Antimony ion doped organic-inorganic hybrid perovskite yellow light-emitting material, preparation method and application

Abstract

The invention belongs to the technical field of materials, and particularly relates to an efficient yellow light-emitting perovskite material, a preparation method thereof and a light-emitting device. Wherein the chemical formula of the hybrid perovskite yellow light-emitting material is (C4H12N) 2In1-xCl5. DMF: Sbx, and x is more than 0 and less than or equal to 0.05. According to the antimony ion doped organic-inorganic hybrid perovskite yellow light-emitting material, the perovskite matrix material provides a suitable crystal field environment for doping of Sb, perovskite doping is achieved by replacing an In site with Sb, efficient yellow light emission of Sb can be achieved under the structure, the light-emitting efficiency is high and is close to 100%, and the structure is stable. In addition, the luminescent material does not contain heavy metal lead, so that the harm of the material to human bodies and the environment can be avoided.

Description

Technical Field

[0002] This application belongs to the field of materials technology, and particularly relates to an antimony-doped organic-inorganic hybrid perovskite yellow light-emitting material, a preparation method, and a light-emitting device. Background Art

[0004] Organic-inorganic lead-free halide materials have attracted much attention due to their excellent optical properties. However, the synthesis of high photoluminescence lead-free organic-inorganic halide materials is still challenging. Therefore, designing a suitable host-guest system with a zero-dimensional (0D) structure can make the luminescent substances more easily embedded into the matrix regularly and promote the formation of efficient self-trapped excitons (STE), which is crucial for the synthesis of highly efficient luminescent materials. Unfortunately, most of them are lead-based hybrid perovskites. Therefore, it is necessary to develop low-cost, environmentally friendly, and highly efficient luminescent materials.

[0005] As a common doping element, Sb3+ has been widely studied in metal halide luminescent materials due to its low toxicity, oxidation stability, and high chemical activity. Although luminescent colors in various wavelength bands can be obtained by selecting appropriate metal halide matrices, its efficiency still needs to be further improved to meet the requirements of practical applications. Summary of the Invention

[0007] The purpose of this application is to provide an antimony-doped organic-inorganic hybrid perovskite yellow light-emitting material, a preparation method, and a light-emitting device, aiming to solve to a certain extent the problems of poor stability, low brightness, low luminescence efficiency of metal halide perovskite luminescent materials, and the fact that they often contain heavy metal lead, which is harmful to the environment and human body.

[0008] To achieve the above application purpose, the technical solution adopted in this application is as follows: An antimony ion-doped organic-inorganic hybrid perovskite yellow light-emitting material, the chemical formula of the light-emitting material is (C4H12N)2In1-xCl5·DMF:Sbx, 0 < x ≤ 0.05, and DMF is N,N-dimethylformamide.

[0009] Furthermore, the crystal structure of the light-emitting material is monoclinic system, space group C12 / c1, and the unit cell parameters are a = 13.7556 Å, b = 11.5098 Å, c = 13.7448 Å, α = γ = 90°, β = 94.594°. In this structure, In3+ coordinates with 5 Cl atoms and 1 DMF molecule to form [InCl5(C3H7NO)]2− polyhedra, which are spatially isolated by [C4H12N]+ cations.

[0010] Further, the chemical formula of the luminescent material is (C4H12N)2In1-xCl5·DMF:Sbx, where x is 0.01.

[0011] A preparation method of the above-mentioned antimony-doped organic-inorganic hybrid perovskite yellow light-emitting material includes the following preparation steps: Obtain an organic cation tetramethylammonium source, an antimony source, and an indium source according to the stoichiometric ratio of the luminescent material; dissolve the above-mentioned tetramethylammonium source, the antimony source, and the indium source in a solvent and perform a hydrothermal reaction, followed by cooling crystallization to obtain the antimony-doped organic-inorganic hybrid perovskite yellow light-emitting material.

[0012] Further, the steps of the hydrothermal reaction include: after dissolving the tetramethylammonium source, the antimony source, and the indium source in the solvent, raise the temperature to 140-160 °C within 1-2 hours and keep the temperature for 10-15 hours.

[0013] Further, the steps of the cooling crystallization include: at a cooling rate of 3-4 °C / h within 30-45 hours, cool the system after the hydrothermal reaction to 50 °C, and then cool the reaction system to 20-30 °C within 1-2 hours, followed by filtration and washing to obtain the antimony-doped organic-inorganic hybrid perovskite yellow light-emitting material.

