Organic-inorganic hybrid zero-dimensional metal halide perovskite near-infrared luminescent material and preparation method and application thereof

Abstract

The invention discloses an organic-inorganic hybrid zero-dimensional metal halide perovskite near-infrared luminescent material as well as a preparation method and application thereof. The chemical general formula of the organic-inorganic hybrid zero-dimensional metal halide perovskite near-infrared luminescent material is (4-Mtp) 2Zn (1-x) Br4: xSb < 3 + >, wherein 4-Mtp is 4-mercaptopyridine, and x is greater than or equal to 0 and less than or equal to 0.2; according to the metal halide near-infrared luminescent material, Sb ions are used for replacing near-infrared luminescence of traditional Cr ions, and the metal halide near-infrared luminescent material can be effectively excited by light within the wavelength range of 325-425 nm to emit near-infrared light with the peak value within the range of 745 nm; as Sb is used as an activating agent, the metal halide calcium near-infrared luminescent material is harmless to the environment and organisms, meanwhile, the metal halide calcium near-infrared luminescent material can be applied to the fields of biological nondestructive testing, long-wave communication, medical treatment, national safety, near-infrared LEDs and the like, the environmental pollution degree is reduced, and the metal halide calcium near-infrared luminescent material has wide application prospects.

Description

Technical Field

[0001] The present invention belongs to the technical field of near-infrared luminescent materials, and specifically relates to an organic-inorganic hybrid zero-dimensional metal halide perovskite near-infrared luminescent material, a preparation method thereof, and an application thereof. Background Art

[0002] Hybrid metal halides (HMHs) with superior photoluminescence (PL) properties are considered promising emitters due to their well-tuned structure and composition and easy synthesis, suitable for various applications such as light-emitting diodes (LEDs), multilayer anti-counterfeiting and sensors. In recent years, 0D HMHs with host-guest structures have attracted much attention due to their high photoluminescence quantum efficiencies (PLQYs). m B n X z , consisting of an organic cation at position A, a metal cation at position B, and a halogen anion at position X.

[0003] Currently, most mainstream near-infrared luminescent materials are realized by doping trivalent Cr ions with different matrix perovskite luminescent materials, which utilize the fact that trivalent Cr ions are easily affected by the crystal field environment to achieve near-infrared luminescence. Halide perovskite materials are the most important scientific discovery in the field of optoelectronic materials science in recent years. By doping Cr ions in organic and inorganic halide perovskites, high near-infrared spectra have been achieved. 3+ -Activated Organic Hafnium Chlorine for Multi-Optoelectronic Applications. Advanced Optical Materials, 2024, 2400437(1-8). Another example is Adam, Kabanski; Maciej, Ptakand; Dagmara, Stefanska; et al., OrganicFramework Optical Thermometer Based on Cr 3+ Ion Luminescence.ACSAppl.Mater.Interfaces 2023,15,5,7074-7082.

[0004] Although a series of excellent results have been achieved in the near-infrared field by doping with Cr ions, Cr ions have potential biological hazards. Summary of the Invention

[0005] To solve the above technical problems, the present invention provides an organic-inorganic hybrid zero-dimensional metal halide perovskite near-infrared luminescent material and its preparation method, which can emit near-infrared light under the excitation of ultraviolet light and can be applied to the fields of biological non-destructive testing, long-wave communication, medical treatment, national security and near-infrared LED, etc., reducing the degree of environmental pollution and having broad application prospects. At the same time, due to Sb 3 The energy level structure of + is relatively rich, which can provide a variety of excitation and emission paths, thereby realizing the design of multifunctional optoelectronic materials.

[0006] The present invention provides an application of the organic-inorganic hybrid zero-dimensional metal halide perovskite near-infrared luminescent material as a night vision material.

[0007] To achieve the above object, the technical solution adopted by the present invention is as follows:

[0008] The present invention provides an organic-inorganic hybrid zero-dimensional metal halide perovskite near-infrared luminescent material, characterized in that the chemical formula of the organic-inorganic hybrid zero-dimensional metal halide perovskite near-infrared luminescent material is: (4-Mtp)2Zn 1-x Br4:xSb 3+ ; Wherein, 4-Mtp is 4-mercaptopyridine, 0<x≤0.2.

