Zero-dimensional hybrid luminescent material with high-efficiency luminescent performance and its preparation method and application

Abstract

The present invention discloses a zero-dimensional hybrid luminescent material with high-efficiency luminescent performance, its preparation method and application, and belongs to the field of solid-state light-emitting and diode display technology. Its technical scheme is as follows: the molecular formula of compound 1 is [H2MPPZ]ZnBr4; the molecular formula of compound 2 is [H2APM]ZnCl4, and the preparation steps are as follows: 1) when preparing compound 1, 1-phenylpiperazine and zinc bromide are dissolved in a mixed solution of methanol, ethylene glycol and hydrobromic acid; when preparing compound 2, N-aminopropylmorpholine and zinc chloride are dissolved in a mixed solution of methanol, ethylene glycol and hydrochloric acid; 2) the reaction vessel containing the mixed solution is sealed and placed in a constant temperature blast drying oven, the reaction is completed, filtered, washed, and dried to obtain a zero-dimensional hybrid luminescent material with high-efficiency luminescent performance. The zero-dimensional hybrid luminescent material with high-efficiency luminescent performance prepared by the present invention has high luminous intensity and good stability, and has potential applications in the fields of solid-state light-emitting and diode display.

Description

Technical Field

[0001] The present invention belongs to the technical field of solid-state light emitting and diode display, and in particular relates to a zero-dimensional hybrid luminescent material with high-efficiency luminescent performance, a preparation method thereof, and an application thereof. Background Art

[0002] Organic-inorganic hybrid metal halide optoelectronic materials have attracted widespread attention from researchers due to their diverse structures, tunable photophysical properties, high fluorescence quantum yield, high carrier mobility, and high luminescence efficiency. These hybrid materials offer several advantages over organic or inorganic materials. First, the inorganic backbone is a semiconductor with a tunable bandgap, endowing the material with excellent semiconductor optoelectronic properties. Second, the rich organic components provide a rich source of raw materials for crystal structure regulation and can improve the material's physical properties, such as solubility and stability. These hybrid materials hold significant potential for application in solid-state lighting, liquid crystal displays, sensing, medical imaging, and X-ray detection.

[0003] Compared to traditional three-dimensional Pb perovskite luminescent materials, low-dimensional metal halides, due to their strong exciton localization, easily generate self-trapped excitons, resulting in spectral broadening and highly susceptible to white light emission, making them more advantageous in fields such as white light-emitting diodes and X-ray scintillation luminescence. Low-dimensional lead-based halides, due to their outstanding optoelectronic properties, once became a research hotspot in the field of optoelectronic materials. However, the severe biological and environmental toxicity of metallic lead ions has limited their application prospects in optoelectronic devices.

[0004] In recent years, a large number of Sn 2+ , Sb 3+ , Cu + ,Bi 3+ , Zn 2+ Metal ions such as ions have been introduced into hybrid metal halide systems. These metals have low biotoxicity, a rich variety of structural types, tunable emission wavelengths, high-efficiency luminescence performance, and great structural stability, making them the best alternatives to lead-based halides. Among them, zinc-based halide materials have attracted much attention due to their simple preparation process, low cost, and environmental friendliness. Therefore, the preparation of organic-inorganic hybrid zinc-based halide optoelectronic materials with high stability and excellent luminescence performance holds great application prospects. Summary of the Invention

[0005] The present invention provides a zero-dimensional hybrid luminescent material with high-efficiency luminescent performance, a preparation method thereof, and an application thereof. The prepared zero-dimensional hybrid luminescent material with high-efficiency luminescent performance has high luminescent intensity and good stability, and has potential applications in the fields of solid-state luminescence and diode display.

[0006] The technical solution of the present invention is:

[0007] In the first aspect, a zero-dimensional hybrid luminescent material with high-efficiency luminescent performance is disclosed. The molecular formula of compound 1 is [H2MPPZ]ZnBr4(C 11 N2H 18 ZnBr4, MPPZ is N-methylphenylpiperazine), space group is P21 / c, unit cell parameters are a=8.1323(3), b=16.4609(6), c=13.2339(5), α=90°, β=105.928(1)°, γ=90°, unit cell volume is V=1703.54(11); the molecular formula of compound 2 is [H2APM]ZnCl4(C7ON2H 18 ZnCl4, APM is N-aminopropylmorpholine), space group is P21 / c, unit cell parameters are a=6.44344(14), b=15.6889(4), c=13.7074(3), α=90°, β=95.0788(19)°, γ=90°, V=1380.25(6).

