阅读说明：本技术 一种晶态红磷薄片的制备方法 (Preparation method of crystalline red phosphorus sheet ) 是由 严清峰 孙召建 于 2021-08-20 设计创作，主要内容包括：本发明属于功能材料技术领域,具体而言,涉及一种晶态红磷薄片的制备方法。该方法包括：将原料非晶红磷、碘和锡按质量比装入反应器的一端,另一端放置尺寸合适的目标衬底；随后加热将反应器真空密封；将反应器水平放置于加热炉中,升温至设定,并保温,然后降温至室温,目标衬底上成功制备晶态红磷薄片。本发明首次提出了在衬底上直接制备晶态红磷薄片的方法；本发明使用商业化的非晶红磷为原料,容易得到,生产成本较低；本发明制备得到的晶态红磷薄片结晶质量极高,取向明确,并且可以根据应用选择目标衬底来制备晶态红磷薄片,为未来晶态红磷在电子、光电子等领域的实际应用奠定坚实基础。(The invention belongs to the technical field of functional materials, and particularly relates to a preparation method of a crystalline red phosphorus sheet. The method comprises the following steps: loading raw materials of amorphous red phosphorus, iodine and tin into one end of a reactor according to the mass ratio, and placing a target substrate with a proper size at the other end; subsequently heating to vacuum seal the reactor; and horizontally placing the reactor in a heating furnace, heating to a set temperature, preserving the heat, then cooling to room temperature, and successfully preparing the crystalline red phosphorus sheet on the target substrate. The invention provides a method for directly preparing crystalline red phosphorus sheets on a substrate for the first time; the invention uses commercial amorphous red phosphorus as raw material, which is easy to obtain and has lower production cost; the crystalline red phosphorus flake prepared by the invention has extremely high crystallization quality and definite orientation, and the crystalline red phosphorus flake can be prepared by selecting the target substrate according to the application, thereby laying a solid foundation for the practical application of the crystalline red phosphorus in the fields of electronics, photoelectrons and the like in the future.)

1. A preparation method of a crystalline red phosphorus flake is characterized by comprising the following steps:

(1) placing raw materials of amorphous red phosphorus, iodine, tin and a target substrate at two ends of a reactor;

(2) carrying out vacuum sealing on the reactor;

(3) and horizontally placing the reactor, heating, preserving heat and cooling to obtain the crystalline red phosphorus slice.

2. The method for preparing the crystalline red phosphorus flake according to claim 1, wherein in the step (1), the mass ratio of the raw materials of the amorphous red phosphorus, the iodine and the tin is (10-30): 1: 1.

3. The method for preparing crystalline red phosphorus flake according to claim 1, wherein in the step (1), the target substrate is SiO₂Any one of a/Si, quartz, silicon, gallium nitride, sapphire, fluorophlogopite, or soda-lime glass substrate.

4. The method for preparing crystalline red phosphorus flake according to claim 1, wherein in the step (2), the degree of vacuum for sealing is in the range of 10^-5～10Pa。

5. The method for preparing the crystalline red phosphorus flake according to claim 1, wherein in the step (3), the specific processes of heating, heat preservation and cooling to obtain the crystalline red phosphorus flake comprise: and heating to 500-700 ℃ within 3 hours, preserving the heat for 5-20 hours, cooling to room temperature within 5-20 hours, and preparing the crystalline red phosphorus sheet on the target substrate.

6. A crystalline red phosphorus flake, characterized by being obtained by the method as claimed in claim 1 to 5.

Technical Field

The invention belongs to the technical field of functional materials, and particularly relates to a preparation method of a crystalline red phosphorus sheet.

Background

Elemental phosphorus has abundant allotropes, mainly including white phosphorus, black phosphorus, red phosphorus and the like. Wherein, compared with white phosphorus and black phosphorus, red phosphorus has the characteristics of stable property, low price, easy obtaining and environmental protection. In daily life, red phosphorus can be prepared into an igniter, a flame retardant, a pesticide, a chemical fertilizer and the like; the method is also widely applied to the fields of semiconductor doping agents, photocatalysis, lithium sodium ion batteries and the like in scientific research.

