example 1, but lacks NaSCN in the raw materials to compare the effect of SCN- ions on the luminescence properties of Sb-doped Cs2NaInCl6 double perovskite luminescent materials.
[0027] Figure 1 The XRD characterization of Example 1 and Comparative Example 1 shows that the XRD patterns of the synthesized Example 1 and Comparative Example 1 are highly consistent, thus confirming the successful synthesis of Sb-doped Cs2NaInCl6 double perovskite nanoparticles. The addition of NaSCN did not change the structure of the Cs2NaInCl6 double perovskite nanoparticles.
[0028] Figure 2 The emission spectrum of the sample under 315 nm light excitation is shown. Both Example 1 and Comparative Example 1 showed blue emission at 460 nm. The emission of the Sb-doped Cs2NaInCl6 double perovskite with the introduction of SCN- ions increased, and the intensity increased by about 4 times.
[0029] Example 2;
[0030] Sb-doped Cs₂NaInCl₆ self-trapped exciton luminescent nanoparticles were prepared using the following steps;
[0031] (1) In a three-necked flask, add 1 mmol of Cs2CO3, 1 mL of oleic acid and 2 mL of 1-octadecene, then raise the reaction temperature to 100°C and provide a stable environment by continuously purging nitrogen gas until the reaction is complete and a transparent Cs oleic acid precursor solution A is formed.
[0032] (2) Place 0.05 mmol of SbCl3, 0.25 mmol of NaSCN, 0.75 mmol of NaCl, and 0.95 mmol of InCl3 into a three-necked flask, and mix with 10 mL of 1-octadecene, 1.5 mL of oleic acid, and 1.5 mL of oleylamine. Then heat the mixture to 120 °C and degas it under vacuum for 1 hour. Then heat it to 160 °C under a nitrogen atmosphere until the reaction is complete and a transparent metal halide precursor solution B is formed.
[0033] (3) Quickly inject Cs oleic acid precursor solution A into metal halide precursor solution B, and then quickly place the mixed solution in an ice-water bath to cool it to room temperature. After cooling, centrifuge the solution to remove unreacted substances from the supernatant, and then wash the precipitate several times in hexane to obtain thiocyanate-treated nanocrystals.
[0034] This invention provides Comparative Example 2, which compares the effects with Example 2, and the synthesis method is as follows:
[0035] (1) In a three-necked flask, add 1 mmol of Cs2CO3, 1 mL of oleic acid and 2 mL of 1-octadecene, then raise the reaction temperature to 100°C and provide a stable environment by continuously purging nitrogen gas until the reaction is complete and a transparent Cs oleic acid precursor solution A is formed.
[0036] (2) Place 0.01 mmol of SbCl3, 1 mmol of NaCl, and 1 mmol of InCl3 into a three-necked flask and mix with 10 mL of 1-octadecene, 1.5 mL of oleic acid, and 1.5 mL of oleylamine. Then heat the mixture to 120 °C and degas it under vacuum for 1 hour. Then heat it to 160 °C under a nitrogen atmosphere until the reaction is complete and a transparent metal halide precursor solution B is formed.
[0037] (3) Quickly inject Cs oleic acid precursor solution A into metal halide precursor solution B, and then quickly place the mixed solution in an ice-water bath to cool it to room temperature. After cooling, centrifuge the solution to remove unreacted substances from the supernatant, and then wash the precipitate several times in hexane to obtain thiocyanate-treated nanocrystals.
[0038] Comparative Example 2 uses the same experimental method as Example 2, but lacks NaSCN in the raw materials to compare the effect of SCN- ions on the luminescence properties of Sb-doped Cs2NaInCl6 double perovskite luminescent materials.
[0039] Figure 3 The emission spectrum of the sample under 315nm light excitation is shown. Both Example 2 and Comparative Example 2 showed blue emission at 460nm. The emission of the Sb-doped Cs2NaInCl6 double perovskite with the introduction of SCN- ions increased, and the intensity increased by about 2 times.
[0040] Example 3;
[0041] Sb-doped Cs₂NaInCl₆ self-trapped exciton luminescent nanoparticles were prepared using the following steps;
[0042] (1) In a three-necked flask, add 1 mmol of Cs2CO3, 1 mL of oleic acid and 2 mL of 1-octadecene, then raise the reaction temperature to 100°C and provide a stable environment by continuously purging nitrogen gas until the reaction is complete and a transparent Cs oleic acid precursor solution A is formed.
[0043] (2) Place 0.1 mmol of SbCl3, 0.5 mmol of NaSCN, 0.5 mmol of NaCl, and 0.9 mmol of InCl3 into a three-necked flask, and mix with 10 mL of 1-octadecene, 1.5 mL of oleic acid, and 1.5 mL of oleylamine. Then heat the mixture to 130 °C and degas it under vacuum for 1 hour. Then heat it to 170 °C under a nitrogen atmosphere until the reaction is complete and a transparent metal halide precursor solution B is formed.
