阅读说明：本技术 一种黑磷单晶片的制备方法 (Preparation method of black phosphorus single crystal wafer ) 是由 喻学锋 喻彬璐 王佳宏 于 2020-03-18 设计创作，主要内容包括：本发明公开一种黑磷单晶片的制备方法,该方法涉及大尺寸二维单晶材料生长方面。制备方法是将磷源、催化剂按照一定质量比例加入密封反应器中,再进行烧结,最终得到大尺寸黑磷单晶片。本方法获得的黑磷单晶片水平尺寸可达厘米级,片状结构完整性高,且成功实现单晶片之间分散成核生长,不互相粘连,能够获得高质量无损单晶黑磷单晶片,有利于下游应用。(The invention discloses a preparation method of a black phosphorus single crystal wafer, and relates to the growth aspect of large-size two-dimensional single crystal materials. The preparation method comprises the steps of adding a phosphorus source and a catalyst into a sealed reactor according to a certain mass ratio, and sintering to finally obtain the large-size black phosphorus single crystal wafer. The black phosphorus single crystal wafer obtained by the method has the horizontal dimension reaching centimeter level, the integrity of the sheet structure is high, the dispersion nucleation growth between the single crystal wafers is successfully realized, the single crystal wafers are not mutually adhered, the high-quality lossless single crystal black phosphorus single crystal wafer can be obtained, and the method is favorable for downstream application.)

1. A preparation method of a black phosphorus single crystal wafer is characterized by comprising two steps: preparing a catalyst and reacting the phosphorus source with the catalyst to obtain the black phosphorus single crystal wafer.

2. The method for preparing the black phosphorus single crystal wafer according to claim 1, wherein the catalyst is a SnIP ternary compound, and the catalyst is prepared by the following steps: weighing the reaction raw materials according to the stoichiometric ratio of the SnIP ternary compound, fully mixing the reaction raw materials uniformly, adding the mixture into a quartz tube, vacuumizing and sealing the quartz tube, and placing the quartz tube in a muffle furnace to process for 2 to 96 hours at the temperature of between 300 and 520 ℃ to obtain the SnIP ternary compound.

3. The method for preparing the black phosphorus single crystal wafer as claimed in claim 2, wherein the SnIP ternary compound is prepared from elemental tin, elemental phosphorus, iodine, stannous iodide or stannic tetraiodide.

4. The method for preparing the black phosphorus single crystal wafer as claimed in claim 1, wherein the reaction of the phosphorus source with the catalyst comprises the following specific steps:

1) adding a phosphorus source and a catalyst into a sealed reactor according to a certain mass ratio;

2) and placing the reactor in a heating device to sinter for a certain time at a certain temperature to finally obtain the black phosphorus single crystal wafer.

5. The method for preparing the black phosphorus single crystal wafer according to claim 4, wherein the phosphorus source in the step 1) is red phosphorus or yellow phosphorus, and the raw material state is preferably granular or block-shaped.

6. The method for preparing the black phosphorus single crystal wafer according to claim 4, wherein the mass ratio of the phosphorus source to the catalyst is (40-0.5): 1.

7. The method for preparing the black phosphorus single crystal wafer according to claim 4, wherein the sealed reactor is a ceramic tube, a stainless steel tube or a fused quartz tube.

8. The method for preparing a black phosphorus single crystal wafer according to claim 4, wherein the heating apparatus in the step 2) is one of a single-temperature-zone tube furnace, a multi-temperature-zone (dual-temperature-zone and higher) tube furnace, a muffle furnace, a box furnace, a microwave furnace and a single crystal furnace.

9. The method for preparing the black phosphorus single crystal wafer according to claim 4, wherein the sintering temperature is 420 to 550 ℃ and the sintering time is 2 to 120 hours.

10. A black phosphorus single crystal wafer obtained by the method for preparing a black phosphorus single crystal wafer according to any one of claims 1 to 9, which is applicable to flexible devices, sensors, microelectrodes, photoelectrocatalysis, batteries and field effect transistors.

Technical Field

The invention relates to growth of a novel two-dimensional single crystal material, in particular to a preparation method of a large-size high-quality black phosphorus single crystal wafer.

