A zero-dimensional antimony-based organic-inorganic hybrid metal halide single crystal material, a preparation method and applications thereof

Abstract

The present application relates to a kind of zero-dimensional antimony-based organic-inorganic hybrid metal halide single crystal material and its preparation method and application, belong to luminescent material technical field.The present application is mainly with ethyl triphenyl phosphine chloride (EPPCl), antimony trichloride (SbCl3) as raw material, with dichloromethane as solvent, ether as anti-solvent preparation single crystal material ((EPP) 2SbCl5·CH2Cl2 single crystal), the preparation method has the characteristics such as convenient, easy to repeat, the antimony-based organic-inorganic hybrid metal halide single crystal prepared exhibits bright orange-red emission and near unit PLQY, has important application in white light solid state lighting.

Description

Technical Field

[0001] This invention belongs to the field of antimony-based single crystal material preparation technology, and relates to a zero-dimensional antimony-based organic-inorganic hybrid metal halide single crystal material, its preparation method and application. Background Technology

[0002] Antimony-based organic-inorganic hybrid metal halides have attracted widespread attention from researchers due to their high photoluminescence quantum yield, long fluorescence lifetime, and low-dimensional structure at the molecular level, making them promising for applications in X-ray detectors, anti-counterfeiting, and light-emitting diodes (LEDs). Currently, most applications of antimony-based organic-inorganic hybrid metal halides in white LEDs involve mixing red, green, and blue materials to achieve bright white light emission under 365nm ultraviolet light excitation. While this method can successfully fabricate white LEDs, the difficulty in controlling the composition of the three materials severely restricts the development of antimony-based organic-inorganic hybrid metal halides in white LEDs.

[0003] Therefore, it is necessary to conduct in-depth research on antimony-based organic-inorganic metal halide single crystals so that they can have good application effects in white LEDs, in order to solve the shortcomings of existing white LED technologies. Summary of the Invention

[0004] In view of this, one objective of the present invention is to provide a method for preparing a zero-dimensional antimony-based organic-inorganic hybrid metal halide single crystal material; another objective of the present invention is to provide a zero-dimensional antimony-based organic-inorganic hybrid metal halide single crystal material; and a third objective of the present invention is to provide an application of a zero-dimensional antimony-based organic-inorganic hybrid metal halide single crystal material in white light solid-state lighting.

[0005] To achieve the above objectives, the present invention provides the following technical solution:

[0006] 1. A zero-dimensional antimony-based organic-inorganic hybrid metal halide single crystal material, wherein the chemical composition of the single crystal material is (EPP)₂SbCl₅·CH₂Cl₂, wherein EPP is ethyltriphenylphosphine (C 20 H 20 P), whose chemical structural formula is as follows:

[0007]

[0008] 2. The preparation method of the above-mentioned zero-dimensional antimony-based organic-inorganic hybrid metal halide single crystal material, the preparation method comprising the following steps:

[0009] Ethyltriphenylphosphine chloride and antimony trichloride were mixed and dissolved in dichloromethane to form a clear and transparent precursor solution. Then, diethyl ether was diffused into the precursor solution at room temperature to form crystals. After washing with diethyl ether and drying under reduced pressure, a zero-dimensional antimony-based organic-inorganic hybrid metal halide single crystal material with the chemical composition (EPP)2SbCl5·CH2Cl2 was obtained.

[0010] Preferably, the mass-to-volume ratio of ethyltriphenylphosphine chloride, antimony trichloride, dichloromethane, and diethyl ether is 0.6536–0.6736:0.2281–0.2481:5–7:10–15, g:g:ml:ml.

[0011] Preferably, the diffusion time is 10 to 12 hours.

[0012] Preferably, the reduced pressure drying specifically involves drying for at least 5 minutes at a vacuum pressure of 100–120 Pa and a temperature of 40°C.

[0013] 3. Application of the above-mentioned zero-dimensional antimony-based organic-inorganic hybrid metal halide single crystal materials in the fabrication of white LED devices.