[0009] The organic-inorganic hybrid zero-dimensional metal halide perovskite near-infrared luminescent material can emit near-infrared light under the excitation of ultraviolet light.

[0010] The present invention also provides a method for preparing the organic-inorganic hybrid zero-dimensional metal halide perovskite near-infrared luminescent material, which comprises the following steps:

[0011] 4-mercaptopyridine, a zinc precursor, an antimony precursor and a hydrobromic acid solution are mixed, heated at 105-115° C. for reaction for 1.5-2.5 hours, cooled and allowed to stand in an environment of 55-65° C. for crystallization, and the precipitated crystals are washed and dried to obtain an organic-inorganic hybrid zero-dimensional metal halide perovskite near-infrared luminescent material.

[0012] The molar ratio of the 4-mercaptopyridine, the zinc precursor and the antimony precursor is 1:(0.40-0.50):(0.01-0.10); the concentration of the 4-mercaptopyridine in the hydrobromic acid solution is 0.1-1.0M.

[0013] Furthermore, the molar ratio of 4-mercaptopyridine, zinc precursor, antimony precursor and hydrogen bromide is 2:1-x:x:4, wherein the 4-Mtp precursor is calculated as 4-Mtp molecules, the Zn precursor is calculated as Zn atoms, the Sb precursor is calculated as Sb atoms, and the hydrogen bromide is calculated as Br atoms.

[0014] The mass concentration of the hydrobromic acid solution is 48%.

[0015] The zinc precursor is at least one of a Zn halide and a Zn hydroxide.

[0016] The zinc precursor is preferably one or more of ZnCl2 and ZnBr2.

[0017] The purity of the Zn precursor is ≥98%.

[0018] The antimony precursor is a halide of Sb.

[0019] The antimony precursor is preferably SbBr3.

[0020] The purity of the Sb precursor is ≥99.5%.

[0021] The crystallization time is 10 to 12 hours.

[0022] The washing is performed using isopropyl alcohol.

[0023] The present invention also provides the use of the organic-inorganic hybrid zero-dimensional metal halide perovskite near-infrared luminescent material as a night vision material.

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] The organic-inorganic hybrid zero-dimensional metal halide perovskite near-infrared luminescent material provided by the present invention replaces the traditional Cr ions with Sb ions to achieve the near-infrared luminescence of (4-Mtp)2ZnBr4. The principle is that Sb 3 Doped zero-dimensional organometallic chlorides achieve efficient broadband NIR emission through lattice distortion and self-trapped exciton (STE) emission. This luminescence mechanism not only improves luminescence efficiency but also significantly enhances the thermal and photostability of the material. It can be effectively excited by light in the 325nm to 425nm wavelength range, emitting near-infrared light with a peak at 745nm. Because Sb is used as an activator, it is environmentally and biohazardous.

[0026] At the same time, compared with traditional perovskite materials, Sb 3+ Doping can enhance the material's environmental stability, reducing the effects of humidity and heat on its performance, thereby increasing the device's lifespan. This allows the prepared near-infrared metal halide luminescent material to be used in fields such as non-destructive monitoring, near-infrared LEDs, security and anti-counterfeiting, and long-wave communications, offering broad application prospects.

[0027] The preparation method of the organic-inorganic hybrid zero-dimensional metal halide perovskite near-infrared luminescent material provided by the present invention is prepared by slow evaporation and crystallization, which is simple to operate and highly efficient, is conducive to industrial production, and is more conducive to the further application and promotion of the material. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 The crystal structure of the (4-Mtp)2ZnBr4 luminescent material prepared in Comparative Example 1;

[0029] Figure 2 The X-ray diffraction patterns of the (4-Mtp)2ZnBr4 luminescent material prepared in Comparative Example 1 are obtained from experimental tests and theoretical simulations;

[0030] Figure 3 The X-ray diffraction patterns of the luminescent materials prepared in various embodiments and comparative examples are shown;

