A large size organic ligand hybrid cu(i) halide material, and a preparation method and application thereof

Abstract

The application discloses a hybrid Cu(I) halide material of large-size organic ligand, and the chemical formula of the hybrid Cu(I) halide material is [A(CnH 2n+1 )3N]2Cu4Br6, wherein A is adamantyl, and n is any integer in 1-4. The flexible scintillation screen prepared from the material has good X-ray light yield and low detection limit, and high-resolution imaging pictures can be obtained for X-ray imaging.

Description

Technical Field

[0001] This invention belongs to the field of optoelectronic materials, specifically relating to a hybrid Cu(I) halide material with large-size organic ligands, its preparation method, and its application. Background Technology

[0002] Scintillator materials used in X-ray imaging can convert X-rays into visible light, and have important applications in non-destructive testing, security inspection, and biomedical imaging. Traditional inorganic scintillator materials containing heavy metal atoms have excellent scintillation properties, but the stringent requirements for bulk crystal growth and the high-temperature, high-pressure reaction conditions during preparation limit their applications.

[0003] Low-dimensional organic-inorganic hybrid metal halide materials possess excellent radiative-luminescence properties and can be prepared using simple solution methods, making them promising candidates for next-generation commercial scintillators. However, many challenges remain in their applications. For instance, while lead-based metal halides exhibit excellent radiative-luminescence performance, their toxicity and poor stability limit their development prospects. Copper(I)-based hybrid metal halides are environmentally friendly materials, and copper is abundant on Earth, which helps reduce preparation costs. Among the developed one-dimensional and two-dimensional hybrid copper(I) halides, many examples still exhibit low luminescence quantum efficiency, which is detrimental to achieving high light yields. Developing hybrid copper(I) halide materials with high luminescence quantum efficiency is a pressing issue in the field of scintillators.

[0004] The luminescence properties of organic-inorganic hybrid copper (I) halides are primarily determined by the material's structure. The abundance of organic ligands contributes to the structural diversity of hybrid copper (I) halides. From a structural perspective, low-dimensional copper (I) halide materials exhibit higher luminescence quantum efficiency than high-dimensional structures because the luminescent centers are separated, enhancing radiative recombination. Furthermore, the structure of the anion luminescent centers in hybrid copper (I) halides is strongly dependent on the size of the cations. The introduction of large-sized organic ligands allows for greater dispersion of the inorganic components of hybrid copper (I) halides, leading to a tendency towards a zero-dimensional structure. Summary of the Invention

[0005] The purpose of this section is to outline some aspects of embodiments of the present invention and to briefly describe some preferred embodiments. Simplifications or omissions may be made in this section, as well as in the abstract and title of this application, to avoid obscuring the purpose of these documents; however, such simplifications or omissions should not be construed as limiting the scope of the invention.

[0006] In view of the problems existing in the above and / or prior art, the present invention is proposed.

[0007] Therefore, the purpose of this invention is to overcome the shortcomings of the prior art and provide a hybrid Cu(I) halide material with large-size organic ligands.

[0008] To solve the above-mentioned technical problems, the present invention provides the following technical solution: the chemical formula of the hybrid Cu(I) halide material is [A(CnH... 2n+1 )3N]2Cu4Br6, where A is an adamantyl alkyl group and n is any integer from 1 to 4.

[0009] In a preferred embodiment of the present invention, the hybrid Cu(I) halide material, when n is 1, has the molecular formula C. 29 H 55 Br6Cu4N3O, with a molecular weight of 1195.38, has a monoclinic crystal system and space group P21 / c; its unit cell parameters are... α=90, β=95.731, γ=90, Z=4.

[0010] Another objective of this invention is to overcome the shortcomings of the prior art and provide a method for preparing hybrid Cu(I) halide materials with large-size organic ligands.

[0011] As a preferred embodiment of the preparation method described in this invention, wherein: A(CnH 2n+1 The protonation reaction of 3NOH and hydrobromic acid yields A(CnH) 2n+1 )3NBr;A(CnH 2n+1 3NBr and cuprous bromide were added to a solvent, followed by hypophosphoric acid. After evaporation under heating for one week, a hybrid Cu(I) halide material with large-sized organic ligands was obtained.

[0012] As a preferred embodiment of the preparation method described in this invention, wherein: the A(CnH 2n+1 The molar ratio of 3NBr to cuprous bromide is 1:1 to 2.

[0013] In a preferred embodiment of the preparation method described in this invention, the solvent is DMF.