[0014] 4. A method for fabricating a white LED device, the method comprising the following steps:

[0015] The above-mentioned zero-dimensional antimony-based organic-inorganic hybrid metal halide single crystal material is mixed with blue light material and ground for 5-10 minutes to obtain a white powder. Polydimethylsiloxane (PDMS) and curing agent are added to it, and grinding is continued to mix it evenly to obtain colloid A. Then, colloid A is evenly coated onto a 365nm ultraviolet lamp. After curing for 2-3 hours, a white LED device can be obtained. The curing agent is DC184 curing agent.

[0016] Preferably, the mass ratio of the zero-dimensional antimony-based organic-inorganic hybrid metal halide single crystal material, polydimethylsiloxane (PDMS), and curing agent is 1:1.5:1.

[0017] Preferably, the molar ratio of the zero-dimensional antimony-based organic-inorganic hybrid metal halide single crystal material to the blue light material is 2:1;

[0018] The blue light material is anthracene.

[0019] 5. White LED device prepared according to the above preparation method.

[0020] The beneficial effects of this invention are as follows: This invention discloses a method for preparing zero-dimensional antimony-based organic-inorganic hybrid metal halide single crystal materials. The method mainly uses ethyltriphenylphosphine chloride, antimony trichloride, and dichloromethane as raw materials to prepare single crystal materials ((EPP)2SbCl5·CH2Cl2 single crystal). The zero-dimensional antimony-based organic-inorganic hybrid metal halide single crystal material ((EPP)2SbCl5·CH2Cl2 single crystal) exhibits bright orange-red luminescence, extremely high PLQY, and ultra-wide half-wavelength peak width, showing good application prospects in the preparation of white LED devices. The white LED device fabricated using the zero-dimensional antimony-based organic-inorganic hybrid metal halide single crystal material ((EPP)2SbCl5·CH2Cl2 single crystal) of this invention has the following characteristics: Due to its ultra-wide half-width, only two materials are needed: the zero-dimensional antimony-based organic-inorganic hybrid metal halide single crystal material ((EPP)2SbCl5·CH2Cl2 single crystal) and the blue light material, to obtain a white LED. Under a current drive of 20mA, the white LED device exhibits color coordinates of (0.33.0.35), a color temperature CCT of 5269K, and a CRI of 93. Furthermore, the fabrication method of this white LED has the advantages of being simple, easy to operate, having low equipment requirements, low cost, low energy consumption, and being suitable for large-scale production.

[0021] Other advantages, objectives, and features of the invention will be set forth in part in the description which follows, and in part will be apparent to those skilled in the art from the following examination, or may be learned from practice of the invention. The objectives and other advantages of the invention can be realized and obtained through the following description. Attached Figure Description

[0022] To make the objectives, technical solutions, and advantages of the present invention clearer, the preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings, wherein:

[0023] Figure 1 A schematic diagram of the (EPP)2SbCl5·CH2Cl2 single crystal prepared in Example 1;

[0024] Figure 2 Images of the (EPP)2SbCl5·CH2Cl2 single crystal prepared in Example 1 under sunlight (a) and ultraviolet light (365nm) (b);

[0025] Figure 3 The X-ray powder diffraction pattern of the (EPP)2SbCl5·CH2Cl2 single crystal prepared in Example 1;

[0026] Figure 4 The absorption spectrum of the (EPP)2SbCl5·CH2Cl2 single crystal prepared in Example 1;

[0027] Figure 5 The emission spectrum (PL) of the (EPP)2SbCl5·CH2Cl2 single crystal prepared in Example 1 was excited at 365 nm.

[0028] Figure 6 The excitation spectrum (PLE) of the (EPP)2SbCl5·CH2Cl2 single crystal prepared in Example 1 is shown as the emission spectrum at 627 nm.