In recent years, crystalline red phosphorus has been demonstrated to have semiconductor properties and photoelectric response properties, demonstrating potential as an electronic and optoelectronic functional material. Currently, the preparation of crystalline red phosphorus nanoplates or nanobelts relies on a top-down approach. Firstly preparing crystalline red phosphorus of a block, then obtaining low-dimensional crystalline red phosphorus through mechanical stripping or liquid phase stripping, and finally transferring the low-dimensional crystalline red phosphorus to a target substrate to construct a device.

Disclosure of Invention

The present invention aims to solve the above technical problems at least to some extent, and based on the discovery and recognition by the inventors of the following facts and problems, the preparation of crystalline red phosphorus nanoplates or nanobelts has a number of disadvantages: 1. the preparation process is complicated; 2. the size and the shape of the prepared crystalline red phosphorus nanosheet or nanobelt are uncontrollable; 3. the stripping and transfer processes can lead to oxidation and contamination of impurities, among other things. In order to fully exploit the potential of the crystalline red phosphorus and lay a cushion for subsequent practical application, a way for directly preparing a crystalline red phosphorus sheet with high crystalline quality and definite orientation on a substrate is urgently needed to be developed.

The invention aims to provide a preparation method of a crystalline red phosphorus sheet, which is a method for directly preparing the crystalline red phosphorus sheet on a substrate and lays a solid foundation for the application of the subsequent crystalline red phosphorus in the fields of electronic devices and photoelectric devices.

The embodiment of the invention provides a preparation method of a crystalline red phosphorus sheet, which comprises the following steps:

(1) placing raw materials of amorphous red phosphorus, iodine, tin and a target substrate at two ends of a reactor;

(2) carrying out vacuum sealing on the reactor;

(3) and horizontally placing the reactor, heating, preserving heat and cooling to obtain the crystalline red phosphorus slice.

The invention firstly provides a method for directly preparing the crystalline red phosphorus sheet on the substrate. The embodiment of the invention uses commercial amorphous red phosphorus as a raw material, is easy to obtain and has lower production cost. The crystalline red phosphorus flake prepared by the method has extremely high crystallization quality and definite orientation. The target substrate can be selected to prepare the crystalline red phosphorus sheet according to the actual application requirements, and a solid foundation is laid for the actual application of the crystalline red phosphorus in the fields of electronics, photoelectrons and the like in the future.

In some embodiments, in the step (1), the mass ratio of the raw amorphous red phosphorus, iodine and tin is (10-30): 1: 1.

In some embodiments, in step (1), the target substrate is SiO₂Any one of a/Si, quartz, silicon, gallium nitride, sapphire, fluorophlogopite, or soda-lime glass substrate.

In some embodiments, in the step (2), the sealed vacuum degree range is 10^-5～10Pa。

In some embodiments, in the step (3), the specific processes of heating, keeping warm, and cooling to obtain the crystalline red phosphorus flake include: and heating to 500-700 ℃ within 3 hours, preserving the heat for 5-20 hours, cooling to room temperature within 5-20 hours, and preparing the crystalline red phosphorus sheet on the target substrate.

According to the preparation method provided by the embodiment of the invention, the advantages are as follows:

the preparation method of the embodiment of the invention firstly provides a method for directly preparing the crystalline red phosphorus sheet on the substrate, and the commercialized amorphous red phosphorus is used as a raw material in the preparation process, so that the preparation method is easy to obtain and the production cost of the red phosphorus is lower.

Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below. It is obvious that the drawings in the following description are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort. The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:

FIG. 1 is an optical microscope image (OM) of a crystalline red phosphorus flake prepared by example 1 of the process of the present invention.

FIG. 2 is an Atomic Force Microscope (AFM) picture of the crystalline red phosphorus flake obtained in example 1.

FIG. 3 is an X-ray diffraction pattern (XRD) of the crystalline red phosphorus flake obtained in example 1.

Fig. 4 is a Raman spectrum (Raman) of the crystalline red phosphorus flake prepared in example 1.

FIG. 5 is a Transmission Electron Micrograph (TEM) of the crystalline red phosphorus flake obtained in example 1.