[0014] Further, the tetramethylammonium source is selected from at least one of tetramethylammonium chloride, tetramethylammonium acetate, and tetramethylammonium sulfate; The antimony source is selected from at least one of SbCl3, Sb2(NO3)3, Sb2(SO4)3, and SbAc3; The indium source is selected from at least one of InCl3, In2(NO3)3, In2(SO4)3, and InAc3; The solvent is selected from HCl and N,N-dimethylformamide.

[0015] An optoelectronic device includes the above-mentioned antimony-doped organic-inorganic hybrid perovskite yellow light-emitting material.

[0016] Further, the optoelectronic device includes a light-emitting chip and a light-emitting glue layer bonded to the surface of the light-emitting chip; wherein, the light-emitting glue layer contains the above-mentioned antimony-doped organic-inorganic hybrid perovskite yellow light-emitting material, and the emission wavelength of the light-emitting chip is 300-320 nm.

[0017] The antimony-doped organic-inorganic hybrid perovskite yellow light-emitting material provided in the first aspect of this application realizes perovskite doping by substituting Sb for In. Since the pure (C4H12N)2InCl5·DMF material does not emit light, the incorporation of Sb serves as the light-emitting center, and self-trapped exciton (STE) luminescence is caused by the Jahn-Teller distortion of the [SbCl6]3− octahedron, achieving efficient yellow light emission. However, if the Sb doping ratio is higher than 0.05, it will cause luminescence quenching. Therefore, the doping molar ratio of Sb is greater than 0 and not higher than 0.05. The perovskite matrix material provides a suitable crystal field environment for the doping of Sb ions. Perovskite doping is realized by substituting Sb for In. Under this structure, Sb ions can achieve efficient yellow light emission, with an emission peak at 596 nm, a full width at half maximum (FWHM) of 130 nm, and a luminescence efficiency as high as 99.3%. In addition, since the system does not contain heavy metal lead, it can avoid the harm of the material to the human body and the environment.

[0018] The preparation method of the antimony-doped organic-inorganic hybrid perovskite yellow light-emitting material provided in the second aspect of this application. After obtaining the organic cation tetramethylammonium source, antimony source, and indium source according to the stoichiometric ratio of the antimony-doped organic-inorganic hybrid perovskite yellow light-emitting material, each raw material component is first dissolved in a DMF solution, and a certain amount of HCl is added and heated for hydrothermal reaction. Then, during the cooling process, the antimony-doped organic-inorganic hybrid perovskite yellow light-emitting material gradually crystallizes and precipitates to obtain the antimony-doped organic-inorganic hybrid perovskite yellow light-emitting material, with the chemical formula (C4H12N)2In1-xCl5·DMF:Sbx, where 0 < x ≤ 0.05. The preparation process is simple, suitable for industrial large-scale production and application, and the prepared antimony-doped perovskite yellow light-emitting material has good structural stability and high luminescence efficiency.

[0019] The optoelectronic device provided in the third aspect of this application. Since it contains the above-mentioned antimony-doped organic-inorganic hybrid perovskite yellow light-emitting material, the antimony-doped organic-inorganic hybrid perovskite yellow light-emitting material has good structural stability, a FWHM of 130 nm, and a luminescence efficiency as high as 99.3%. Therefore, the light-emitting device has excellent performance such as luminescence stability and luminescence efficiency. Description of the Drawings

[0021] In order to more clearly illustrate the technical solutions in the embodiments of this application, the following will briefly introduce the drawings required for use in the embodiments or the description of the prior art. Obviously, the following drawings are only some embodiments of this application. For those of ordinary skill in the art, without creative efforts, other drawings can be obtained based on these drawings.

[0022] Figure 1It is the crystal structure diagram of the antimony-doped organic-inorganic hybrid perovskite yellow light-emitting material provided in Embodiment 1 of the present application; Figure 2 It is the XRD test diagram of the antimony-doped organic-inorganic hybrid perovskite yellow light-emitting material provided in Embodiment 1 of the present application; Figure 3 It is the fluorescence spectrum diagram of the antimony-doped organic-inorganic hybrid perovskite yellow light-emitting material provided in Embodiment 1 of the present application; Figure 4 It is the chromaticity diagram of the antimony-doped organic-inorganic hybrid perovskite yellow light-emitting material provided in Embodiment 1 of the present application; Figure 5 It is the spectrum diagram of the LED light-emitting device provided in Embodiment 2 of the present application. Detailed implementation manners

[0024] The first aspect of the embodiments of the present application provides an antimony-doped organic-inorganic hybrid perovskite yellow light-emitting material. The chemical formula of the antimony-doped perovskite yellow light-emitting material is (C4H12N)2In1-xCl5·DMF:Sbx, where 0 < x ≤ 0.05. The antimony-doped perovskite yellow light-emitting material provided in the first aspect of the embodiments of the present application can achieve efficient yellow light by doping Sb ions in this system. The full width at half maximum is 130 nm, the luminous efficiency is as high as 99.3%, and the material has good stability and has good application prospects.

