Preparation method of copper-based complex luminescent material
By using dimethyl sulfoxide and hypophosphorous acid to react with cuprous iodide to prepare copper-based complexes, the problems of high temperature, high pressure and highly toxic reagents in the prior art have been solved. This has enabled the efficient preparation of copper-based complexes and their application in flexible scintillator films, improving yield and resolution.
Patent Information
- Application Number
- CN202511738898.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-11-25
- Publication Date
- 2026-01-02
AI Technical Summary
Existing methods for synthesizing copper-based complexes are complex, require high temperature and pressure, use highly toxic reagents, and have low yields.
Using dimethyl sulfoxide, hypophosphorous acid, and cuprous iodide as raw materials, copper-based complex luminescent materials were prepared by reacting at a relatively low temperature, filtering, and drying under nitrogen, thus avoiding the use of highly toxic reagents and simplifying the operation process.
Significantly reducing synthesis temperature and time, increasing yield, suitable for commercial synthesis conditions, and applying copper-based complexes to flexible scintillator films to achieve high transparency and uniform distribution, resulting in high spatial resolution.
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Figure CN121248638A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of luminescent materials technology, specifically relating to a method for preparing a copper-based complex luminescent material. Background Technology
[0002] Copper-based complexes, due to their excellent optical properties, low cost, and environmental friendliness, have broad application prospects in fields such as light-emitting diodes, sensors, and scintillators. In the prior art, Cu(I) metal complexes [(CuI)4(CH3SCH3)3]... n The synthesis method involves adding the reactants CuI, P2S5, and (CH3CH2)4NBr to a mixed solvent of toluene and dimethyl sulfoxide, reacting them in an autoclave at a temperature above 140°C for 4 days, and then allowing the product to precipitate after washing for 3 weeks. The yield is only about 32% (based on Cu metal).
[0003] The synthesis scheme is complex, requires high temperature and long time, uses highly toxic reagents (such as P2S5, (CH3CH2)4NBr) and dangerous solvents (such as toluene), and has a low sample yield. Summary of the Invention
[0004] To address the problems mentioned in the background art, this invention provides a method for preparing copper-based complex luminescent materials, thereby solving the problems of high toxicity, harsh reaction conditions, long cycle, and low yield in existing methods.
[0005] The technical solution of the present invention is as follows: This invention provides a method for preparing a copper-based complex luminescent material, wherein dimethyl sulfoxide, hypophosphorous acid and cuprous iodide are mixed and reacted at 100-110°C for 22-24 hours, filtered, and dried under nitrogen to obtain the copper-based complex luminescent material; The mass-to-volume ratio of cuprous iodide to dimethyl sulfoxide is 0.05 g: 1.8-2.1 mL; the mass-to-volume ratio of cuprous iodide to hypophosphorous acid is 0.05 g: 0.47-0.52 mL.
[0006] Furthermore, the mass-to-volume ratio of cuprous iodide to dimethyl sulfoxide is 0.05 g: 2 mL; the mass-to-volume ratio of cuprous iodide to hypophosphite is 0.05 g: 0.5 mL.
[0007] Furthermore, the mixing time at room temperature is 8-12 minutes.
[0008] The copper-based complex luminescent material is orthorhombic with space group Cmce and cell parameters a=12.9650(9)Å, b=30.059(2)Å, c=10.7727(7)Å, α=90°, β=90°, γ=90°; the mass percentages of carbon, sulfur, and hydrogen are 7.46%, 9.98%, and 1.69%, respectively.
[0009] The copper-based complex luminescent material emits 564nm yellow fluorescence when excited by 352nm ultraviolet light, with a fluorescence decay lifetime of 5.08μs.
[0010] The present invention also provides an application of the copper-based complex luminescent material prepared by the above preparation method in a scintillator.
[0011] Specifically, the application of copper-based complex luminescent materials in the preparation of flexible scintillator thin films.