[0014] In a preferred embodiment of the preparation method described in this invention, the volume ratio of the solvent to hypophosphoric acid is 1:0.5 to 1.

[0015] In a preferred embodiment of the preparation method described in this invention, the heating temperature is 50–60°C.

[0016] Another objective of this invention is to overcome the shortcomings of the prior art and provide an application of hybrid Cu(I) halide materials in the fabrication of flexible scintillator screens, X-ray detectors, and imaging.

[0017] As a preferred embodiment of the preparation method described in this invention, the flexible scintillator screen is prepared by grinding large-size rigid organic ligand copper (I) halide material crystals, sieving them into powder, uniformly mixing them with polymethyl methacrylate in chloroform, drop-coating the mixed solution onto a glass plate, and drying it at room temperature.

[0018] The final objective of this invention is to overcome the shortcomings of the prior art and provide an application of hybrid Cu(I) halide materials in information encryption storage and anti-counterfeiting materials.

[0019] Beneficial effects of this invention:

[0020] (1) This invention discloses a novel hybrid copper (I) halide material based on large-size organic ligands and its preparation method. The preparation process is simple and does not involve dangerous or complex operations. The raw materials used in the preparation are abundant, inexpensive, and environmentally friendly.

[0021] (2) This invention discloses a hybrid copper (I) halide material based on a large-size organic rigid ligand and a method for fabricating a flexible scintillation screen thereof. The flexible scintillation screen prepared from the material has good X-ray light yield and low detection limit, and can obtain high-resolution imaging images when used for X-ray imaging.

[0022] (3) The hybrid copper (I) halide material based on large-size organic ligands described in this invention has a large Stokes shift and high photoluminescence quantum efficiency (PLQY), wherein [A(CnH 2n+1 [3N]2Cu4Br6 emits a yellow-orange light under ultraviolet light. Attached Figure Description

[0023] To more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort. Wherein:

[0024] Figure 1 This is a schematic diagram of the crystal structure of the organic-inorganic hybrid copper (I) halide material in Embodiment 1 of the present invention.

[0025] Figure 2 The normalized solid-state emission spectrum of the organic-inorganic hybrid copper (I) halide material in Example 1 of this invention is shown.

[0026] Figure 3 This is the photoluminescence quantum yield spectrum of the organic-inorganic hybrid copper (I) halide material in Example 1 of the present invention.

[0027] Figure 4This is the solid-state photoluminescence lifetime decay curve of the organic-inorganic hybrid copper (I) halide material in Example 1 of the present invention.

[0028] Figure 5 The thermogravimetric analysis (TGA) spectrum of the organic-inorganic hybrid copper (I) halide material in Example 1 of this invention.

[0029] Figure 6 The flexible scintillator screen prepared by [A(CH3)3N]2Cu4Br6 in this invention is used for X-ray imaging of the object and the corresponding X-ray image obtained.

[0030] Figure 7 This is the synthesis roadmap.

[0031] Figure 8 This is a photograph of the light emitted, which is a comparative example 1 of the present invention.

[0032] Figure 9 This is a photoluminescence quantum efficiency diagram of Comparative Example 2 of Embodiment 1 of the present invention.

[0033] Figure 10 This is a crystal structure diagram of Comparative Example 1 of the present invention.

[0034] Figure 11 This is a crystal structure diagram of Comparative Example 2 of the present invention. Detailed Implementation

[0035] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, the specific embodiments of the present invention will be described in detail below with reference to the examples in the specification.

[0036] Many specific details are set forth in the following description in order to provide a full understanding of the invention. However, the invention may also be practiced in other ways different from those described herein, and those skilled in the art can make similar extensions without departing from the spirit of the invention. Therefore, the invention is not limited to the specific embodiments disclosed below.

[0037] Secondly, the term "one embodiment" or "embodiment" as used herein refers to a specific feature, structure, or characteristic that may be included in at least one implementation of the present invention. The phrase "in one embodiment" appearing in different places in this specification does not necessarily refer to the same embodiment, nor is it a single or selective embodiment that is mutually exclusive with other embodiments.

[0038] A hybrid copper(I) halide material based on a large-size organic ligand, characterized in that the material is an organic-inorganic hybrid copper(I) halide material with a zero-dimensional structure; the material exhibits Cu(I) polymer characteristics and has the general chemical formula [A(CnH2O)2]. 2n+1 [3N]2Cu4Br6, where A is an adamantyl alkyl group, and the chemical formula is C 10H 16 n is any integer from 1 to 4.