[0025] In some embodiments, the optoelectronic device includes a light-emitting chip and a light-emitting glue layer bonded to the surface of the light-emitting chip; wherein, the light-emitting glue layer contains the antimony-doped perovskite yellow light-emitting material, and the emission wavelength of the light-emitting chip is 250~350nm. In some specific embodiments, the antimony-doped perovskite yellow light-emitting material is ground into powder and then mixed with polymer materials such as polydimethylsiloxane, and after making a colloid with appropriate viscosity, the colloid is coated on the light-emitting chip and the colloid is cured to form a light-emitting glue layer, and the light-emitting device can be obtained by assembly.

[0026] In some embodiments, when the emission wavelength of the light-emitting chip is 310nm, a strong yellow light emission peak can be obtained in the light-emitting glue layer under the excitation condition of this wavelength, so that the light-emitting device can realize yellow LED lighting.

[0027] To enable those skilled in the art to clearly understand the above implementation details and operations of the present application, and to significantly reflect the advanced performance of the antimony-doped perovskite yellow light-emitting material and its preparation method and the light-emitting device in the embodiments of the present application, the following uses multiple embodiments to illustrate the above technical solutions.

[0028] Embodiment 1 A (C4H12N)2In0.99Cl5·DMF:Sb0.01 perovskite yellow light-emitting material, and its preparation includes the steps: First, dissolve 1.98 mmol of InCl3, 0.02 mmol of SbCl3, and 4 mmol of TMAC in 8 mL of DMF solution. Then transfer it to a reaction kettle and add 2 mL of HCl. Keep the mixture at 150 °C for 12 hours, and then slowly cool it to 30 °C within 45 hours. Synthesize transparent bulk crystals, wash them with DMF, and dry them overnight in a vacuum oven at 65 °C.

[0029] Example 2 An LED light-emitting device, and its preparation includes the steps: Package the crystal grown in Example 1 into an LED device by the following method. Grind the crystal into powder and mix it with PDMS (polydimethylsiloxane) to obtain a colloid with appropriate viscosity. Select a suitable chip (emission spectrum is around 310 nm) with the gold wire already welded, and then coat the colloid on the chip to obtain an LED light-emitting device. Put the above device into an oven and cure the colloid at 50 °C for 2 hours to obtain the final LED light-emitting device.

[0030] Furthermore, in order to verify the progressiveness of the embodiments of the present application, the antimony-doped perovskite yellow light-emitting material prepared in Example 1 and the LED light-emitting device prepared in Example 2 are respectively subjected to the following performance tests: 1. Perform single-crystal X-ray diffraction tests on the antimony-doped perovskite yellow light-emitting material prepared in Example 1 respectively, and its crystal structure is as shown in the appendix Figure 1 as shown. It can be seen from the appendix Figure 1 that the structure prepared in Example 1 is monoclinic system, space group C12 / c1, and the unit cell parameters are a = 13.7556 Å, b = 11.5098 Å, c = 13.7448 Å, α = γ = 90°, β = 94.594°. In this structure, In3+ coordinates with 5 Cl atoms and 1 DMF molecule to form [InCl5(C3H7NO)]2− polyhedra, which are spatially isolated by [C4H12N]+ cations

[0031] 2. Perform X-ray diffraction tests on the antimony-doped perovskite yellow light-emitting material prepared in Example 1 respectively, and the powder XRD test pattern is as shown in the appendix Figure 2 as shown. It can be seen from the appendix Figure 2 that the antimony-doped perovskite yellow light-emitting material prepared in Example 1 is consistent with the single-crystal simulation results, indicating that the doping of Sb does not change the structure.

[0032] 3. Test the fluorescence spectra of the antimony-doped perovskite yellow light-emitting materials prepared in Example 1 respectively; among them, the fluorescence spectrum of the rare-earth-doped perovskite red light-emitting material in Example 1 is as shown in the appendix Figure 3 and a strong yellow light emission peak can be obtained under 320 nm excitation, and the emission peak position is 596 nm. 4. Test the chromaticity diagrams of the antimony-doped perovskite yellow light-emitting materials prepared in Example 1 respectively; among them, the chromaticity diagram of the rare-earth-doped perovskite red light-emitting material in Example 1 is as shown in the appendix Figure 4 and the chromaticity coordinate position of the chromaticity diagram under 320 nm excitation is (0.503, 0.468). 5. Test the spectrum of the LED light-emitting device prepared in Example 2. As shown in the appendix Figure 5 it can be seen from the spectrogram that the antimony-doped perovskite yellow light-emitting material has good absorption of the violet chip and can be used for yellow light LED lighting.