[0008] In a second aspect, a method for preparing the zero-dimensional hybrid luminescent material with high-efficiency luminescent performance is disclosed, comprising the following steps:

[0009] 1) When preparing compound 1, 1-phenylpiperazine and zinc bromide are dissolved in a mixed solution of methanol, ethylene glycol and hydrobromic acid, and the mixture is placed in a reactor, stirred at room temperature until completely dissolved, and then sealed; when preparing compound 2, N-aminopropylmorpholine and zinc chloride are dissolved in a mixed solution of methanol, ethylene glycol and hydrochloric acid, and the mixture is placed in a reactor, stirred at room temperature until completely dissolved, and then sealed;

[0010] 2) placing the reaction container containing the mixed solution in a constant temperature forced air drying oven, and after the reaction is completed, naturally cooling to room temperature, filtering, washing, and drying to obtain a zero-dimensional hybrid luminescent material with high-efficiency luminescent performance.

[0011] Preferably, in step 1), the molar ratio of compound 1 to 1-phenylpiperazine and zinc bromide is (0.8-1.2):1, and the molar ratio of compound 2 to N-aminopropylmorpholine and zinc chloride is (0.8-1.2):1.

[0012] Preferably, the reaction temperature in step 2) is 80-100° C., and the reaction time is 5-8 days.

[0013] Preferably, in step 1), the volume ratio of methanol, ethylene glycol and hydrobromic acid used in compound 1 is (5-8):(5-8):1, and the volume ratio of methanol, ethylene glycol and hydrochloric acid used in compound 2 is (2-4):(2-4):1.

[0014] In a third aspect, the application of the zero-dimensional hybrid luminescent material with high-efficiency luminescent performance in the field of solid-state luminescence and diode display is disclosed.

[0015] Compared with the prior art, the present invention has the following beneficial effects:

[0016] The zero-dimensional hybrid luminescent materials with high-efficiency luminescence performance described in the present invention: Compound 1 [H2MPPZ] ZnBr4 and Compound 2 [H2(APM)2] ZnCl4, both emit blue light under ultraviolet light excitation, with emission peaks of 445nm and 449nm, respectively, and average lifetimes of 2.835ns and 5.634ns, respectively. The maximum photon quantum yield (PLQY) is 18.89%. When mixed with commercial phosphors to assemble white light LEDs, the highest color rendering index CRT is 94.5. This series of compounds shows good application prospects in fields such as solid-state lighting and display devices. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 It is the crystal structure diagram of compound 1 (a) and compound 2 (b) of the present invention.

[0018] Figure 2 It is the X-ray powder diffraction pattern of compound 1 (a) and compound 2 (b) of the present invention.

[0019] Figure 3 It is the solid ultraviolet-visible absorption spectrum of compound 1 (a) and compound 2 (b) of the present invention.

[0020] Figure 4 These are the excitation spectra and emission spectra of Compound 1(a) and Compound 2(b) of the present invention at room temperature.

[0021] Figure 5 This is a schematic diagram of the light-emitting positions of compound 1 (a) and compound 2 (b) in the International Commission on Illumination (CIE) 1931 color coordinate diagram of the present invention.

[0022] Figure 6 PLQY emission spectra of compound 1 (a) and compound 2 (b) of the present invention.

[0023] Figure 7 The photoluminescence decay graph and fitting curve graph of compound 1 (a) and compound 2 (b) of the present invention at room temperature are shown.

[0024] Figure 8 This is an electroluminescence spectrum of a white light LED device assembled with compound 1 (a) and compound 2 (b) of the present invention under current driving.

[0025] Figure 9 It is a current-dependent luminescence emission spectrum diagram of a white light LED device assembled with compound 1 (a) and compound 2 (b) of the present invention and a normalized peak intensity change diagram at different operating currents. DETAILED DESCRIPTION

[0026] Example 1 Preparation of Compound 1 [H2MPPZ] ZnBr4

[0027] 1) Dissolve 1-phenylpiperazine (0.0811 g) and zinc bromide (0.1125 g) in a mixture of methanol (3 mL), ethylene glycol (3 mL), and hydrobromic acid (0.5 mL). Place the mixture in a 15 mL glass bottle, stir at room temperature until completely dissolved, and then seal the bottle.

[0028] 2) The glass bottle was placed in a constant temperature forced air drying oven and reacted at 80° C. for 5 days. After the reaction was completed, the mixture was cooled to room temperature, filtered, washed, and dried to obtain a zero-dimensional hybrid luminescent material compound 1[H2MPPZ]ZnBr4.

[0029] Example 2 Preparation of Compound 2[H2APM]ZnCl4

[0030] 1) Dissolve N-aminopropylmorpholine (0.0721 g) and zinc chloride (0.0681 g) in a mixture of methanol (3 mL), ethylene glycol (3 mL), and hydrochloric acid (1 mL). Place the mixture in a 15 mL glass bottle, stir at room temperature until completely dissolved, and then seal the bottle.