[0012] Application methods include: Ethylene-vinyl acetate copolymer is dissolved in cyclohexane and stirred. The copper-based complex luminescent material dispersed in cyclohexane is added to it, and stirring is continued until a fluid is formed. The fluid is coated onto a glass substrate, and after the solvent is evaporated at room temperature, a flexible scintillator film is obtained.
[0013] Furthermore, the mass ratio of the copper-based luminescent material to the ethylene-vinyl acetate copolymer is 0.5:2-3.
[0014] Beneficial effects This invention proposes a novel synthetic strategy for preparing (Cu4I4)(DMS)3 composite materials. This method eliminates the need for complex procedures, utilizing dimethyl sulfoxide, hypophosphite, and cuprous iodide as raw materials. It avoids the use of highly toxic reagents (such as P2S5) and hazardous solvents (such as toluene), significantly reducing the required synthesis time and temperature while substantially increasing the yield, making it more suitable for commercial synthesis. Furthermore, by combining ethylene-vinyl acetate copolymer with powdered (Cu4I4)(DMS)3, a highly transparent and uniformly distributed flexible scintillator film is constructed, achieving a thickness as high as 14.85 lpmm. -1 Spatial resolution. Attached Figure Description
[0015] Figure 1 This is a schematic diagram of the preparation process of the copper-based complex luminescent material of the present invention.
[0016] Figure 2The photoluminescence properties of (Cu4I4)(DMS)3 were studied, including (a) PL excitation and emission spectra; (b) CIE coordinates; (c) PL decay curve at 300 K; (d) comparison of PL quantum yield of (Cu4I4)(DMS)3 with other copper-based complexes; (e) temperature-dependent PL emission spectrum; and (f) curve of integral photoluminescence intensity as a function of the reciprocal of temperature.
[0017] Figure 3 Photographs, fluorescence spectra, and XRD diffraction patterns of (Cu4I4)(DMS)3 crystals are shown, where (a–c) represent crystals after water immersion for different times; and (d–f) represent crystals after immersion in acidic or alkaline solutions with different pH values.
[0018] Figure 4 The scintillator properties of (Cu4I4)(DMS)3 were studied, including (a) the absorption coefficient of (Cu4I4)(DMS)3 and LuAG:Ce as a function of photon energy; (b) the comparison of light yield of (Cu4I4)(DMS)3 with other copper-based complex scintillators; (cd) the RL spectrum under X-ray irradiation at different dose rates; (e) the linear relationship between RL intensity and dose rate; (f) the X-ray induced afterglow curve; (g) the RL stability under alternating X-ray irradiation; (h) the scintillation spectrum at different powers; and (i) the linear relationship between RL intensity and different powers.
[0019] Figure 5 (a) shows a photograph of the target object and its corresponding X-ray image; (b) shows an X-ray image of the test pattern plate; and (c) shows the modulation transfer function curve of the flexible thin film based on the inclined plane method (inset). Detailed Implementation
[0020] The following examples are intended to illustrate the present invention, and not to further limit the invention.
[0021] This invention provides a method for preparing a copper-based complex luminescent material. Dimethyl sulfoxide (DMSO), hypophosphorous acid, and cuprous iodide are mixed and reacted at 100-110°C for 22-24 hours. The mixture is then filtered and dried under nitrogen to obtain the copper-based complex luminescent material (CuI)4(CH3SCH3)3, denoted as (Cu4I4)(DMS)3.
[0022] The equation is as follows: .
[0023] The mass-to-volume ratio of cuprous iodide to dimethyl sulfoxide is 0.05 g: 1.8-2.1 mL; the mass-to-volume ratio of cuprous iodide to hypophosphorous acid is 0.05 g: 0.47-0.52 mL.
[0024] Preferably, the mass-to-volume ratio of cuprous iodide to dimethyl sulfoxide is 0.05 g: 2 mL; and the mass-to-volume ratio of cuprous iodide to hypophosphorous acid is 0.05 g: 0.5 mL.