Background

Large-size single crystal materials have always played a significant role in the development of national economy. With the increase of the size of single crystal materials, the development of an industry is rapidly promoted, wherein the most prominent material is silicon, and the single crystal silicon expands from four inches before to eighteen inches nowadays, thereby greatly continuing the explosive development of integrated circuits. The black phosphorus is used as a novel two-dimensional semiconductor material, has excellent performance in a field effect transistor due to high carrier mobility and on-off ratio, and has great application prospect in the fields of photoelectrocatalysis, energy storage, flexible devices, biological agents and the like. The allotropes of various phosphorus are unstable in atmospheric environment, and individual substances are extremely toxic, while black phosphorus shows the characteristics of stability and no toxicity at room temperature and is easy to process, so the development prospect of black phosphorus is very good in the scientific research and industrial fields.

The reported black phosphorus preparation methods such as a high-pressure method, a bismuth recrystallization method and a mechanical ball milling method can not obtain large-size black phosphorus single crystal wafers. Meanwhile, red phosphorus, simple substance tin and tin tetraiodide are used as reaction raw materials in a classical chemical vapor transport method, the growth form of black phosphorus crystals cannot be effectively regulated, the obtained black phosphorus crystals are often gathered together and grow into clusters, and high-quality large-size black phosphorus single crystal wafers cannot be obtained.

As a new semiconductor two-dimensional material, the black phosphorus has excellent performance in field effect transistors and is considered as a chip substrate with great potential by the scientific research community and the industrial community. However, the known industrial chip substrate, monocrystalline silicon, has reached eighteen inches at most, and no related patent documents report a method capable of effectively regulating and controlling the growth of black phosphorus crystal into a sheet structure, the growth of black phosphorus single crystal wafer into centimeter-level and wafer-level is only a vision at present, and further promotion of the practicability of black phosphorus in the semiconductor industry is required, and the development of a method for growing large-size black phosphorus single crystal wafer is not slow.

Disclosure of Invention

The invention aims to provide a preparation method for effectively regulating and controlling black phosphorus to grow into a specific sheet structure. The nucleation growth mode of the black phosphorus single crystal wafer is obviously different from that of the black phosphorus crystal prepared by the classical chemical vapor transport method, the nucleation points of the black phosphorus single crystal wafer are concentrated, and the reaction potential barrier under the action of a new catalyst is greatly reduced, so that the large-size black phosphorus single crystal wafer can be obtained. The nucleation points of the black phosphorus crystal prepared by the classical chemical vapor transport method are dispersed, and the shape of the nucleation points is often formed into clusters or clusters. The black phosphorus single crystal wafer obtained by the method has uniform appearance and horizontal size reaching centimeter level.

The invention provides a preparation method of a black phosphorus single crystal wafer, which comprises the following two steps: preparing a catalyst and reacting the phosphorus source with the catalyst to obtain the black phosphorus single crystal wafer.

Specifically, the catalyst is a SnIP ternary compound, and the preparation of the catalyst is as follows: weighing the reaction raw materials according to the stoichiometric ratio of the SnIP ternary compound, fully mixing the reaction raw materials uniformly, adding the mixture into a quartz tube, vacuumizing and sealing the quartz tube, and placing the quartz tube in a muffle furnace to process for 2 to 96 hours at the temperature of between 300 and 520 ℃ to obtain the SnIP ternary compound.

Furthermore, the preparation raw materials of the SnIP ternary compound are the combination of elementary substance tin, elementary substance phosphorus, elementary substance iodine, stannous iodide or stannic tetraiodide.

Specifically, the reaction of the phosphorus source and the catalyst comprises the following specific steps:

1) adding a phosphorus source and a catalyst into a sealed reactor according to a certain mass ratio;

2) and placing the reactor in a heating device to sinter for a certain time at a certain temperature to finally obtain the black phosphorus single crystal wafer.

Specifically, the phosphorus source in the step 1) is red phosphorus or yellow phosphorus, and the raw material state is preferably granular or blocky.

Specifically, the mass ratio of the phosphorus source to the catalyst is (40-0.5): 1.

Specifically, the sealed reactor is a ceramic tube, a stainless steel tube or a fused quartz tube.

Specifically, the heating device in the step 2) is one of a single-temperature-zone tube furnace, a multi-temperature-zone (dual-temperature-zone and above) tube furnace, a muffle furnace, a box furnace, a microwave furnace or a single crystal furnace.

Specifically, the sintering temperature is 420-550 ℃, and the sintering time is 2-120 h.

The black phosphorus single crystal wafer obtained by the preparation method of the black phosphorus single crystal wafer can be applied to flexible devices, sensors, microelectrodes, photoelectrocatalysis, batteries and crystal field effect transistors.

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

(1) the invention can control the growth of black phosphorus into a sheet structure with large size and specific shape, and the structure is not reported in documents.