[0039] Hybrid copper (I) halide luminescent materials based on large-size organic ligands, using A(CnH 2n+1 The protonation reaction of 3NOH and hydrobromic acid yields A(CnH) 2n+1 )3NBr. A(CnH 2n+1 Single-crystal materials were prepared by "volatile crystallization" of 3NBr and cuprous bromide under heating conditions. The synthetic route is as follows: Figure 7 As shown.

[0040] Unless otherwise specified, all raw materials used in the embodiments of this invention are commercially available.

[0041] Table 1

[0042]

[0043] Example 1

[0044] This invention provides a method for preparing a hybrid Cu(I) halide material [A(CH3)3N]2Cu4Br6 with large-size organic ligands:

[0045] (1) Add 1 mmol of N,N,N-trimethyl-1-adamantyl ammonium hydroxide to a reaction flask, then add 10 ml of ethanol and 2 ml of hydrobromic acid. After stirring the reaction solution magnetically at room temperature for 5 hours, evaporate the solution to dryness using a rotary evaporator to obtain A(CH3)3NBr powder. 2n+1 The protonation reaction of 3NOH and hydrobromic acid yields A(CnH) 2n+1 Add A(CH3)3NBr and cuprous bromide to the reactor, followed by hypophosphorous acid and DMF. The ratio of cuprous bromide to DMF is 1:5 (mmol:ml), and the ratio of hypophosphorous acid to DMF is 1:2 (ml:ml).

[0046] (2) Sonicate until the solid in the reactor is completely dissolved to obtain the precursor liquid.

[0047] (3) The precursor solution was placed on a heating platform at 50°C to evaporate and crystallize. After 7 days, crystals precipitated in the precursor solution and were filtered to obtain the target product single crystal.

[0048] The single-crystal structure of the organic-inorganic hybrid copper(I) halide was determined using a single-crystal diffractometer. The test results showed that the chemical formula of [A(CH3)3N]2Cu4Br6 is C 29 H 55 N3OCu4Br6, space group P21 / c, crystal structure as follows: Figure 1 As shown in a.

[0049] Table 2

[0050]

[0051] Example 2

[0052] SC-XRD data were obtained on a Bruker SmartApex CCD diffractometer at room temperature using ω-2θ scanning technique with graphite monochromatic Mo-Kα. The structure of [A(CH3)3N]2Cu4Br6 is a radiation source. The solution and refinement results obtained using Olex2 and SHELXS (full matrix least squares over F2) are as follows: Figure 1 As shown.

[0053] TGA measurements were performed using a NETZSCH STA-2500 Regulus thermal analyzer. The heating rate was 10 K / min at a nitrogen atmosphere of 30 mL / min, and the temperature range was 25-500 °C. The test results are as follows: Figure 5 As shown, the actual decomposition temperature of the [A(CH3)3N]2Cu4Br6 material is approximately 245.13℃, demonstrating its high thermal stability.

[0054] The excitation-emission, luminescence quantum efficiency, and luminescence lifetime decay curves were measured using an Edinburgh FLS-980 spectrophotometer. A 450W xenon lamp was used for excitation-emission measurements, with an excitation spectrum ranging from 250 nm to 400 nm and an emission spectrum ranging from 400 nm to 800 nm. The test results are as follows: Figure 2 As shown, the emission peak of [A(CH3)3N]2Cu4Br6 is located at 600 nm (orange-yellow).

[0055] The photoluminescence quantum yield was measured using an integrating sphere mode under a 450W xenon lamp light source. The test results are as follows: Figure 3 As shown, the photoluminescence quantum efficiency of the material prepared in Example 1 is 99.86%.

[0056] The luminescence lifetime decay curve test was conducted using a 375nm laser, and the test results are as follows: Figure 4 As shown.

[0057] The luminescence lifetime of the material prepared in Example 1 was 35.28 μs.

[0058] Example 3

[0059] Taking the [A(CH3)3N]2Cu4Br6 material prepared in Example 1 as an example, a flexible scintillator screen was prepared. The specific steps are as follows:

[0060] (1) Grind the [A(CH3)3N]2Cu4Br6 material crystals thoroughly and pass them through a 200-mesh sieve to obtain crystal powder;

[0061] (2) Add [A(CH3)3N]2Cu4Br6 crystal powder and polymethyl methacrylate to chloroform and stir for 5 hours to make the mixture uniform.

