Liquid semiconductor and its preparation method and application

Abstract

The present invention belongs to the field of semiconductor preparation technology, and in particular relates to a liquid semiconductor and its preparation method and application. The preparation method comprises the following steps: a metal salt and an imidazole derivative are used to synthesize a ZIF-8 material by a solvent thermal method; a double bond is introduced into the ZIF-8 material to obtain a ZIFs precursor; a hydrogel precursor, a ZIFs precursor and a photoinitiator are dissolved in a buffer solution to obtain a mixed solution; the mixed solution or a substrate coated with the mixed solution is subjected to laser treatment to obtain the liquid semiconductor. The present invention greatly simplifies the cumbersome steps of the current synthesis of liquid semiconductors, broadens the scope of existing liquid semiconductors, and realizes the universal preparation of liquid semiconductors in a simple and mild environment. The present invention can realize the universal preparation of MOF-based semiconductors in liquid form on substrates of any material under normal temperature and pressure conditions.

Description

Technical Field

[0001] The present invention belongs to the technical field of semiconductor preparation, and in particular relates to a liquid semiconductor and a preparation method and application thereof. Background Art

[0002] Liquid semiconductors are a special form of semiconductor material (compound) that exhibits semiconductor-like conductive behavior in a liquid state, such as band gap characteristics and carrier transport capacity. Hydrogel-based liquid semiconductors, as a new generation of room-temperature liquid semiconductor materials, are an important representative of liquid semiconductors and offer numerous advantages. Liquid semiconductor material properties can be dynamically manipulated by varying conditions, such as the type of semiconductor and hydrogel precursor. Furthermore, liquid semiconductors can operate at room temperature, making them suitable for flexible electronics and biointerface applications. Their good compatibility with biological tissues allows for use in implantable devices. However, compared to traditional semiconductors, the development of liquid semiconductor materials is still in its infancy. Current preparation methods for semiconductors and hydrogels are incompatible, resulting in simple physical mixing of the two, resulting in single networks or unstructured frameworks. Furthermore, there are a limited number of n-type liquid semiconductors. Summary of the Invention

[0003] In response to the above-mentioned problems existing in the prior art, the present invention provides a liquid semiconductor and a preparation method and application thereof, which can realize the universal preparation of liquid semiconductors in a simple and mild environment.

[0004] To achieve the above-mentioned purpose, the technical solution provided by the present invention is as follows:

[0005] In a first aspect, the present application provides a method for preparing a liquid semiconductor, comprising the following steps:

[0006] ZIF-8 materials were synthesized by solvothermal method using metal salts and imidazole derivatives;

[0007] Double bonds or thiol groups are introduced into ZIF-8 materials to obtain ZIFs precursors;

[0008] The hydrogel precursor, ZIFs precursor and photoinitiator are dissolved in a buffer solution to obtain a mixed solution;

[0009] Laser processing the mixed liquid or a substrate drop-coated with the mixed liquid to obtain the liquid semiconductor;

[0010] Among the hydrogel precursor and the ZIFs precursor, one contains a double bond and the other contains a thiol group.

[0011] Optionally, the preparation of the ZIFs precursor comprises the following steps: dispersing ZIF-8 material and 2-mercaptoimidazole or an imidazole derivative with an olefin substituent in a solvent, reacting at 50-60° C., and purifying after the reaction to obtain the ZIFs precursor.

[0012] Optionally, the imidazole derivative with an olefin substituent includes one or more of 2-vinylimidazole and 1-allyl-1H-imidazole.

[0013] Optionally, the preparation of the ZIFs precursor comprises the following steps: mixing ZIF-8 material, acryloyl chloride and an acid scavenger, reacting at 50-60° C., and purifying after the reaction to obtain the ZIFs precursor.

[0014] Optionally, the acid scavenger comprises pyridine.

[0015] Optionally, the laser treatment conditions include: power density 10 5 -10 9 W / cm 2 , frequency 1 Hz-80 kHz, laser wavelength range is ultraviolet.

[0016] Optionally, the laser used in the laser processing includes nanosecond laser or femtosecond laser.

[0017] Optionally, the laser processing environment is one of liquid phase, vacuum phase and gas phase.

[0018] Optionally, the metal salt includes one or more of chlorides, sulfates, nitrates, and acetates of iron, cobalt, nickel, zinc, and manganese; the imidazole derivative includes 2-methylimidazole; and the solvent is water or an organic solvent.

