阅读说明：本技术 黑磷烯量子点与石墨烯复合纳米材料的制备方法 (Preparation method of black phosphorus quantum dot and graphene composite nano material ) 是由 朱宝华 李璐瑶 顾玉宗 王芳芳 于 2020-07-30 设计创作，主要内容包括：本发明属于半导体材料制备技术领域,公开了一种黑磷烯量子点与石墨烯复合纳米材料的制备方法,包括以下步骤：将氧化石墨烯粉末分散到N-甲基吡咯烷酮中,在磁力搅拌器上搅拌10min后超声处理1小时,加入黑磷烯量子点分散液和水合肼,搅拌10min,得到原料液；将原料液转移到反应釜中,放入140℃的真空干燥箱中反应6h；反应结束后,将反应釜迅速放入冰水中淬灭,将冷却后的反应液分别用去离子水和无水乙醇多次洗涤后于60℃真空干燥,即得RGO/BP复合纳米材料。本发明通过水合肼来调控复合材料中黑磷烯量子点的浓度,随水合肼加入量增多,复合材料非线性光学响应越强。(The invention belongs to the technical field of semiconductor material preparation, and discloses a preparation method of a black phosphorus quantum dot and graphene composite nano material, which comprises the following steps: dispersing graphene oxide powder into N-methyl pyrrolidone, stirring for 10min on a magnetic stirrer, then carrying out ultrasonic treatment for 1 hour, adding black phosphorus quantum dot dispersion liquid and hydrazine hydrate, and stirring for 10min to obtain a raw material liquid; transferring the raw material liquid into a reaction kettle, and putting the reaction kettle into a vacuum drying box at 140 ℃ for reaction for 6 hours; after the reaction is finished, the reaction kettle is quickly put into ice water for quenching, the cooled reaction liquid is respectively washed by deionized water and absolute ethyl alcohol for a plurality of times and then is dried in vacuum at the temperature of 60 ℃, and the RGO/BP composite nano material is obtained. According to the invention, the concentration of the black phosphorus alkene quantum dots in the composite material is regulated and controlled through hydrazine hydrate, and the nonlinear optical response of the composite material is stronger along with the increase of the addition amount of the hydrazine hydrate.)

1. A preparation method of a black phosphorus quantum dot and graphene composite nano material is characterized by comprising the following steps:

a: dispersing graphene oxide powder into N-methyl pyrrolidone, stirring for 10min on a magnetic stirrer, then carrying out ultrasonic treatment for 1 hour, adding black phosphorus quantum dot dispersion liquid and hydrazine hydrate, and stirring for 10min to obtain a raw material liquid;

b: transferring the raw material liquid into a reaction kettle, and putting the reaction kettle into a vacuum drying box at 140 ℃ for reaction for 6 hours;

c: after the reaction is finished, the reaction kettle is quickly put into ice water for quenching, the cooled reaction liquid is respectively washed by deionized water and absolute ethyl alcohol for a plurality of times and then is dried in vacuum at the temperature of 60 ℃, and the RGO/BP composite nano material is obtained.

2. The method for preparing the black phosphorus alkene quantum dot and graphene composite nanometer material according to claim 1, wherein the method for preparing the black phosphorus alkene quantum dot dispersion liquid comprises the following steps:

c: putting red phosphorus, tin powder and iodine into a quartz tube, putting the quartz tube into a tube furnace with a single temperature area in a high vacuum state, heating the quartz tube to 750 ℃, reacting the quartz tube at a constant temperature for 600 minutes, cooling the quartz tube to 200 ℃, naturally cooling the quartz tube, putting a reaction product into a mixed solution of hydrochloric acid and water to remove impurities, washing the reaction product with deionized water and absolute ethyl alcohol, and drying the reaction product in a vacuum oven at 50 ℃ for 24 hours to obtain black phosphorus single crystals;

d: grinding the black phosphorus single crystal and sodium hydroxide into powder, dispersing the powder into N-methyl pyrrolidone, reacting for 6 hours at 160 ℃ under the protection of nitrogen, centrifuging for 20 minutes after the reaction is finished, and taking supernatant to obtain the black phosphorus alkene quantum dot dispersion liquid.

3. The preparation method of the black phosphorus quantum dot and graphene composite nanomaterial according to claim 1, wherein the preparation method of the graphene oxide comprises the following steps: mixing and grinding graphite powder and potassium permanganate, adding the mixture into a mixed solution of phosphoric acid and sulfuric acid, reacting for 24 hours at 50 ℃, washing with hydrochloric acid and deionized water, and freeze-drying to obtain the graphene oxide.

4. The method for preparing the black phosphorus alkene quantum dot and graphene composite nanometer material according to claim 1, wherein the ratio of the graphene oxide to the black phosphorus alkene quantum dot dispersion liquid is 1 mg: 1ml, wherein the addition volume ratio of the black phosphorus quantum dot dispersion liquid to hydrazine hydrate is 2000: 0.1 to 5.

Technical Field

The invention belongs to the technical field of semiconductor material preparation, and relates to a preparation method of a black phosphorus quantum dot and graphene composite nano material.

Background

The graphene is a zero-band-gap two-dimensional nano material, has excellent electron mobility and nonlinear optical characteristics, and can be widely applied to the novel nonlinear photoelectronic fields of photovoltaic devices, optical switches, optical limiters and the like.