[0062] (3) The solid-liquid ratio of the crystalline powder, polymethyl methacrylate, and chloroform (g:g:ml) is 0.1:0.2:2;

[0063] (4) The mixture is coated onto a glass plate and dried at room temperature for 5 hours to obtain a flexible scintillator film.

[0064] In this embodiment, the [A(CH3)3N]2Cu4Br6 flexible scintillator film is used as a flexible scintillator screen, and the spring and chip encapsulated in a capsule are used as the imaging objects. The final scintillator imaging result is as follows. Figure 6 As shown, clear imaging results can be obtained and internal information of the imaged object can be observed. Its X-ray imaging results have good imaging contrast and resolution.

[0065] Comparative Example 1

[0066] The difference from Example 1 is that in step (1), a large-sized ligand, methyltri-n-butylammonium bromide, and CuBr were used to prepare the compound (MtTBA)2Cu4Br6 (MtTPPh = methyltri-n-butylammonium cation). The crystal data are as follows. The crystal structure is as follows: Figure 10 As shown. After the solution prepared from the crystal is removed, the material undergoes severe oxidation within one hour, resulting in a significant decrease in luminescence intensity, such as... Figure 8 As shown.

[0067] Table 3

[0068]

[0069] Comparative Example 2

[0070] The difference from Example 1 is that in step (1), ethyltriphenylphosphonium bromide and CuBr were used to prepare the compound (EtTPPh)2Cu4Br6 (EtTPPh = ethyltriphenylphosphonium). The crystal diagram is shown below. Figure 11 As shown, the data is as follows. The photophysical properties of this material are as follows: Figure 9 As shown, PLQY is 60%, which is lower than the preferred material of Example 1 (99%).

[0071] Table 4

[0072]

[0073]

[0074] Comparative Example 3

[0075] The difference from Example 1 is that isopropanol was used as the solvent in step (1). Specifically, 1 mmol of the ligand and 1 mmol of CuBr were added to a 10 ml / 2 ml mixture of isopropanol and hypophosphite, heated at 60°C for 5 hours, and then the undissolved raw materials in the reaction flask were filtered off while hot. The filtrate was then cooled to room temperature at a rate of 5°C / h to obtain (TMAA)₂Cu₄Br₆ crystals. Compared to the preferred solvent DMF, the material prepared using isopropanol as a solvent has lower purity. Furthermore, (TMAA)₂Cu₄Br₆ cannot be prepared in solvents such as methanol, ethanol, dichloroethanol, and toluene.

[0076] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all such modifications or substitutions should be covered within the scope of the present invention.

Claims

1. A hybrid Cu(I) halide material with a large-size organic ligand, characterized in that: The chemical formula of the hybrid Cu(I) halide material is [A(CnH] 2n+1 )3N]2Cu4Br6, where A is an adamantyl alkyl group and n is any integer from 1 to 4.

2. The hybrid Cu(I) halide material as described in claim 1, characterized in that: The molecular formula of the hybrid Cu(I) halide material is C 29 H 55 Br6Cu4N3O has a molecular weight of 1195.38, a monoclinic crystal system, and a space group of P21 / c. Its unit cell parameters are a = 14.3386 Å, b = 15.7336 Å, c = 17.2818 Å, and V = 3879.2 Å. 3 , α=90, β=95.731, γ=90, Z =4.

3. The method for preparing the hybrid Cu(I) halide material as described in claim 1 or 2, characterized in that: include, A(CnH 2n+1 The protonation reaction of 3NOH and hydrobromic acid yields A(CnH) 2n+1 )3NBr;A(CnH 2n+1 )3NBr and cuprous bromide were added to a solvent, followed by hypophosphoric acid. After evaporation under heating for one week, a hybrid Cu(I) halide material with large-sized organic ligands was obtained. The A(CnH) 2n+1 The molar ratio of 3NBr to cuprous bromide is 1:1~2; The solvent is DMF; The volume ratio of the solvent to hypophosphoric acid is 1:0.5~1; The heating temperature is 50~60℃.

4. The application of the hybrid Cu(I) halide material as described in claim 1 in the preparation of flexible scintillator screens and X-ray detectors.

5. The application as described in claim 4, characterized in that: The flexible scintillator screen is made by grinding large-size rigid organic ligand copper(I) halide material crystals, sieving them into powder, uniformly mixing them with polymethyl methacrylate in chloroform, and then drop-coating the mixture onto a glass plate and drying it at room temperature.

6. The application of the hybrid Cu(I) halide material as described in claim 1 in information encryption storage and anti-counterfeiting materials.

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