[0025] In addition, the mixing time at room temperature is 8-12 minutes.
[0026] Compared to existing technologies, this invention does not use toxic chemicals such as P2S5 and (CH3CH2)4NBr as raw materials. Furthermore, while existing synthesis methods require high-temperature hydrothermal treatment above 140°C, this invention only requires 100-110°C, greatly simplifying the process and improving synthesis safety. Secondly, the synthesis time of this invention does not exceed 24 hours, significantly shortening the synthesis cycle.
[0027] Structurally, the copper-based complex luminescent material is orthorhombic with space group Cmce and cell parameters a=12.9650(9)Å, b=30.059(2)Å, c=10.7727(7)Å, α=90°, β=90°, γ=90°; the mass percentages of carbon, sulfur, and hydrogen are 7.46%, 9.98%, and 1.69%, respectively.
[0028] In terms of luminescence properties, the copper-based complex luminescent material emits 564nm yellow fluorescence under 352nm ultraviolet light excitation, with a fluorescence decay lifetime of 5.08μs.
[0029] The present invention also provides an application of the copper-based complex luminescent material prepared by the above preparation method in a scintillator.
[0030] Specifically, the application of copper-based complex luminescent materials in the preparation of flexible scintillator thin films.
[0031] Application methods include: Ethylene-vinyl acetate copolymer is dissolved in cyclohexane and stirred. The copper-based complex luminescent material dispersed in cyclohexane is added to it, and stirring is continued until a fluid is formed. The fluid is coated onto a glass substrate, and after the solvent is evaporated at room temperature, a flexible scintillator film is obtained.
[0032] Preferably, the mass ratio of the copper-based luminescent material to the ethylene-vinyl acetate copolymer is 0.5:2-3.
[0033] The flexible scintillator film achieves a spatial resolution of 14.85 lpmm when the modulation transfer function is 0.2. -1 .
[0034] In summary, this invention proposes a novel synthetic strategy for preparing (Cu4I4)(DMS)3 composite materials. This method eliminates the need for complex procedures, avoids the use of highly toxic reagents (such as P2S5) and hazardous solvents (such as toluene), and significantly reduces the required synthesis time and temperature while substantially increasing the yield, making it more suitable for commercial synthesis. Furthermore, by combining ethylene-vinyl acetate copolymer (EVA) with powdered (Cu4I4)(DMS)3, a highly transparent and uniformly distributed flexible scintillator film was constructed, achieving a thickness as high as 14.85 lpmm. -1 Spatial resolution.
[0035] Example 1 like Figure 1 As shown, this embodiment provides a method for preparing a copper-based complex luminescent material: 2 mL of dimethyl sulfoxide, 0.5 mL of hypophosphoric acid, and 0.05 g of CuI were mixed in a 15 mL reaction vessel and stirred for 10 minutes. Finally, the mixture was placed in a 100 °C oven and reacted for 24 hours. After filtration and drying with nitrogen, a single crystal sample was obtained, denoted as (Cu4I4)(DMS)3.
[0036] Example 2 Based on Example 1, this example provides an application of a copper-based complex luminescent material in the preparation of flexible scintillator thin films: 2.0 g of ethylene-vinyl acetate copolymer (EVA) was completely dissolved in 5 mL of cyclohexane and stirred at 60 °C for 1 hour. Then, (Cu4I4)(DMS)3 dispersed in 1 mL of cyclohexane was added to the solution, and the mixture was stirred until a homogeneous, viscous fluid was formed. This fluid was coated onto a glass substrate and gradually evaporated at room temperature in a fume hood to finally obtain a flexible scintillator film.
[0037] Experimental results 1. Structural characterization The single-crystal sample (Cu4I4)(DMS)3 obtained in Example 1 was analyzed using single-crystal X-ray diffraction (SCXRD), as shown in Table 1, confirming the crystal structure and molecular formula of (Cu4I4)(DMS)3. C6H 18 Theoretical elemental analysis of S3Cu4I4: C 7.60%, S 10.14%, H 1.91%; Experimental measured values: C 7.46%, S 9.98%, H 1.69%.