[0019] Optionally, the preparation of the ZIF-8 material includes the following steps: mixing an imidazole derivative with a solvent to obtain an imidazole solution; mixing a metal salt with a solvent to obtain a metal salt solution, mixing the metal salt solution with the imidazole solution and reacting them at 80-150° C., washing and drying to obtain the ZIF-8 material.

[0020] Optionally, the substrate includes one or more of a carbon paper substrate, a metal substrate, an organic material substrate, and an inorganic material substrate.

[0021] Optionally, the hydrogel precursor containing a thiol group includes one or more of HS-PEG-HS, 4ARM-PEG-SH and 8ARM-PEG-SH; the hydrogel precursor containing a double bond includes PEGDA.

[0022] Optionally, the photoinitiator includes one or more of phenyl 2,4,6-trimethylbenzoyl phosphate lithium salt and 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone.

[0023] Optionally, the hydrogel precursor, the ZIFs precursor and the photoinitiator are dissolved in a buffer solution and dispersed by ultrasound to obtain a mixed solution.

[0024] In a second aspect, the present application also provides a liquid semiconductor prepared according to the method described in the first aspect.

[0025] In a third aspect, the present application also provides an application of the liquid semiconductor described in the second aspect in an electrode.

[0026] Compared with the prior art, this application has at least the following beneficial effects:

[0027] The present invention greatly simplifies the current cumbersome steps for synthesizing liquid semiconductors, broadens the existing range of liquid semiconductors, and realizes the universal preparation of liquid semiconductors in a simple and mild environment.

[0028] By synthesizing and modifying ZIF-8 materials, and utilizing the ZIFs precursor to react with the double bonds and thiol groups in the hydrogel precursor, the ZIFs precursor and the aqueous gel precursor are connected by covalent bonds, thereby realizing the preparation of organic-inorganic hybrid liquid semiconductors. The prepared liquid semiconductors have both the high carrier mobility characteristics of inorganic semiconductors and the flexibility of organic semiconductors.

[0029] The present invention can realize the universal preparation of liquefied MOF-based semiconductors on substrates of any material under normal temperature and pressure conditions. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 This is a scanning electron micrograph of the freeze-dried liquid semiconductor obtained in Example 1 of the present invention, where the scales in (a) and (b) are 50 μm and 10 μm, respectively; (c) is a liquid semiconductor sample with the NJU character printed on it, prepared using the designed laser optical path;

[0031] Figure 2 This is the UV-visible spectrum of the liquid semiconductor in Example 1 of the present invention, where a shows the change in the band gap and b shows the positions of two new absorption peaks;

[0032] Figure 3 The test spectrum of the liquid semiconductor obtained in Example 2 of the present invention; wherein (a) and (b) are infrared spectrum and Raman spectrum respectively;

[0033] Figure 4 This is the photocurrent it image of the liquid semiconductor self-supporting electrode obtained in Example 3 of the present invention. DETAILED DESCRIPTION

[0034] The present invention is described in further detail below with reference to the accompanying drawings:

[0035] Unless otherwise specified, the experimental methods used in the embodiments of the present invention are conventional methods.

[0036] The reagents and materials used in this example can be purchased conventionally. The quantitative experiments involved in the examples were repeated at least three times, and the results were averaged.

[0037] Source of raw materials:

[0038] HS-PEG-SH (MW 2000): purchased from Aladdin Reagent (Shanghai) Co., Ltd.

[0039] Example 1

[0040] A universal preparation method for liquid semiconductors based on laser comprises the following steps:

[0041] (1) Add 4.54 g of 2-methylimidazole to 60 mL of deionized water and stir for 20 min to dissolve to obtain an imidazole solution. Simultaneously, add 0.2726 g of zinc chloride to 20 mL of deionized water and stir for 10 min to dissolve to obtain a metal salt solution. Then, the prepared metal salt solution and imidazole solution were mixed and stirred for 4 min, transferred to a polytetrafluoroethylene autoclave (100 mL), and hydrothermally reacted at 120 ° C for 6 h. The resulting solution was centrifuged twice with deionized water and methanol, respectively, and finally dried in vacuum at 70 ° C overnight to obtain ZIF-8 material.

[0042] (2) 500 mg of ZIF-8 and 500 mg of 1-allyl-1H-imidazole were weighed and added to 10 mL of methanol solvent and ultrasonically dispersed to obtain a uniformly dispersed suspension. The suspension was reacted in an oven at 55°C for 24 h. After cooling to room temperature, the suspension was centrifuged with methanol until the supernatant became colorless. Finally, the centrifuged mixture was vacuum dried at 70°C overnight to obtain the ZIFs precursor.

