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CN-121976290-A - Preparation method of phosphorus single crystal and heterojunction

CN121976290ACN 121976290 ACN121976290 ACN 121976290ACN-121976290-A

Abstract

The application relates to the field of semiconductor technology and chemical preparation, and provides a preparation method of a phosphorus single crystal and a heterojunction. The method comprises the steps of sequentially carrying out first temperature rising treatment, first heat preservation treatment and first cooling treatment on raw material phosphorus, and carrying out second heat preservation treatment, second cooling treatment and second natural cooling treatment on a first cooling treatment product, so as to obtain a phosphorus single crystal or heterojunction, wherein the temperature difference between a raw material end and a product end is not more than 5 ℃. The method can selectively prepare the black phosphorus single crystal, the purple phosphorus single crystal or the black phosphorus-purple phosphorus heterojunction by using the same reaction system but different reaction parameters, has the advantages of simple process, lower energy consumption, high product purity or product quality, easily obtained raw materials, lower cost and the like, and can be widely applied to the fields of transistor channel materials, photoelectric detectors, photoelectric synapses and the like.

Inventors

  • XIE DAN
  • YANG SHUYUAN
  • WANG HUAIPENG
  • CAI SHENGXI
  • REN TIANLING

Assignees

  • 清华大学

Dates

Publication Date
20260505
Application Date
20251210

Claims (15)

  1. 1. A method for preparing a phosphorus single crystal and a heterojunction, comprising the steps of: Sequentially heating, maintaining and cooling the raw material phosphorus, and Subjecting the first temperature-reduced treated product to a second soak treatment and optionally a second temperature-reduced treatment and a second natural cooling treatment to obtain a phosphorus single crystal or heterojunction; wherein the temperature difference between the raw material end and the product end is not more than 5 ℃.
  2. 2. The method according to claim 1, wherein the temperature after the first cooling treatment is 500 ℃ to 550 ℃, the temperature during the second heat preservation treatment is 500 ℃ to 550 ℃, the time of the second heat preservation treatment is 2 hours to 10 hours, the cooling rate of the second cooling treatment is 40 ℃ per hour to 60 ℃ per hour, and the second natural cooling treatment is performed to room temperature after the cooling to 250 ℃ to 300 ℃ so as to obtain the black phosphorus single crystal.
  3. 3. The method according to claim 1, wherein the temperature after the first cooling treatment is 490 ℃ to 510 ℃, the temperature during the second heat preservation treatment is 490 ℃ to 510 ℃, the time of the second heat preservation treatment is 90 h to 150 h, and then the second natural cooling treatment is performed to room temperature, so as to obtain the purple phosphorus single crystal.
  4. 4. The method according to claim 1, wherein the temperature after the second cooling treatment is 490 ℃ to 510 ℃, the temperature during the second heat preservation treatment is 490 ℃ to 510 ℃, the time of the second heat preservation treatment is 10 hours to 50 hours, and then the second natural cooling treatment is performed to room temperature, so as to obtain the black phosphorus-purple phosphorus natural heterojunction.
  5. 5. The method of claim 1, wherein the feedstock phosphorus comprises amorphous red phosphorus.
  6. 6. The method of claim 1, wherein the preparation is performed under the catalysis of a transport agent; Optionally, the transport agent includes metallic tin and iodine.
  7. 7. The method according to claim 5 or 6, wherein the mass ratio of the amorphous red phosphorus, the metallic tin and the iodine in the preparation method is (10-20): 2-1): 1, preferably (15-20): 1.5-1): 1, more preferably (16-20): 1.4-1): 1.
  8. 8. The method of claim 1 or 6, wherein the feedstock phosphorus and the transport agent are both located at the feedstock end of the preparation process.
  9. 9. The process of claim 1, wherein the preparation process is carried out in a reaction vessel; Optionally, the reaction vessel comprises a vacuum ampoule.
  10. 10. The method according to claim 1 or 9, wherein the preparation is carried out by evacuating the reaction vessel to an internal pressure of less than 0.1 Pa before the preparation and sealing.
  11. 11. The method according to claim 1 or 9, characterized in that the distance between the raw end and the product end in the reaction vessel is 120 mm-180 mm, preferably 140 mm-160 mm.
  12. 12. The method according to claim 1, wherein the preparation method is performed by adjusting the temperature control conditions of the reaction vessel using a temperature gradient heating device; optionally, the temperature gradient heating device comprises a single temperature zone tube furnace.
  13. 13. The method according to claim 1, wherein the temperature-rising rate of the first temperature-rising treatment is 0.1 ℃ per minute to 10 ℃ per minute.
  14. 14. The method according to claim 1, wherein the temperature after the first temperature raising treatment is 550 ℃ to 700 ℃, the temperature of the first heat preserving treatment is 550 ℃ to 700 ℃, preferably 600 ℃ to 650 ℃, and the time of the first heat preserving treatment is 3h to 5 h.
  15. 15. The method of claim 1, wherein the first cooling treatment has a cooling rate of 0.1 ℃ per minute to 10 ℃ per minute.