[0031] Figure 4 This is the mapping spectrum of the organic-inorganic hybrid metal halide near-infrared luminescent material prepared in Example 1;

[0032] Figure 5 The excitation and emission spectra of the organic-inorganic hybrid metal halide near-infrared luminescent materials prepared in Comparative Example 1 and Example 1 are shown;

[0033] Figure 6 Emission spectrum curves of the organic-inorganic hybrid metal halide near-infrared luminescent materials prepared in various embodiments;

[0034] Figure 7 The emission spectra of the organic-inorganic hybrid zero-dimensional metal halide prepared in Example 1 and Comparative Example 2 under the same excitation at 402 nm;

[0035] Figure 8 This is the emission spectrum of the organic-inorganic hybrid zero-dimensional metal halide prepared in Comparative Example 3 under 420nm excitation;

[0036] Figure 9 Figure 1 is a picture of a toy bear and a basketball under natural light (a), and a picture of a toy bear and a basketball taken under dark conditions using a near-infrared camera under illumination of the organic-inorganic hybrid zero-dimensional metal halide perovskite near-infrared luminescent material in Example 1 (b). DETAILED DESCRIPTION

[0037] The present invention is described in detail below with reference to the embodiments.

[0038] The 4-mercaptopyridine, ZnBr2, and SbBr3 used in the examples and comparative examples were all analytically pure, and the hydrobromic acid solution used had a mass concentration of 48%. All of the above raw materials were commercially available.

[0039] Comparative Example 1

[0040] A (4-Mtp)2ZnBr4 luminescent material, the preparation method of which is as follows:

[0041] (1) Weigh 0.5 mmol of 4-mercaptopyridine and 0.25 mmol of ZnBr2 and 1 mL of hydrobromic acid solution into the culture bottle and heat at 110°C for 2 h;

[0042] (2) After the mixed solution in (1) cools to room temperature, transfer it to a 60°C drying oven and keep it warm for 12 hours to allow it to evaporate and crystallize;

[0043] (3) The crystal was washed three times with isopropyl alcohol and dried in a vacuum drying oven at 60° C. for 12 h to obtain a (4-Mtp) 2 ZnBr 4 luminescent material, which was designated as B1.

[0044] Example 1

[0045] The same method as Comparative Example 1 was used, except that 0.25 mmol of ZnBr2 was replaced by 0.213 mmol of ZnBr2 and 0.0375 mmol of SbBr3 to obtain an organic-inorganic hybrid zero-dimensional metal halide perovskite near-infrared luminescent material, which was recorded as B2.

[0046] Example 2

[0047] The same method as Comparative Example 1 was used, except that 0.25 mmol of ZnBr2 was replaced by 0.235 mmol of ZnBr2 and 0.015 mmol of SbBr3 to obtain an organic-inorganic hybrid zero-dimensional metal halide perovskite near-infrared luminescent material, which was recorded as B3.

[0048] Example 3

[0049] The same method as Comparative Example 1 was used, except that 0.25 mmol of ZnBr2 was replaced by 0.225 mmol of ZnBr2 and 0.025 mmol of SbBr3 to obtain an organic-inorganic hybrid zero-dimensional metal halide perovskite near-infrared luminescent material, which was recorded as B4.

[0050] Example 4

[0051] The same method as Comparative Example 1 was used, except that 0.25 mmol of ZnBr2 was replaced by 0.20 mmol of ZnBr2 and 0.05 mmol of SbBr3 to obtain an organic-inorganic hybrid zero-dimensional metal halide perovskite near-infrared luminescent material, which was recorded as B5.

[0052] Comparative Example 2

[0053] The same method as Example 2 was used, except that 1 mL of hydrobromic acid solution was replaced by 1 mL of hydrochloric acid solution. The obtained organic-inorganic zero-dimensional metal halide was recorded as B6.

[0054] Comparative Example 3

[0055] The rest is the same as Example 2, except that 0.25 mmol 4-mercaptopyridine is replaced by 0.25 mmol tetraethylammonium chloride. The obtained organic-inorganic zero-dimensional metal halide is recorded as B7.