FIG. 6 is a High Resolution Transmission Electron Micrograph (HRTEM) of the crystalline red phosphorus flakes obtained in example 1.

Fig. 7 is an optical microscope photograph and a raman spectrum of the crystalline red phosphorus flake prepared in example 2.

Fig. 8 is an optical microscope photograph and a raman spectrum of the crystalline red phosphorus flake obtained in example 3.

Fig. 9 is an optical microscope photograph and a raman spectrum of the crystalline red phosphorus flake prepared in example 4.

Fig. 10 is an optical microscope photograph and a raman spectrum of the crystalline red phosphorus flake obtained in example 5.

Fig. 11 is an optical microscope photograph and a raman spectrum of the crystalline red phosphorus flake obtained in example 6.

Fig. 12 is an optical microscope photograph and a raman spectrum of the crystalline red phosphorus flake obtained in example 7.

Detailed Description

The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.

The embodiment of the invention provides a preparation method of a crystalline red phosphorus sheet, which comprises the following steps:

(1) placing raw materials of amorphous red phosphorus, iodine, tin and a target substrate at two ends of a reactor;

(2) carrying out vacuum sealing on the reactor;

(3) and horizontally placing the reactor, heating, preserving heat and cooling to obtain the crystalline red phosphorus slice.

The preparation method of the invention takes the amorphous red phosphorus as the raw material, which is easy to obtain, thus the production cost is lower. The crystalline red phosphorus flake prepared by the method has extremely high crystallization quality and definite orientation. The target substrate can be selected to prepare the crystalline red phosphorus sheet according to the actual application requirements, and a solid foundation is laid for the actual application of the crystalline red phosphorus in the fields of electronics, photoelectrons and the like in the future.

According to the preparation method of the crystalline red phosphorus flake, in the step (1), the mass ratio of the raw materials of amorphous red phosphorus, iodine and tin is (10-30): 1: 1. The raw materials used, amorphous red phosphorus, iodine and tin, can be in the form of powders, flakes or blocks.

The preparation method of the crystalline red phosphorus flake, according to the invention, wherein, in the step (1), the target substrate is SiO₂Any one of a/Si, quartz, silicon, gallium nitride, sapphire, fluorophlogopite, or soda-lime glass substrate.

The preparation method can select a target substrate to prepare the crystalline red phosphorus flake according to the application, for example, the electrical and photoelectric properties of the crystalline red phosphorus flake need to be determined, and an insulating substrate, such as SiO, needs to be selected₂A substrate of/Si, sapphire and fluorine crystal mica; if the optical properties of crystalline red phosphorus are to be characterized, transparent substrates, such as fluorophlogopite and soda-lime glass substrates, need to be selected.

The preparation method of the crystalline red phosphorus flake, provided by the invention, comprises the step (2) of sealing the vacuum degree in a range of 10^-5-10 Pa. The high vacuum degree is beneficial to obtaining the crystalline red phosphorus with higher crystallinity.

According to the preparation method of the crystalline red phosphorus slice, the specific process of heating, heat preservation and cooling in the step (3) to obtain the crystalline red phosphorus slice is as follows: and heating to 500-700 ℃ within 3 hours, preserving the heat for 5-20 hours, cooling to room temperature within 5-20 hours, and preparing the crystalline red phosphorus sheet on the target substrate.

In some embodiments, it is proposed to prepare crystalline red phosphorus flakes using the above method.

The invention provides a method for directly preparing crystalline red phosphorus sheets on a substrate for the first time; the invention uses the commercialized amorphous red phosphorus as the raw material, is easy to obtain, has lower production cost, and the prepared crystalline red phosphorus slice has extremely high crystallization quality and definite orientation, and can select the target substrate to prepare the crystalline red phosphorus slice according to the application, thereby laying a solid foundation for the practical application of the crystalline red phosphorus in the fields of electronics, photoelectrons and the like in the future.

The present invention will be described in detail below by way of examples.