(2) The grown black phosphorus single crystal wafer is dispersed and nucleated, is not adhered to each other, and is favorable for obtaining high-quality lossless single crystals; meanwhile, the horizontal dimension of the black phosphorus single crystal wafer can reach centimeter level, and one complete black phosphorus single crystal wafer can be stripped into a plurality of thinner single crystal wafers, so that the method has great economic value.

(3) The preparation method is simple, has low requirements on equipment, has wide and rich raw material sources and low price, and has industrial production potential.

Drawings

FIG. 1 is an XRD pattern of the SnIP catalyst in example 1 of the present invention;

FIG. 2 is an optical photograph of a black phosphorus single crystal wafer in example 2 of the present invention;

FIG. 3 is an XRD pattern of a black phosphorus single crystal wafer in example 2 of the present invention.

FIG. 4 is a SEM image of a cross-section of a black phosphorus single crystal wafer in example 2 of the present invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The application of the principles of the present invention will now be described in further detail with reference to specific embodiments.

Example 1

Preparation of SnIP catalyst: 0.31g of red phosphorus powder, 1.18g of tin powder and 1.26g of iodine simple substance are respectively weighed in a glove box, the three raw materials are fully and uniformly mixed, added into a quartz tube with the length of 11cm and the inner diameter of 11mm, the quartz tube is sealed by an oxyhydrogen machine after being vacuumized, and placed in a muffle furnace to react for 96 hours at the temperature of 300 ℃, and the XRD results of the obtained SnIP substances are respectively shown in figure 1.

Example 2

60mg of the SnIP substance obtained in example 1 and 2.4g of red phosphorus particles were charged into a quartz tube having a length of 10cm and an inner diameter of 16mm, and the quartz tube was sealed with an oxyhydrogen gas after evacuation. And (3) placing the sealed quartz tube in a double-temperature-zone tube furnace, wherein the temperature of the raw material end (left end) is 510 ℃, the temperature of the right end is 490 ℃, the reaction time is 24 hours, obtaining the black phosphorus single crystal wafer on the tube wall after cooling, and respectively showing an optical photographic diagram and an XRD result as shown in figures 2 and 3. It is apparent from fig. 2 that the size of the black phosphorus single crystal wafer can reach the centimeter level. The XRD result in FIG. 3 shows that the obtained black phosphorus is really black phosphorus, and the peak shape is sharp and the intensity is high, which fully shows that the crystallinity of the black phosphorus single crystal wafer is high. As can be seen from the SEM cross section of the black phosphorus single crystal wafer in FIG. 4, the single crystal wafer has a certain thickness and a multi-layer structure, and can be peeled into a plurality of pieces.

Example 3

Preparation of SnIP catalyst: 0.31g of red phosphorus powder, 0.60g of tin powder and 1.86g of stannous iodide are respectively weighed in a glove box, the three raw materials are fully and uniformly mixed, added into a quartz tube with the length of 12cm and the inner diameter of 18mm, the quartz tube is sealed by an oxyhydrogen machine after being vacuumized, and the quartz tube is placed in a muffle furnace to react for 2 hours at 520 ℃ to obtain the SnIP substance.

Example 4

150mg of the SnIP substance obtained in example 3 and 3g of red phosphorus were charged in a quartz tube having a length of 20cm and an inner diameter of 16mm, and the quartz tube was sealed with an oxyhydrogen gas after evacuation. And (3) placing the sealed quartz tube in a box furnace, reacting for 2 hours at the temperature of 550 ℃, and cooling to obtain the black phosphorus single crystal wafer on the tube wall.

Example 5

Preparation of SnIP catalyst: 0.31g of red phosphorus powder, 0.885g of tin granules and 1.57g of tin tetraiodide are respectively weighed in a glove box, the three raw materials are fully and uniformly mixed, added into a quartz tube with the length of 10cm and the inner diameter of 11mm, the quartz tube is sealed by an oxyhydrogen machine after being vacuumized, and the quartz tube is placed in a muffle furnace to react for 40 hours at the temperature of 470 ℃ to obtain the SnIP substance.

Example 6

200mg of the SnIP substance obtained in example 5 and 100mg of yellow phosphorus particles were charged into a stainless steel tube having a length of 18cm and an inner diameter of 16 mm. And (3) placing the sealed stainless steel reactor in a muffle furnace, wherein the temperature of a raw material end is 420 ℃, the reaction time is 35 hours, and obtaining the black phosphorus single crystal wafer on the tube wall after cooling.