[0029] Figure 7 The image shows the electroluminescence (EL) spectrum of the white LED device prepared in Example 1 at a current of 70 mA. Detailed Implementation

[0030] The following specific examples illustrate the implementation of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and various details in this specification can be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention. It should be noted that the illustrations provided in the following embodiments are only schematic representations of the basic concept of the present invention. Unless otherwise specified, the following embodiments and features can be combined with each other.

[0031] Example 1

[0032] 1. A zero-dimensional antimony-based organic-inorganic hybrid metal halide single crystal material (its chemical composition is (EPP)2SbCl5·CH2Cl2, wherein EPP is ethyltriphenylphosphine (C 20 H 20 P), its chemical structural formula is as follows:

[0033] Its preparation method is as follows:

[0034] 0.6536 g of ethyltriphenylphosphine chloride (EPPCl) and 0.2281 g of antimony trichloride were mixed and placed in a 10 mL bottle. 5 mL of dichloromethane was added and stirred for 10 min to dissolve the mixture. The bottle was then opened and placed in a 50 mL container. 10 mL of diethyl ether was added to the container (without adding it to the bottle), and the mixture was allowed to evaporate overnight (10–12 h) for crystal growth. The resulting crystal was washed with diethyl ether and dried under reduced pressure (120 Pa pressure, 40 °C temperature, 5 min) to obtain a zero-dimensional antimony-based organic-inorganic hybrid metal halide single crystal material ((EPP)2SbCl5·CH2Cl2 single crystal), with the chemical composition (EPP)2SbCl5·CH2Cl2. A schematic diagram of the single crystal is shown below. Figure 1 (As shown).

[0035] A schematic diagram of the single crystal of the zero-dimensional antimony-based organic-inorganic hybrid metal halide single crystal material ((EPP)2SbCl5·CH2Cl2 single crystal) prepared in Example 1 with the chemical composition (EPP)2SbCl5·CH2Cl2 is shown below. Figure 1 As shown, its images under sunlight and under ultraviolet light (365nm) are as follows: Figure 2 As shown in a and b.

[0036] Example 2

[0037] A white LED device is fabricated as follows:

[0038] The zero-dimensional antimony-based organic-inorganic hybrid metal halide single crystal material ((EPP)2SbCl5·CH2Cl2 single crystal) prepared in Example 1 above was ground and sieved to obtain single crystal powder. Then, it was mixed with anthracene, a blue light material, at a molar ratio of 1:1.5:1 and ground together for 5-10 minutes to obtain white powder. Then, PDMS and curing agent (DC184) (where the molar ratio of zero-dimensional antimony-based organic-inorganic hybrid metal halide single crystal material to blue light material is 2:1) were added to the white powder and ground for another 5-10 minutes to make it uniformly mixed to obtain colloid A. Then, colloid A was uniformly coated onto a 365nm ultraviolet lamp and cured for 2-3 hours to obtain a white LED device.

[0039] Example 3

[0040] 1. A zero-dimensional antimony-based organic-inorganic hybrid metal halide single crystal material (its chemical composition is (EPP)2SbCl5·CH2Cl2, wherein EPP is ethyltriphenylphosphine (C 20 H 20 P), its chemical structural formula is as follows:

[0041] Its preparation method is as follows:

[0042] 0.6536 g of ethyltriphenylphosphine chloride (EPPCl) and 0.2481 g of antimony trichloride were mixed and placed in a 10 mL bottle. 7 mL of dichloromethane was added and stirred for 10 min to dissolve the mixture. The bottle was then opened and placed in a 50 mL container. 15 mL of diethyl ether was added to the container (without adding it to the bottle). The mixture was allowed to evaporate overnight (10-12 h) to grow crystals. The resulting crystals were washed with diethyl ether and dried under reduced pressure (100 Pa pressure and 40 °C for 10 min) to obtain a zero-dimensional antimony-based organic-inorganic hybrid metal halide single crystal material ((EPP)2SbCl5·CH2Cl2 single crystal) with the chemical composition (EPP)2SbCl5·CH2Cl2.