Example 1

Taking 500mg of blocky amorphous red phosphorus, 20mg of powdery iodine simple substance and 20mg of powdery tin simple substance, uniformly mixing, filling the mixture into one end of a quartz tube (the length is 200mm, the outer diameter is 12mm, and the inner diameter is 10mm), and placing SiO (the length is multiplied by the width is 10mm multiplied by 6 mm) at the other end₂a/Si substrate. The quartz tube is vacuum sealed by a hydrogen flame vacuum tube sealing machine, and the vacuum degree is controlled to be 10^-4Pa. The quartz tube is horizontally placed in a tube furnace, heated to 620 ℃ within 3 hours, kept warm for 10 hours, and then cooled to room temperature within 10 hours. Breaking of quartz tube, SiO₂The crystalline red phosphorus flake is successfully prepared on the Si substrate.

Wherein FIG. 1 is an optical microscope photograph of the crystalline red phosphorus flake obtained in example 1. As can be seen from FIG. 1, the crystalline red phosphorus flakes appear as regular rectangles with a length of about 10-20 μm. FIG. 2 is an Atomic Force Microscope (AFM) picture of the crystalline red phosphorus flake obtained in example 1, having a thickness of 37 nm. Fig. 3 is an X-ray diffraction pattern (XRD) of the crystalline red phosphorus flake obtained in example 1, and sharp diffraction peaks in fig. 3 confirm the excellent crystallinity and (001) plane orientation growth of the crystalline red phosphorus flake. Fig. 4 is a Raman spectrum (Raman) of the crystalline red phosphorus flake prepared in example 1. The raman spectrum confirmed that this crystalline red phosphorus is a class iv red phosphorus, also known as fibrous red phosphorus. FIG. 5 is a Transmission Electron Micrograph (TEM) of the crystalline red phosphorus flake obtained in example 1. Fig. 6 is a High Resolution Transmission Electron Micrograph (HRTEM) of the crystalline red phosphorus flake obtained in example 1, whose regular lattice fringes again confirm the excellent crystalline properties of the crystalline red phosphorus.

Example 2

600mg of flake amorphous red phosphorus, 20mg of powdery iodine simple substance and 20mg of block tin simple substance are taken, uniformly mixed and then put into one end of a quartz tube (the length is 200mm, the outer diameter is 12mm, and the inner diameter is 10mm), and a quartz substrate with the length multiplied by the width of 10mm multiplied by 4mm is placed at the other end. The quartz tube is vacuum sealed by a hydrogen flame vacuum tube sealing machine, and the vacuum degree is controlled to be 10^-5Pa. The quartz tube is horizontally placed in a tube furnace, heated to 700 ℃ within 3 hours, kept warm for 20 hours, and then cooled to room temperature within 20 hours. And breaking the quartz tube to successfully prepare the crystalline red phosphorus sheet on the quartz substrate.

Wherein, fig. 7 is an optical microscope photograph and a corresponding raman spectrum of the crystalline red phosphorus flake obtained in example 2, showing that the crystalline red phosphorus flake is in a regular rectangular shape, and a sharp raman spectrum peak confirms its excellent crystallization property.

Example 3

200mg of blocky amorphous red phosphorus, 20mg of powdery iodine simple substance and 20mg of powdery tin simple substance are taken, uniformly mixed and then put into one end of a quartz tube (the length is 200mm, the outer diameter is 12mm, and the inner diameter is 10mm), and a silicon substrate with the length multiplied by the width of 10mm multiplied by 6mm is placed at the other end. The quartz tube is vacuum sealed by a hydrogen flame vacuum tube sealing machine, and the vacuum degree is controlled to be 10^-3Pa. The quartz tube is horizontally placed in a tube furnace, heated to 500 ℃ within 3 hours, kept warm for 5 hours, and then cooled to room temperature within 5 hours. The quartz tube is broken, and the crystalline red phosphorus sheet is successfully prepared on the silicon substrate. Fig. 8 is an optical microscope photograph and corresponding raman spectrum of the crystalline red phosphorus flake obtained in example 3, showing that the crystalline red phosphorus flake has a regular rectangular shape and sharp raman peaks confirm its excellent crystallization properties.