[0038] Table 1. Structural parameters of (Cu4I4)(DMS)3 a R 1 = (Σ|| F o | − |F c ||) / Σ| F o | b wR 2 = {Σ w ( F o 2 - F c 2 ) 2 / Σ wF o 2} 1 / 2 . 2. Study on photoluminescence properties like Figure 2 As shown in (a), at ambient temperature, the (Cu4I4)(DMS)3 single crystal of Example 1 emits 564nm yellow light when excited by 352nm ultraviolet light, with a full width at half maximum (FWHM) of 125nm. The International Commission on Illumination (CIE) coordinates of (Cu4I4)(DMS)3 are (0.41, 0.53), which are standard yellow and... Figure 1 The fluorescence emitted by the single crystals in the samples is of the same color. Figure 2 (b)). Furthermore, Figure 2 Figure (c) shows the decay curve of (Cu4I4)(DMS)3 (5.08 μs). The PLQY of (Cu4I4)(DMS)3 measured at room temperature is 99%, which is far superior to similar complexes. Figure 2 (d)). For example Figure 2 In Figure (e), the waveform did not split during heating, confirming that the fluorescence originates from a single emission center. Furthermore, the PL intensity exhibits a monotonically decreasing trend with increasing temperature, which can be attributed to the dominant role of thermally activated non-radiative recombination over radiative recombination. Figure 2 The calculated Ea value (132.54 meV) in (f) exceeds the thermal energy of the bound exciton (26 meV), thus hindering the decomposition of the exciton.
[0039] 3. Single Crystal Stability Study like Figure 3 In Example 1, the (Cu4I4)(DMS)3 single crystal remained stable in water for eight months, exhibiting no significant changes in fluorescence intensity or XRD data, indicating its water stability. Figure 3In the middle (df) test, to evaluate acid stability, the (Cu4I4)(DMS)3 of Example 1 was immersed in a solution prepared with concentrated hydrochloric acid and water; while to evaluate alkaline stability, it was placed in an alkaline solution prepared with concentrated ammonia. However, regardless of whether it was in an acidic or alkaline environment, the fluorescence intensity and XRD characteristic peaks of the single crystal did not change significantly, indicating that the single crystal has extremely excellent stability in acidic and alkaline environments.
[0040] 4. Study on the characteristics of scintillators To evaluate its scintillator performance, this invention calculated the absorption coefficient of (Cu4I4)(DMS)3 in Example 1 at different photon energies and compared it with that of the commercial scintillator LuAG:Ce. Figure 4 As shown in (a), the X-ray absorption coefficient of (Cu4I4)(DMS)3 is only slightly lower than that of commercial LuAG:Ce scintillators, indicating that it has excellent X-ray absorption characteristics over a wide energy range.
[0041] like Figure 4 As shown in (b), the calculated light yield of (Cu4I4)(DMS)3 is 64,500 photons / MeV, which is significantly better than most commercial scintillators.
[0042] The sensitivity of (Cu4I4)(DMS)3 to X-rays was evaluated by measuring the RL emission intensity at different doses. Figure 4 As shown in (cd), the RL intensity exhibits a linear increase in X-ray dose ranges of 5 to 50 μGy / s and 5000 to 50000 μGy / s, indicating that the material has the potential for scintillator applications under both low and high dose conditions.
[0043] Figure 4 In section (e), the detection limit was determined by fitting the relationship between RL intensity and X-ray dose. The results showed that the detection limit of (Cu4I4)(DMS)3 was 57.6 nGy. -1 This value is far lower than the 5.5 μGy required for routine medical X-ray diagnosis. -1 Thresholds can significantly reduce radiation exposure during medical examinations. For example... Figure 4 As shown in (f), after X-ray irradiation was stopped, the relative afterglow intensity of (Cu4I4)(DMS)3 rapidly decreased from 100% to 0.1% within 2.14 milliseconds, fully demonstrating the material's excellent X-ray imaging performance.