[0031] 2) The glass bottle was placed in a constant temperature forced air drying oven and reacted at 80° C. for 5 days. After the reaction was completed, the mixture was cooled to room temperature, filtered, washed, and dried to obtain a zero-dimensional hybrid luminescent material compound 2[H2APM]ZnCl4.

[0032] Figure 1 The crystal structures of compounds 1(a) and 2(b) are shown. Compound 1 [H2MPPZ]ZnBr4, space group P21 / c, unit cell parameters a = 8.1323(3), b = 16.4609(6), c = 13.2339(5), α = 90°, β = 105.928(1)°, γ = 90°, unit cell volume V = 1703.54(11); Compound 2 [H2APM]ZnCl4, space group P21 / c, unit cell parameters a = 6.44344(14), b = 15.6889(4), c = 13.7074(3), α = 90°, β = 95.0788(19)°, γ = 90°, V = 1380.25(6).

[0033] Figure 2 The X-ray powder diffraction patterns of Compound 1 (a) and Compound 2 (b) are consistent with the theoretical data from single crystal structure simulations of the polycrystalline powders of Compound 1 [H2MPPZ]ZnBr4 and Compound 2 [H2APM]ZnCl4. These patterns indicate that the polycrystalline powders are of high purity.

[0034] Figure 3 The solid-state UV-visible absorption spectra of compounds 1(a) and 2(b) are shown. As shown in the figure, compound 1 [H2MPPZ]ZnBr4 exhibits distinct absorption peaks at 220nm and 261nm, with an optical band gap of 5.11eV; while compound 2 [H2APM]ZnCl4 exhibits distinct absorption peaks at 270nm and 300nm, with an optical band gap of 4.97eV.

[0035] Figure 4 The excitation and emission spectra of compounds 1(a) and 2(b) at room temperature are shown. As shown in the figure, compound 1 [H2MPPZ]ZnBr4 and compound 2 [H2APM]ZnCl4 both produce high-frequency emission peaks at 445nm and 449nm, respectively, with Stokes shifts of 94nm and 81nm, and half-widths of 47nm and 68nm, under excitation with 351nm and 368nm UV light, respectively.

[0036] Figure 5 The International Commission on Illumination (CIE) 1931 color coordinate diagram shows the emission locations of compounds 1 (a) and 2 (b). The corresponding chromaticity coordinates for compound 1 [H2MPPZ]ZnBr4 and compound 2 [H2APM]ZnCl4 are (0.16237, 0.10882) and (0.16852, 0.16526), ​​respectively, both falling within the blue emission region.

[0037] Figure 6 is the PLQY emission spectrum of compound 1 (a) and compound 2 (b). The calculation formula is η QE =I S / (E R -E S ), where I S is the luminescence emission spectrum of the sample, E R is the spectrum of the excitation light from the empty integrating sphere (without sample), E S The PLQYs of compound 1 [H2MPPZ] ZnBr4 and compound 2 [H2APM] ZnCl4 are 5.61% and 18.89%, respectively.

[0038] Figure 7The photoluminescence decay graphs and fitting curves for compounds 1(a) and 2(b) at room temperature are shown. The time-resolved emission spectra of compound 1 [H2MPPZ]ZnBr4 and compound 2 [H2APM]ZnCl4 were monitored at 445 nm and 449 nm, respectively. Both were fitted using a single exponential function: I(t) = I0exp(-t / τ), where I(t) represents the luminescence intensity, I0 is the fluorescence intensity at time 0, t is the time after excitation, and τ is the luminescence lifetime. The average lifetimes for the two compounds were 2.835 ns and 5.634 ns, respectively.

[0039] Example 3 Assembling white light LED devices using compound 1 [H2MPPZ] ZnBr4

[0040] Compound 1[H2MPPZ]ZnBr4, (Ba, Sr)SiO4:Eu 2+ Commercial green phosphor, K2SiF6:Mn 4+ Commercial red phosphor and epoxy resin were mixed in a ratio of 20:1:1.2:20 and stirred continuously for 10 minutes. The mixture was then coated on the surface of a 365nm ultraviolet light-emitting diode chip and cured under vacuum conditions for 30 minutes to obtain a white light LED device.

[0041] Example 4 Assembling a white light LED device using compound 2[H2(APM)2]ZnCl4

[0042] Compound 1[H2(APM)2]ZnCl4, (Ba, Sr)SiO4:Eu 2+ Commercial green phosphor, K2SiF6:Mn 4+ Commercial red phosphor and epoxy resin were mixed in a ratio of 15:1:1.5:15 and stirred continuously for 10 minutes. The mixture was then coated on the surface of a 365nm ultraviolet light-emitting diode chip and cured under vacuum conditions for 30 minutes to obtain a white light LED device.