Example 4

Taking 300mg of blocky amorphous red phosphorus, 20mg of powdery iodine simple substance and 20mg of powdery tin simple substance, uniformly mixing, then filling the mixture into one end of a quartz tube (with the length of 200mm, the outer diameter of 12mm and the inner diameter of 10mm), and placing a gallium nitride substrate with the length multiplied by the width of 10mm multiplied by 5mm at the other end. The quartz tube is vacuum sealed by a hydrogen flame vacuum tube sealing machine, and the vacuum degree is controlled to be 10^-2Pa. The quartz tube is horizontally placed in a tube furnace, heated to 550 ℃ within 3 hours and kept warm for 1After 0 hour, the temperature was reduced to room temperature within 8 hours. The quartz tube is broken, and the crystalline red phosphorus sheet is successfully prepared on the gallium nitride substrate.

Wherein, fig. 9 is an optical microscope photograph and a corresponding raman spectrum of the crystalline red phosphorus flake obtained in example 4, showing that the crystalline red phosphorus flake has a regular rectangular shape and a sharp raman spectrum peak confirms its excellent crystallization property.

Example 5

400mg of blocky amorphous red phosphorus, 20mg of blocky iodine simple substance and 20mg of powdery tin simple substance are taken, uniformly mixed and then put into one end of a quartz tube (the length is 200mm, the outer diameter is 12mm, and the inner diameter is 10mm), and a sapphire substrate with the length multiplied by the width of 9mm multiplied by 7mm is placed at the other end. The quartz tube is vacuum sealed by a hydrogen flame vacuum tube sealing machine, and the vacuum degree is controlled to be 10^-1Pa. The quartz tube is horizontally placed in a tube furnace, heated to 600 ℃ within 3 hours, kept warm for 15 hours, and then cooled to room temperature within 10 hours. And crushing the quartz tube, and successfully preparing the crystalline red phosphorus sheet on the sapphire substrate.

Wherein, fig. 10 is an optical microscope photograph and a corresponding raman spectrum of the crystalline red phosphorus flake obtained in example 5, showing that the crystalline red phosphorus flake has a regular rectangular shape and a sharp raman spectrum peak confirms its excellent crystallization property.

Example 6

500mg of blocky amorphous red phosphorus, 20mg of powdery iodine simple substance and 20mg of powdery tin simple substance are taken, uniformly mixed and then put into one end of a quartz tube (the length is 200mm, the outer diameter is 12mm, and the inner diameter is 10mm), and a fluorophlogopite substrate with the length multiplied by the width of 10mm multiplied by 8mm is placed at the other end. And (3) carrying out vacuum sealing on the quartz tube by using a hydrogen flame vacuum tube sealing machine, and controlling the vacuum degree to be 1 Pa. The quartz tube is horizontally placed in a tube furnace, heated to 650 ℃ within 3 hours, kept warm for 20 hours, and then cooled to room temperature within 10 hours. The quartz tube is broken, and the crystalline red phosphorus flake is successfully prepared on the fluorophlogopite substrate. Fig. 11 is an optical microscope photograph and corresponding raman spectrum of the crystalline red phosphorus flake obtained in example 6, showing that the crystalline red phosphorus flake has a regular rectangular shape and sharp raman peaks confirm its excellent crystallization properties.

Example 7

600mg of blocky amorphous red phosphorus, 20mg of powdery iodine simple substance and 20mg of powdery tin simple substance are taken, uniformly mixed and then put into one end of a quartz tube (the length is 200mm, the outer diameter is 12mm, and the inner diameter is 10mm), and a calcium sodium glass substrate with the length multiplied by the width of 10mm multiplied by 5mm is placed at the other end. The quartz tube is vacuum sealed by a hydrogen flame vacuum tube sealing machine, and the vacuum degree is controlled to be 10 Pa. The quartz tube is horizontally placed in a tube furnace, heated to 700 ℃ within 3 hours, kept warm for 10 hours, and then cooled to room temperature within 10 hours. The quartz tube is broken, and the crystalline red phosphorus sheet is successfully prepared on the calcium-sodium glass substrate. Fig. 12 is an optical microscope photograph and corresponding raman spectrum of the crystalline red phosphorus flake obtained in example 7, showing that the crystalline red phosphorus flake has a regular rectangular shape and sharp raman peaks confirm its excellent crystallization properties.

The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.

It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.