[0056] Test Example 1

[0057] The crystal structure of the crystal B1 obtained in Comparative Example 1 was analyzed by single crystal X-ray diffraction, and its crystal structure was constructed using VESTA, as shown in FIG. Figure 1 Its crystal structure data are shown in Table 1.

[0058] The data in Table 1 record the crystal system, space group, lattice constant, atomic species and atomic positions of the crystal B1 prepared in Comparative Example 1. Using this data, the shape of the lattice and the atomic arrangement in the lattice can be determined.

[0059] Table 1

[0060]

[0061]

[0062]

[0063] In the data shown in Table 1, lattice constants a, b, and c represent the unit lattice axis lengths of the organic-inorganic hybrid metal halide near-infrared luminescent material (4-Mtp)2ZnBr4 crystal prepared in Comparative Example 1, α, β, and γ represent the angles between the axes of the unit lattice, and atomic coordinates x, y, and z are values ​​between 0 and 1 with the unit lattice as the unit to represent the position of each atom in the unit lattice.

[0064] It can be seen from the data in Table 1 that there are atoms of H, C, N, S, Zn, and Br in the (4-Mtp)2ZnBr4 crystal, among which H, C, N, and S come from the organic substance 4-mercaptopyridine.

[0065] As can be seen from Table 1, the organic-inorganic hybrid metal halide near-infrared luminescent material prepared in Comparative Example 1 belongs to the triclinic system and the P-1 group (the second space group in the International Tables for Crystallography). In the (4-Mtp)2ZnBr4 crystal, Zn has a tetrahedral structure.

[0066] Test Example 2

[0067] The organic-inorganic hybrid metal halide near-infrared luminescent materials B1-B5 prepared in Comparative Example 1 and Examples 1-4 were analyzed by powder X-ray diffraction and compared with the data obtained in Comparative Example 1. Figure 3 shown.

[0068] Depend on Figure 3 It can be seen that the X-ray diffraction data of the luminescent materials obtained in Examples 1-4 are consistent with the diffraction peak results of the crystal data analyzed in Comparative Example 1, and no obvious miscellaneous peaks are observed.

[0069] Test Example 3

[0070] The metal halide near-infrared luminescent material prepared in Example 1 was analyzed using a scanning electron microscope. Figure 4 shown.

[0071] Depend on Figure 4 It can be seen that after using mapping to analyze its components, it can be clearly observed that N, S, Zn, Br, Sb and other elements are contained in its structure. According to the mapping results, it can be reflected that the near-infrared luminescence of this metal halide at 742nm is Sb 3+ caused by ion doping.

[0072] Test Example 4

[0073] The metal halide near-infrared luminescent materials prepared in Comparative Example 1 and Example 1 were analyzed using a fluorescence spectrometer. The results are as follows: Figure 5 As shown. Figure 5 It can be seen that the comparative example 1 is not doped with Sb 3+ The emission peak position of the material obtained by ion is located at 587nm, which does not reach the near-infrared emission region. The emission peak of the metal halide near-infrared luminescent material prepared in Example 1 under 424nm excitation is located in the near-infrared region of 754nm, which can show long-wavelength near-infrared luminescence characteristics. It can be seen that the metal halide near-infrared luminescent material can be excited by ultraviolet light to emit near-infrared light, so that the luminescent material can convert ultraviolet light into near-infrared light. And its emission in the near-infrared region comes from Sb 3+ The successful doping of ions resulted in

[0074] Figure 6 is the emission spectrum of the metal halide near-infrared luminescent materials prepared in Examples 1-4 under the same excitation (402 nm), Figure 6 It can be seen that the maximum emission peak position of the metal halide near-infrared luminescent materials prepared in Examples 1-4 did not change significantly, but the luminous intensity of the metal halide near-infrared luminescent material prepared in Example 1 was significantly better than that of the other examples, which shows that its Sb 3+The incorporation concentration of ions is more appropriate.

[0075] Figure 7 The emission spectra of the organic-inorganic hybrid zero-dimensional metal halide prepared in Example 1 and Comparative Example 2 under the same excitation wavelength of 402 nm are shown. It can be seen that after the solvent is replaced with hydrochloric acid, the main position of the emission peak is located at 660 nm, which does not reach the near-infrared region.