[0044] (3) Quickly inject Cs oleic acid precursor solution A into metal halide precursor solution B, and then quickly place the mixed solution in an ice-water bath to cool it to room temperature. After cooling, centrifuge the solution to remove unreacted substances from the supernatant, and then wash the precipitate several times in hexane to obtain thiocyanate-treated nanocrystals.
[0045] This invention provides Comparative Example 3, which compares the effects with Example 3, and the synthesis method is as follows:
[0046] (1) In a three-necked flask, add 1 mmol of Cs2CO3, 1 mL of oleic acid and 2 mL of 1-octadecene, then raise the reaction temperature to 100°C and provide a stable environment by continuously purging nitrogen gas until the reaction is complete and a transparent Cs oleic acid precursor solution A is formed.
[0047] (2) Place 0.01 mmol of SbCl3, 1 mmol of NaCl, and 1 mmol of InCl3 into a three-necked flask and mix with 10 mL of 1-octadecene, 1.5 mL of oleic acid, and 1.5 mL of oleylamine. Then heat the mixture to 120 °C and degas it under vacuum for 1 hour. Then heat it to 160 °C under a nitrogen atmosphere until the reaction is complete and a transparent metal halide precursor solution B is formed.
[0048] (3) Quickly inject Cs oleic acid precursor solution A into metal halide precursor solution B, and then quickly place the mixed solution in an ice-water bath to cool it to room temperature. After cooling, centrifuge the solution to remove unreacted substances from the supernatant, and then wash the precipitate several times in hexane to obtain thiocyanate-treated nanocrystals.
[0049] Comparative Example 3 uses the same experimental method as Example 3, but lacks NaSCN in the raw materials to compare the effect of SCN- ions on the luminescence properties of Sb-doped Cs2NaInCl6 double perovskite luminescent materials.
[0050] Figure 4 The emission spectrum of the sample under 315nm light excitation is shown. Both Example 3 and Comparative Example 3 showed blue emission at 460nm. The emission of the Sb-doped Cs2NaInCl6 double perovskite with the introduction of SCN- ions increased, and the intensity increased by about 2.5 times.
[0051] The preferred embodiments of the present invention have been described in detail above. It should be understood that those skilled in the art can make numerous modifications and variations based on the concept of the present invention without creative effort. Therefore, all technical solutions that can be obtained by those skilled in the art based on the concept of the present invention through logical analysis, reasoning, or limited experimentation on the basis of existing technology should be within the scope of protection defined by the claims.
Claims
1. A method for preparing Sb-doped Cs₂NaInCl₆ self-trapped exciton luminescent nanoparticles, wherein Sb-doped Cs₂NaInCl₆ self-trapped exciton luminescent nanoparticles are prepared by a hot-injection method; characterized in that; During the preparation process, SCN- ions are introduced. These SCN- ions can passivate surface and internal defects of Cs2NaInCl6 material, suppress nonradiative recombination caused by defect trap centers, enhance electron-phonon coupling strength, and promote the formation of self-trapped excitons, thereby increasing the self-trapped exciton luminescence performance of Sb-doped lead-free perovskite Cs2NaInCl6.
2. The method for preparing Sb-doped Cs₂NaInCl₆ self-trapped exciton luminescent nanoparticles as described in claim 1, characterized in that: The purpose of introducing SCN- ions is achieved by using NaSCN as an additive.
3. The method for preparing Sb-doped Cs₂NaInCl₆ self-trapped exciton luminescent nanoparticles as described in claim 1, characterized in that: The preparation process includes the following steps; Step 1: In a container, add 1 mmol of Cs2CO3, 1 mL of oleic acid, and 2 mL of 1-octadecene. Then raise the reaction temperature to 100-130℃ until the reaction is complete and a transparent Cs oleic acid precursor solution A is formed. Step 2: Place 0.01-0.1 mmol of SbCl3, 0.01-0.5 mmol of NaSCN, 0.5-1 mmol of NaCl, and 0.9-1 mmol of InCl3 into a container and mix with 10 mL of 1-octadecene, 1.5 mL of oleic acid, and 1.5 mL of oleylamine; then heat the mixture to 100-130 °C and degas it under vacuum for 1 hour, and then heat it to 150-170 °C under a nitrogen atmosphere until the reaction is complete and a transparent metal halide precursor solution B is formed. Step 3: Quickly inject Cs oleic acid precursor solution A into metal halide precursor solution B, and then quickly place the mixed solution in an ice-water bath to cool it to room temperature; after cooling, centrifuge the solution to remove unreacted substances in the supernatant, and then wash the precipitate several times in hexane to obtain SCN- ion-treated nanocrystals.
4. The method for preparing Sb-doped Cs₂NaInCl₆ self-trapped exciton luminescent nanoparticles as described in claim 3, characterized in that: The container used in step 1 is a three-necked flask; and a stable environment is provided in the three-necked flask by continuously purging nitrogen gas.