[0043] (3) Dissolve 400 mg of HS-PEG-SH in PBS buffer (PBS phosphate powder 0.01 mol / L, pH 7.2-7.4), add 200 mg of ZIFs precursor, and ultrasonicate to ensure uniform dispersion and prevent particle aggregation; then add LAP (phenyl 2,4,6-trimethylbenzoyl phosphate lithium salt) photoinitiator at a concentration of 0.5 wt% to obtain a mixed solution.

[0044] (4) The mixed solution was placed in a transparent reaction container and a nanosecond laser was used with an average laser power density of 2×105 W / cm 2 , frequency is 30kHz, and irradiation is performed with a UV laser light source of 355 nm wavelength for 30 s to obtain a liquid semiconductor. Figure 1 shown.

[0045] from Figure 2 From the UV-visible spectrum, it can be seen that the band gap change of the liquid semiconductor synthesized in Example 1 is in line with expectations, wherein the band gap Eg(ZIF-8)=Eg(ZIFs precursor)≤Eg(liquid semiconductor)≤Eg(HS-PEG-SH); two new absorption peaks appeared in both the freeze-dried (the liquid semiconductor synthesized in Example 1 was freeze-dried for the convenience of testing) and liquid samples, which are the absorption peaks of the photoinitiator APL.

[0046] Example 2

[0047] A universal preparation method for liquid semiconductors based on laser, comprising the following steps:

[0048] (1) Add 4.54 g of 2-methylimidazole to 60 mL of deionized water and stir for 20 min to dissolve to obtain an imidazole solution. Simultaneously, add 0.2726 g of zinc chloride to 20 mL of deionized water and stir for 10 min to dissolve to obtain a metal salt solution. Then, the prepared metal salt solution and imidazole solution were mixed and stirred for 4 min, transferred to a polytetrafluoroethylene autoclave (100 mL), and hydrothermally reacted at 120 ° C for 6 h. The resulting solution was centrifuged twice with deionized water and methanol, respectively, and finally dried in vacuum at 70 ° C overnight to obtain ZIF-8 material.

[0049] (2) Weigh 500 mg of ZIF-8 material, add 500 mg of acryloyl chloride and 200 mg of pyridine (as an acid scavenger), and stir at 55 °C for 24 hours to allow the acryloyl group to be partially grafted onto the uncoordinated sites on the surface of ZIF-8. After the reaction is completed, centrifuge, wash to remove unreacted reagents, and dry to obtain the ZIFs precursor.

[0050] (3) Dissolve 400 mg of HS-PEG-SH in PBS buffer (PBS phosphate powder 0.01 mol / L, pH 7.2-7.4), add 200 mg of ZIFs precursor, and ultrasonicate to ensure uniform dispersion and prevent particle aggregation; then add LAP (phenyl 2,4,6-trimethylbenzoyl phosphate lithium salt) photoinitiator at a concentration of 0.5 wt% to obtain a mixed solution.

[0051] (4) The mixed solution was placed in a transparent reaction container and a nanosecond laser was used with an average laser power density of 2×10 5 W / cm 2, frequency is 30 kHz, and a UV laser light source with a wavelength of 355 nm is irradiated for 30 s to obtain a liquid semiconductor.

[0052] from Figure 3 The infrared spectrum (a) and Raman spectrum (b) show that the double bonds in the ZIFs of the liquid semiconductor synthesized in Example 2 are bonded to the thiol groups to form CSC bonds, which indicates that the liquid semiconductor synthesized in Example 2 is not a mixture, but a liquid semiconductor compound.

[0053] Example 3

[0054] A universal preparation method for liquid semiconductors based on laser, comprising the following steps:

[0055] (1) Add 4.54 g of 2-methylimidazole to 60 mL of deionized water and stir for 20 min to dissolve to obtain an imidazole solution. Simultaneously, add 0.2726 g of zinc chloride to 20 mL of deionized water and stir for 10 min to dissolve to obtain a metal salt solution. Then, the prepared metal salt solution and imidazole solution were mixed and stirred for 4 min, transferred to a polytetrafluoroethylene autoclave (100 mL), and hydrothermally reacted at 120 ° C for 6 h. The resulting solution was centrifuged twice with deionized water and methanol, respectively, and finally dried in vacuum at 70 ° C overnight to obtain ZIF-8 material.