[0044] The stability of (Cu4I4)(DMS)3 was evaluated by alternating X-ray irradiation. The results showed that after 30 consecutive irradiation cycles within 60 minutes, the RL intensity decreased by only 10%, demonstrating good X-ray tolerance. Figure 4In the power range of 0.45 mW to 108.15 mW, the radiative emission intensity of (Cu4I4)(DMS)3 showed a significant linear relationship with the laser power, indicating that the radiative emission mechanism remained stable. Figure 4 (hi)
[0045] 5. X-ray optical imaging capability of flexible scintillator thin films Given the excellent radiative emission properties of (Cu4I4)(DMS)3, the X-ray optical imaging capability of the (Cu4I4)(DMS)3@EVA thin film of Example 2 was then evaluated. Figure 5 (a) shows a photograph and X-ray image of the headphones, in which the circuit board is clearly visible under X-ray irradiation due to differences in absorption coefficients. Two sets of optical photographs and X-ray images of insects were subsequently taken; the X-ray images clearly show the insects' skeletal structure. Measured using a standard X-ray resolution tester, it exhibits a resolution of 14 lpmm. -1 High spatial resolution ( Figure 5 (b) The modulation transfer function (MTF) of the scintillator was determined using the hypotenuse method. When the MTF = 0.2, the spatial frequency of (Cu4I4)(DMS)3@EVA reached 14.85 lpmm. -1 The resolution limit is consistent with that measured by the standard line pair graph. Figure 5 (c)
Claims
1. A method for preparing a copper-based complex luminescent material, characterized in that, The dimethyl sulfoxide, hypophosphorous acid and cuprous iodide are mixed and reacted at 100-110 ℃ for 22-24 hours, filtered, dried by nitrogen to obtain the copper-based complex luminescent material; The mass-volume ratio of cuprous iodide to dimethyl sulfoxide is 0.05 g: 1.8-2.1 mL; the mass-volume ratio of cuprous iodide to hypophosphorous acid is 0.05 g: 0.47-0.52 mL.
2. The production method according to claim 1, characterized by, The mass-volume ratio of cuprous iodide to dimethyl sulfoxide is 0.05 g: 2 mL; the mass-volume ratio of cuprous iodide to hypophosphorous acid is 0.05 g: 0.5 mL.
3. The production method according to claim 1, characterized by, The mixing and stirring time at room temperature is 8-12 min.
4. The preparation method according to claim 1, characterized in that, The copper-based complex luminescent material is orthorhombic, the space group is Cmce, the cell parameters are a=12.9650(9) Å, b=30.059(2) Å, c=10.7727(7) Å, α=90°, β=90°, γ=90°; the mass percentage of carbon, sulfur and hydrogen is 7.46%, 9.98% and 1.69%, respectively.
5. The preparation method according to claim 1, characterized in that, The copper-based complex luminescent material emits 564 nm yellow fluorescence under 352 nm ultraviolet light excitation, and the fluorescence decay lifetime is 5.08 μs.
6. The copper-based complex luminescent material prepared by the preparation method of claim 1 is applied in a scintillator.
7. Use according to claim 6, characterized in that, The copper-based complex luminescent material is applied in the preparation of a flexible scintillator film.
8. Use according to claim 7, characterized in that, The application method comprises: The ethylene-vinyl acetate copolymer is dissolved in cyclohexane and stirred, the copper-based complex luminescent material dispersed in cyclohexane is added thereto, and the stirring is continued until a fluid is formed; the fluid is coated on a glass substrate, and after the solvent is evaporated at room temperature, a flexible scintillator film is obtained.
9. Use according to claim 8, characterized in that, The mass ratio of the copper-based complex luminescent material to ethylene-vinyl acetate copolymer is 0.5:2-3.