[0076] Figure 8 This is the emission spectrum of Comparative Example 3 under 420 nm excitation, the main position of the emission peak is located at 630 nm, which does not reach the near infrared region.

[0077] Application Example 1

[0078] Application of the organic and inorganic metal halide near-infrared luminescent material obtained in Example 1 as a night vision luminescent material

[0079] The method is as follows: Organic AB glue is mixed with the luminescent material prepared in Example 1 at a mass ratio of 2:1 and stirred for 10 minutes. The mixture is then evenly applied to a 10W UV lamp with a wavelength of 420nm. The mixture is then dried at 60°C for 12 hours to solidify, thereby producing a UV lamp coated with the luminescent material prepared in Example 1. A dark test is performed: The prepared UV lamp is powered on and illuminated on a toy bear and a basketball, and night vision images are captured using a near-infrared camera.

[0080] The results are as follows Figure 9 shown. Figure 9 Figure (a) shows a toy bear and basketball under natural light. Figure 9 Figure (b) shows a picture of a toy bear and a basketball taken with a near-infrared camera under the illumination of the organic-inorganic metal halide near-infrared luminescent material prepared in Example 1. The toy bear and the basketball can still be clearly seen under dark conditions, demonstrating the application of the organic-inorganic metal halide near-infrared luminescent material obtained in Example 1 in night vision.

[0081] The preferred embodiments of the present invention are described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, and these simple modifications all fall within the scope of protection of the present invention.

[0082] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any appropriate manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

[0083] In addition, the various embodiments of the present invention may be arbitrarily combined, and as long as they do not violate the concept of the present invention, they should also be regarded as the contents disclosed by the present invention.

Claims

1. An organic-inorganic hybrid zero-dimensional metal halide perovskite near-infrared luminescent material, characterized in that: The chemical formula of the organic-inorganic hybrid zero-dimensional metal halide perovskite near-infrared luminescent material is: (4-Mtp)2Zn 1-x Br4:xSb 3+ ; Wherein, 4-Mtp is 4-mercaptopyridine, 0<x≤0.

2.

2. The organic-inorganic hybrid zero-dimensional metal halide perovskite near-infrared luminescent material according to claim 1, characterized in that: The organic-inorganic hybrid zero-dimensional metal halide perovskite near-infrared luminescent material can emit near-infrared light under the excitation of ultraviolet light.

3. The method for preparing the organic-inorganic hybrid zero-dimensional metal halide perovskite near-infrared luminescent material according to claim 1 or 2, characterized in that: The preparation method comprises the following steps: 4-mercaptopyridine, a zinc precursor, an antimony precursor and a hydrobromic acid solution are mixed, heated at 105-115° C. for reaction for 1.5-2.5 hours, cooled and allowed to stand in an environment of 55-65° C. for crystallization, and the precipitated crystals are washed and dried to obtain an organic-inorganic hybrid zero-dimensional metal halide perovskite near-infrared luminescent material.

4. The preparation method according to claim 3, characterized in that The molar ratio of the 4-mercaptopyridine, the zinc precursor and the antimony precursor is 1:(0.40-0.50):(0.01-0.10); the concentration of the 4-mercaptopyridine in the hydrobromic acid solution is 0.1-1.0M.

5. The preparation method according to claim 3 or 4, characterized in that The zinc precursor is at least one of a Zn halide and a Zn hydroxide.

6. The preparation method according to claim 3 or 4, characterized in that The antimony precursor is a halide of Sb.

7. The preparation method according to claim 3 or 4, characterized in that The zinc precursor is one or more of ZnCl2 and ZnBr2; the antimony precursor is SbBr3.

8. The preparation method according to claim 3 or 4, characterized in that The crystallization time is 10 to 12 hours.

9. The preparation method according to claim 3 or 4, characterized in that The washing is performed using isopropyl alcohol.

10. Use of the organic-inorganic hybrid zero-dimensional metal halide perovskite near-infrared luminescent material as claimed in claim 1 or 2 as a night vision material.

Images