Description

Preparation method of phosphorus single crystal and heterojunction Technical Field The application relates to the field of semiconductor technology and chemical preparation, in particular to a preparation method of a phosphorus single crystal and a heterojunction. Background Black phosphorus is an important two-dimensional semiconductor material, has the most wide application in phosphorus group simple substance, and has tunable inter-frequency band gap of up to 10 4cm2 V1s1 The hole mobility and anisotropic light transmission property are candidates with wide application prospect and excellent property in the novel photoelectric device. The purple phosphorus is another allotrope of phosphorus, has higher thermal decomposition temperature than black phosphorus, has more stable structure and environmental tolerance, has anisotropy and high carrier mobility, has wide band gap and excellent thermal stability, is easy to strip, and is a novel two-dimensional phosphorus semiconductor material with very good application prospect. The heterojunction of black phosphorus-purple phosphorus can construct a well-matched heterogeneous interface, a built-in electric field is generated to inhibit charge recombination, the problem that a black phosphorus single crystal has a fast photo-generated electron-hole pair recombination speed or a short plate with low photo-generated charge separation efficiency of the purple phosphorus single crystal is solved, meanwhile, the heterojunction can realize wider band gap customization, can adapt to the requirements of different photoelectric application scenes, and realizes more flexible band gap regulation capability than single black phosphorus or purple phosphorus single crystal. In the field of semiconductor material preparation, the preparation method for black phosphorus comprises a chemical vapor transport method, a chemical vapor deposition method and the like, but the chemical vapor input method needs a heating device controlled by a plurality of temperature areas to ensure parallel adjustment of a high temperature area and a low temperature area, has larger energy consumption and high equipment requirement, and the heterogeneous temperature difference can influence the nucleation and growth of crystals. The chemical vapor deposition method has high equipment requirement, needs to accurately control a plurality of parameters, has high energy consumption, and has poor thickness uniformity and high defect rate of the prepared black phosphorus film. The chemical vapor transport method for preparing the purple phosphorus has the problems of high energy consumption, high equipment requirement, low product purity, long reaction period and low preparation efficiency, and the chemical vapor deposition method for preparing the purple phosphorus also has a plurality of problems and is still in a research stage, and large-scale application is not realized yet. The preparation method of the black phosphorus-purple phosphorus heterojunction has the problems of complex process, high cost and the like, the black phosphorus and the purple phosphorus are used as raw materials for artificial preparation, extremely high requirements are imposed on the raw materials and the operation, and the prepared artificial heterojunction is easy to have the defects of uneven composite proportion of the black phosphorus and the purple phosphorus, non-tight interlayer combination, grain boundary or vacancy in part of the region and the like. Therefore, a method for preparing a heterojunction for black phosphorus single crystal, purple phosphorus single crystal or black phosphorus-purple phosphorus has yet to be developed and improved. Disclosure of Invention The present application aims to solve the problems of the prior art to some extent. Therefore, the application provides a preparation method of the phosphorus single crystal or the heterojunction, and the method can be used for selectively preparing the black phosphorus single crystal, the purple phosphorus single crystal or the black phosphorus-purple phosphorus heterojunction by using the same reaction system but under different reaction parameters, has the advantages of simple process, low energy consumption, high product purity or product quality, easily obtained raw materials, low cost and the like, and the prepared black phosphorus single crystal, purple phosphorus single crystal and the natural heterojunction of the two can be widely used in the fields of transistor channel materials, photoelectric detectors, photoelectric synapses and the like, thereby providing a foundation for the large-scale preparation of the follow-up phosphorus crystal materials. In one aspect of the application, the application provides a preparation method of a phosphorus single crystal or heterojunction, according to an embodiment of the application, the method comprises the steps of sequentially carrying out first temperature rising treatment, first heat preservation tr