[0033] From the above test results, it can be known that the chemical formula of the product prepared in the embodiment of the present application is (C4H12N)2In1-xCl5·DMF:Sbx, where 0 < x ≤ 0.05. This zero-dimensional lead-free perovskite has high-performance yellow light, the fluorescence quantum yield reaches 99.3%, and it has good structural stability. Moreover, it does not contain heavy metal lead, reducing the harm to the human body and the environment, and has broad application prospects in optoelectronic devices.

[0034] The above are only the preferred embodiments of the present application and are not intended to limit the present application. Any modifications, equivalent replacements, and improvements made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. An antimony ion-doped organic-inorganic hybrid perovskite yellow light-emitting material, characterized in that, The chemical formula of the luminescent material is (C4H12N)2In1-xCl5·DMF:Sbx, where 0 < x ≤ 0.05, and DMF is N,N-dimethylformamide.

2. The yellow light-emitting antimony-doped organic-inorganic hybrid perovskite material according to claim 1, wherein The crystal structure of the luminescent material is monoclinic system, space group C12 / c1, and the unit cell parameters are a = 13.7556 Å, b = 11.5098 Å, c = 13.7448 Å, α = γ = 90°, β = 94.594°. In this structure, In3+ coordinates with 5 Cl atoms and 1 DMF molecule to form [InCl5(C3H7NO)]2− polyhedra, which are spatially isolated by [C4H12N]+ cations.

3. The yellow light-emitting antimony-doped organic-inorganic hybrid perovskite material according to claim 2, wherein The chemical formula of the luminescent material is (C4H12N)2In1-xCl5·DMF:Sbx, where x is 0.

01.

4. A preparation method of an antimony-doped organic-inorganic hybrid perovskite yellow light-emitting material as described in any one of claims 1 to 3, characterized in that, It includes the following preparation steps: Obtain the organic cation tetramethylammonium source, antimony source and indium source according to the stoichiometric ratio of the luminescent material; dissolve the above-mentioned tetramethylammonium source, antimony source and indium source in a solvent for hydrothermal reaction, and cool and crystallize to obtain the antimony-doped organic-inorganic hybrid perovskite yellow light-emitting material.

5. The preparation method of an antimony-doped organic-inorganic hybrid perovskite yellow light-emitting material according to claim 4, characterized in that, The steps of the hydrothermal reaction include: after dissolving the tetramethylammonium source, antimony source and indium source in the solvent, heat up to 140 - 160 °C within 1 - 2 hours and keep warm for 10 - 15 hours.

6. The preparation method of an antimony-doped organic-inorganic hybrid perovskite yellow light-emitting material according to claim 5, characterized in that, The steps of the cooling crystallization include: at a cooling rate of 3 - 4 °C / h within 30 - 45 hours, cool the system after the hydrothermal reaction to 50 °C, and then cool the reaction system to 20 - 30 °C within 1 - 2 hours, filter and wash to obtain the antimony-doped organic-inorganic hybrid perovskite yellow light-emitting material.

7. A preparation method of an antimony-doped organic-inorganic hybrid perovskite yellow light-emitting material according to any one of claims 4 to 6, characterized in that, The tetramethylammonium source is selected from at least one of tetramethylammonium chloride, tetramethylammonium acetate, and tetramethylammonium sulfate; The antimony source is selected from at least one of SbCl3, Sb2(NO3)3, Sb2(SO4)3, and SbAc3; The indium source is selected from at least one of InCl3, In2(NO3)3, In2(SO4)3, and InAc3; The solvent is selected from HCl and N,N-dimethylformamide.

8. An optoelectronic device, characterized in that, The optoelectronic device contains an antimony-doped organic-inorganic hybrid perovskite yellow light-emitting material as described in any one of claims 1 - 3.

9. The optoelectronic device according to claim 8, characterized in that, The optoelectronic device includes a light-emitting chip and a light-emitting glue layer bonded to the surface of the light-emitting chip; wherein, the light-emitting glue layer contains the antimony-doped organic-inorganic hybrid perovskite yellow light-emitting material, and the emission wavelength of the light-emitting chip is 300 - 320 nm.

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