[0043] Figure 8The following are the EL spectra of white light LED devices assembled with compounds 1(a) and 2(b) driven by currents of 60mA and 120mA, respectively. The photoelectric characteristics of the LEDs, including emission spectra, color temperature (CCT), color rendering index (Ra), and CIE color coordinates, were collected using an integrating sphere spectroradiometer system (EVERFINE HAAS-2000). The LED devices emitted bright white light under current drive, and the electroluminescence emission spectra covered the entire visible light region. The white light LED device prepared with compound 1 had a correlated color temperature (CCT) of 5176K and a color rendering index (CRT) of 89.2. The white light LED device prepared with compound 2 had a correlated color temperature (CCT) of 4898K and a color rendering index (CRT) of 94.5. This indicates that the prepared zero-dimensional organic-inorganic hybrid zinc halide luminescent material has potential applications in solid-state lighting and diode displays.

[0044] Figure 9 The following graphs show the current-dependent emission spectra of white-light LED devices assembled with compounds 1(a) and 2(b), along with the normalized peak intensity changes at different operating currents. As shown in the figure, the white-light LED exhibits good spectral stability at different operating currents, and the emission intensity steadily increases as the current increases from 20mA to 120mA, demonstrating the potential application of the prepared zero-dimensional organic-inorganic hybrid zinc halide luminescent material in high-power optoelectronic devices.

[0045] Although the present invention has been described in detail with reference to the accompanying drawings and in conjunction with preferred embodiments, the present invention is not limited thereto. Without departing from the spirit and substance of the present invention, persons of ordinary skill in the art may make various equivalent modifications or substitutions to the embodiments of the present invention, and such modifications or substitutions are intended to fall within the scope of the present invention. Therefore, the scope of protection of the present invention shall be subject to the scope of protection of the claims.

Claims

1. A method for preparing a zero-dimensional hybrid luminescent material with high-efficiency luminescent performance, characterized in that: The molecular formula of compound 1 is [H2MPPZ]ZnBr4, namely C 11 N2H 18 ZnBr4, where MPPZ is N-methylphenylpiperazine, and the space group is P2 1 / c， Unit cell parameters a =8.1323(3), b = 16.4609(6), c = 13.2339(5), α = 90°, β = 105.928(1)°, γ =90°, the unit cell volume is V = 1703.54(11); the molecular formula of compound 2 is [H2APM]ZnCl4, namely C7ON2H 18 ZnCl4, where APM is N-aminopropylmorpholine, and the space group is P2 1 / c , the unit cell parameters are a = 6.44344(14), b = 15.6889(4), c = 13.7074(3), α = 90°, β = 95.0788(19)°, γ = 90°, V = 1380.25(6); The preparation method comprises the following steps: 1) When preparing compound 1, 1-phenylpiperazine and zinc bromide are dissolved in a mixed solution of methanol, ethylene glycol, and hydrobromic acid, and the mixture is placed in a reactor. The mixture is stirred at room temperature until completely dissolved, and then sealed. When preparing compound 2, N-aminopropylmorpholine and zinc chloride are dissolved in a mixed solution of methanol, ethylene glycol, and hydrochloric acid, and the mixture is placed in a reactor. The mixture is stirred at room temperature until completely dissolved, and then sealed. 2) placing the reaction vessel containing the mixed solution in a constant temperature forced air drying oven. After the reaction is completed, naturally cooling to room temperature, filtering, washing, and drying to obtain a zero-dimensional hybrid luminescent material with high-efficiency luminescence performance; The reaction temperature in step 2) is 80-100°C and the reaction time is 5-8 days; In step 1), when preparing compound 1, the volume ratio of methanol, ethylene glycol and hydrobromic acid is (5-8):(5-8):1; when preparing compound 2, the volume ratio of methanol, ethylene glycol and hydrochloric acid is (2-4):(2-4):

1.

2. The method for preparing a zero-dimensional hybrid luminescent material with high-efficiency luminescence performance according to claim 1, wherein: In step 1), when preparing compound 1, the molar ratio of 1-phenylpiperazine to zinc bromide is (0.8-1.2):1; when preparing compound 2, the molar ratio of N-aminopropylmorpholine to zinc chloride is (0.8-1.2):

1.

3. Application of Compound 1 and Compound 2 prepared by the method for preparing a zero-dimensional hybrid luminescent material with high-efficiency luminescent performance as claimed in claim 1 in the fields of solid-state luminescence and diode display.

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