[0056] (2) Weigh 500 mg of ZIF-8 and 500 mg of 1-allyl-1H-imidazole and add them to 10 mL of methanol solvent for ultrasonic dispersion to obtain a uniformly dispersed suspension. The suspension was preheated in an oven at 55°C for 24 h. After cooling to room temperature, it was centrifuged with methanol until the supernatant became colorless. Finally, the mixture was vacuum-dried at 70°C overnight to obtain the ZIFs precursor.

[0057] (3) Dissolve 400 mg of HS-PEG-SH in PBS buffer (PBS phosphate powder 0.01 mol / L, pH 7.2-7.4), add 200 mg of ZIFs precursor, and ultrasonicate to ensure uniform dispersion and prevent particle aggregation; then add LAP (phenyl 2,4,6-trimethylbenzoyl phosphate lithium salt) photoinitiator at a concentration of 0.5 wt% to obtain a mixed solution.

[0058] (4) The mixed solution was evenly dropped onto the nickel foam substrate, and the average laser power density was set to 2×10 5 W / cm 2 , frequency is 30 kHz, and a UV laser light source with a wavelength of 355 nm is used for irradiation for 30 s to obtain a liquid semiconductor supported on a nickel electrode.

[0059] The liquid semiconductor synthesized in Example 3 was successfully supported on the nickel foam electrode, and a self-supporting electrode (corresponding to the application of semiconductor) was successfully prepared. Figure 4 As shown, the photocurrent it test was carried out using the liquid semiconductor self-supporting electrode, and the photocurrent it image of the liquid semiconductor was obtained, proving that it has semiconductor properties.

[0060] The basic principles, main features and advantages of the present invention are shown and described above. It should be understood by those skilled in the art that the present invention is not limited to the above embodiments. The above embodiments and descriptions are merely illustrative of the principles of the present invention. Various changes and improvements may be made to the present invention without departing from the spirit and scope of the present invention. The scope of protection claimed in the present invention is defined by the appended claims, the description and their equivalents.

Claims

1. A method for preparing a liquid semiconductor, characterized in that: include: ZIF-8 materials were synthesized by solvothermal method using metal salts and imidazole derivatives; Double bonds or thiol groups are introduced into ZIF-8 materials to obtain ZIFs precursors; The hydrogel precursor, ZIFs precursor and photoinitiator are dissolved in a buffer solution to obtain a mixed solution; subjecting the mixed solution or the substrate drop-coated with the mixed solution to laser processing to obtain the liquid semiconductor; Of the hydrogel precursor and the ZIFs precursor, one contains a double bond and the other contains a thiol group; The hydrogel precursor containing thiol groups includes one or more of HS-PEG-HS, 4ARM-PEG-SH and 8ARM-PEG-SH.

2. The method for preparing a liquid semiconductor according to claim 1, wherein: The preparation of the ZIFs precursor comprises: dispersing ZIF-8 material and 2-mercaptoimidazole or an imidazole derivative with an olefin substituent in a solvent, reacting at 50-60° C., and purifying after the reaction to obtain the ZIFs precursor.

3. The method for preparing a liquid semiconductor according to claim 2, wherein: The imidazole derivatives with olefin substituents include one or more of 2-vinylimidazole and 1-allyl-1H-imidazole.

4. The method for preparing a liquid semiconductor according to claim 1, wherein: The preparation of the ZIFs precursor comprises: mixing ZIF-8 material, acryloyl chloride and an acid scavenger, reacting at 50-60° C., and purifying after the reaction to obtain the ZIFs precursor.

5. The method for preparing a liquid semiconductor according to claim 1, wherein: The laser used in the laser treatment meets the following requirements: power density 10 5 -10 9 W / cm 2 , frequency 1 Hz-80 kHz, laser wavelength range is ultraviolet.

6. The method for preparing a liquid semiconductor according to claim 1, wherein: The preparation of the ZIF-8 material includes: mixing an imidazole derivative with a solvent to obtain an imidazole solution; mixing a metal salt with a solvent to obtain a metal salt solution; mixing the metal salt solution with the imidazole solution and reacting them at 80-150° C., washing, and drying to obtain the ZIF-8 material.

7. The method for preparing a liquid semiconductor according to claim 1, wherein: The substrate includes one or more of a metal substrate, an organic material substrate, and an inorganic material substrate.

8. The method for preparing a liquid semiconductor according to claim 1, wherein: The substrate includes a carbon paper substrate.

9. A liquid semiconductor prepared according to the method according to any one of claims 1 to 8.

10. Use of the liquid semiconductor according to claim 9 in an electrode.

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