Although the nonlinear optical properties of graphene are relatively large, the requirements in the field of nonlinear optics cannot be met, so with the emergence of another two-dimensional material, namely black phosphorus, and the excellent optoelectronic properties exhibited by the black phosphorus, researchers begin to compound graphene and black phosphorus quantum dots to improve the nonlinear optical properties of the material. At present, the preparation method of graphene and black phosphorus quantum dots is mainly a thermal stirring method, firstly, black phosphorus is ground, secondly, the black phosphorus is heated and stirred into black phosphorus quantum dots, the size of the quantum dots is controlled by the stirring times, and then, the black phosphorus quantum dots and the graphene are heated and stirred. Therefore, it is necessary to develop a synthetic method of RGO/BP composite nanomaterial with synthetic bond, low cost, simple process and good nonlinear optical performance.

Disclosure of Invention

The invention aims to provide a preparation method of a black phosphorus alkene quantum dot and graphene composite nano material, wherein the concentration of the black phosphorus alkene quantum dot in the composite material is regulated and controlled by hydrazine hydrate, and the stronger the nonlinear optical response of the composite material is along with the increase of the addition of the hydrazine hydrate, so that the composite material can be applied to the novel light control fields of light control type phase modulators, refraction rate modulators, real-time holography, light correlators, phase conjugation, light phase recovery photodiodes and the like.

In order to achieve the purpose, the invention adopts the following technical scheme:

the invention provides a preparation method of a black phosphorus quantum dot and graphene composite nano material, which comprises the following steps:

a: dispersing graphene oxide powder into N-methyl pyrrolidone, stirring for 10min on a magnetic stirrer, then carrying out ultrasonic treatment for 1 hour, adding black phosphorus quantum dot dispersion liquid and hydrazine hydrate, and stirring for 10min to obtain a raw material liquid;

b: transferring the raw material liquid into a reaction kettle, and putting the reaction kettle into a vacuum drying box at 140 ℃ for reaction for 6 hours;

c: after the reaction is finished, the reaction kettle is quickly put into ice water for quenching, the cooled reaction liquid is respectively washed by deionized water and absolute ethyl alcohol for a plurality of times and then is dried in vacuum at the temperature of 60 ℃, and the RGO/BP composite nano material is obtained.

Preferably, the preparation method of the black phosphorus quantum dot dispersion liquid comprises the following steps:

c: putting red phosphorus, tin powder and iodine into a quartz tube, putting the quartz tube into a tube furnace with a single temperature area in a high vacuum state, heating the quartz tube to 750 ℃, reacting the quartz tube at a constant temperature for 600 minutes, cooling the quartz tube to 200 ℃, naturally cooling the quartz tube, putting a reaction product into a mixed solution of hydrochloric acid and water to remove impurities, washing the reaction product with deionized water and absolute ethyl alcohol, and drying the reaction product in a vacuum oven at 50 ℃ for 24 hours to obtain black phosphorus single crystals;

d: grinding the black phosphorus single crystal and sodium hydroxide into powder, dispersing the powder into N-methyl pyrrolidone, reacting for 6 hours at 160 ℃ under the protection of nitrogen, centrifuging for 20 minutes after the reaction is finished, and taking supernatant to obtain the black phosphorus alkene quantum dot dispersion liquid.

Preferably, the preparation method of the graphene oxide comprises the following steps: mixing and grinding graphite powder and potassium permanganate, adding the mixture into a mixed solution of phosphoric acid and sulfuric acid, reacting for 24 hours at 50 ℃, washing with hydrochloric acid and deionized water, and freeze-drying to obtain the graphene oxide.

Preferably, the ratio of the graphene oxide to the black phosphorus quantum dot dispersion is 1 mg: 1ml, wherein the addition volume ratio of the black phosphorus quantum dot dispersion liquid to hydrazine hydrate is 2000: 0.1 to 5.

Compared with the prior art, the invention has the beneficial effects that:

the method takes the black phosphorus alkene quantum dots and the graphene oxide as reaction sources, takes hydrazine hydrate as a reducing agent, adopts a one-step synthesis method to prepare the black phosphorus alkene quantum dot and graphene composite nano material, and the nonlinear optical property of the obtained composite nano material is stronger than that of the black phosphorus alkene or the graphene monomer; the concentration of the black phosphorus alkene quantum dots in the composite material is regulated and controlled through hydrazine hydrate, the nonlinear optical response of the composite material is stronger along with the increase of the addition of the hydrazine hydrate, and the composite material can be applied to novel light control fields of light control type phase modulators, refraction rate modulators, real-time holography, light correlators, phase conjugation, light phase recovery photodiodes and the like. The preparation method has the advantages of nontoxic and easily-obtained raw materials, low cost, simple process, time saving, convenience and safety.

Drawings

FIG. 1 is a TEM image of an RGO/BP-2 composite nanomaterial prepared in example 2 of the present invention.

FIG. 2 is an infrared spectrum of an RGO/BP-2 composite nanomaterial prepared in example 2 of the present invention.

FIG. 3 is a TEM image of an RGO/BP-3 composite nanomaterial prepared in example 3 of the present invention.

FIG. 4 is a TEM image of an RGO/BP-4 composite nanomaterial prepared in example 4 of the present invention.

FIG. 5 is a TEM image of an RGO/BP-5 composite nanomaterial prepared in example 5 of the present invention.

FIG. 6 is a Z-scan open pore diagram of RGO/BP composite nanomaterials prepared in examples 1-5 of the present invention.

FIG. 7 is a Z-scan closed-pore diagram of RGO/BP composite nanomaterials prepared in examples 1-5 of the present invention.

Detailed Description

The following examples are intended to illustrate the invention, but are not intended to limit the scope of the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. The test methods in the following examples are conventional methods unless otherwise specified.