[0043] Example 4

[0044] 1. A zero-dimensional antimony-based organic-inorganic hybrid metal halide single crystal material (its chemical composition is (EPP)2SbCl5·CH2Cl2, wherein EPP is ethyltriphenylphosphine (C 20 H 20 P), its chemical structural formula is as follows:

[0045] Its preparation method is as follows:

[0046] 0.6736 g of ethyltriphenylphosphine chloride (EPPCl) and 0.2281 g of antimony trichloride were mixed and placed in a 10 mL bottle. 5 mL of dichloromethane was added and stirred for 10 min to dissolve the mixture. The bottle cap was then opened and the mixture was placed in a 50 mL container. 10 mL of diethyl ether was added to the container (without adding it to the bottle). The mixture was allowed to evaporate overnight (10-12 h) to grow crystals. The resulting crystals were washed with diethyl ether and dried under reduced pressure (120 Pa pressure and 40 °C for 5 min) to obtain a zero-dimensional antimony-based organic-inorganic hybrid metal halide single crystal material ((EPP)2SbCl5·CH2Cl2 single crystal) with the chemical composition (EPP)2SbCl5·CH2Cl2.

[0047] Performance testing

[0048] The zero-dimensional antimony-based organic-inorganic hybrid metal halide single crystal material ((EPP)2SbCl5·CH2Cl2 single crystal) prepared in Example 1 was subjected to the following operations: (1) X-ray powder diffraction (XRD) was used for detection, and the obtained X-ray powder diffraction pattern is as follows. Figure 3 As shown. From Figure 3 It can be seen that the XRD of the (EPP)2SbCl5·CH2Cl2 single crystal prepared in Example 1 is consistent with the simulated XRD after single crystal analysis, proving that the preparation method of Example 1 of this invention can indeed prepare the structure of (EPP)2SbCl5·CH2Cl2 single crystal. (2) The (EPP)2SbCl5·CH2Cl2 single crystal prepared in Example 1 was tested using a UV-Vis spectrophotometer, and the UV absorption spectrum was obtained, as shown in the figure. Figure 4 As shown. From Figure 4 It can be seen that the (EPP)2SbCl5·CH2Cl2 single crystal prepared in the example has multiple absorption peaks. (3) The (EPP)2SbCl5·CH2Cl2 single crystal prepared in Example 1 was tested using a steady transient fluorescence spectrometer, and the emission spectrum (PL) at 365 nm and the excitation spectrum (PLE) at 627 nm were obtained, as shown in the figure. Figure 5 and Figure 6 As shown. From Figure 5(Emission) It can be seen that the zero-dimensional antimony-based organic-inorganic hybrid metal halide single crystal material prepared in Example 1 has an emission peak at 627 nm when excited at 365 nm; from Figure 6 (Excitation) It can be seen that when the emission is at 627nm, the excitation peak is located at 372nm.

[0049] The electroluminescence (EL) spectrum of the white LED device prepared in Example 2 at a current of 70 mA is as follows: Figure 7 As shown. From Figure 7 It can be seen that, driven by a current of 70mA, the white LED device prepared in Example 2 has a color temperature CTT = 3723K and a color rendering index CRI = 92.

[0050] Similarly, the zero-dimensional antimony-based organic-inorganic hybrid metal halide single crystal materials ((EPP)2SbCl5·CH2Cl2 single crystal) prepared under different conditions in Examples 3 and 4 were subjected to corresponding performance tests. The results were similar to those of the zero-dimensional antimony-based organic-inorganic hybrid metal halide single crystal materials ((EPP)2SbCl5·CH2Cl2 single crystal) prepared in Example 1 (ultra-wide half-wavelength). When applied to prepare related LED devices in Example 2, the color coordinates, color temperature (CCT), and CRI=93 exhibited by the LED devices in Example 2 under a current drive of 20mA were also similar to those in Example 2.

[0051] In summary, this invention discloses a zero-dimensional antimony-based organic-inorganic hybrid metal halide single crystal material ((EPP)₂SbCl₅·CH₂Cl₂ single crystal), its preparation method, and its applications. Its chemical composition is (EPP)₂SbCl₅·CH₂Cl₂, and its chemical structural formula is as follows: (C 20 H 20 (EPP)₂SbCl₅·CH₂Cl₂. This invention mainly uses ethyltriphenylphosphine chloride, antimony trichloride, and dichloromethane as raw materials to prepare (EPP)₂SbCl₅·CH₂Cl₂ single crystals. The prepared (EPP)₂SbCl₅·CH₂Cl₂ single crystals exhibit bright orange-red luminescence, extremely high PLQY, and an ultra-wide half-width at half-maximum (HWHM). Its application in the preparation of white LED devices has the following characteristics: due to its ultra-wide HWHM, only the aforementioned antimony-based single crystal and blue light-emitting material are needed to obtain white LED devices. The prepared white LED device, driven by a 20mA current, exhibits color coordinates of (0.33.0.35), a color temperature CCT of 5269K, and a CRI of 93. Furthermore, the preparation method of this white LED device has advantages such as simplicity, ease of operation, low equipment requirements, low cost, low energy consumption, and suitability for large-scale production.

[0052] Finally, 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 present invention, and all such modifications or substitutions should be covered within the scope of the claims of the present invention.

Claims

1. A zero-dimensional antimony-based organic-inorganic hybrid metal halide single crystal material, characterized in that, The chemical composition of the single-crystal material is (EPP)₂SbCl₅·CH₂Cl₂, where EPP is ethyltriphenylphosphine, and its chemical structural formula is as follows:

2. The method for preparing the zero-dimensional antimony-based organic-inorganic hybrid metal halide single crystal material according to claim 1, characterized in that, The preparation method includes the following steps: Ethyltriphenylphosphine chloride and antimony trichloride were mixed and dissolved in dichloromethane to form a clear and transparent precursor solution. Then, diethyl ether was diffused into the precursor solution at room temperature to form crystals. After washing with diethyl ether and drying under reduced pressure, a zero-dimensional antimony-based organic-inorganic hybrid metal halide single crystal material with the chemical composition (EPP)2SbCl5·CH2Cl2 was obtained.

3. The preparation method according to claim 2, characterized in that, The mass-to-volume ratio of the ethyltriphenylphosphine chloride, antimony trichloride, dichloromethane, and diethyl ether is 0.6536–0.6736:0.2281–0.2481:5–7:10–15, g:g:ml:ml.

4. The preparation method according to claim 2, characterized in that, The diffusion time is 10 to 12 hours.

5. The preparation method according to claim 2, characterized in that, The vacuum drying process specifically involves drying for at least 5 minutes at a vacuum pressure of 100–120 Pa and a temperature of 40°C.

6. The application of the zero-dimensional antimony-based organic-inorganic hybrid metal halide single crystal material of claim 1 in the fabrication of white LED devices.

7. A method for fabricating a white LED device, characterized in that, The preparation method includes the following steps: The zero-dimensional antimony-based organic-inorganic hybrid metal halide single crystal material of claim 1 is mixed with blue light material and ground for 5-10 minutes to obtain a white powder. Polydimethylsiloxane and curing agent are added to it, and grinding is continued to make it mix evenly to obtain colloid A. Then, colloid A is evenly coated onto a 365nm ultraviolet lamp. After curing for 2-3 hours, a white LED device can be obtained, wherein the curing agent is DC184 curing agent.

8. The preparation method according to claim 7, characterized in that, The mass ratio of the zero-dimensional antimony-based organic-inorganic hybrid metal halide single crystal material, polydimethylsiloxane, and curing agent is 1:1.5:

1.

9. The preparation method according to claim 7, characterized in that, The molar ratio of the zero-dimensional antimony-based organic-inorganic hybrid metal halide single crystal material to the blue light material is 2:1; The blue light material is anthracene.

10. A white LED device prepared by the preparation method according to any one of claims 7 to 9.

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