Method for preparing orthorhombic crystal system black phosphorus single crystal

A technology of orthorhombic system and black phosphorus, which is applied in the field of optoelectronic semiconductor two-dimensional materials, can solve problems such as limited application, reduced purity, high temperature control and high requirements for red phosphorus raw materials, and achieve shortened reaction time, optimized reaction temperature, simplified The effect of heating process

Pending Publication Date: 2019-02-05
NANJING UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the highly toxic and pyrophoric properties of white phosphorus limit the application of these methods
In 2007, Nilges, Tom utilized Au, Sn and SnI 4 As a combined catalyst, red phosphorus is heated to 600°C in a vacuum environment to obtain black phosphorus, but the introduction of noble metals increases the production cost and the purity of black phosphorus decreases; CA105133009A, CA105460910 and CA105565289 also published improvements to this method , but the requirements for temperature control and red phosphorus raw materials are higher, and the catalyst selection has certain limitations (only limited to Au, Sn, I 2 or their mutual reaction products) and have not been reused; in 2010, Cheol-Min Park used a high-energy ball mill to synthesize a composite material of red phosphorus and black phosphorus, but the high-energy ball mill method is difficult to accurately control the pressure and temperature inside the reactor , affecting the controllability of the preparation process
Therefore, the more commonly used synthesis methods are high-pressure (10kbar) methods, but these methods have extremely high requirements for experimental instruments.

Method used

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  • Method for preparing orthorhombic crystal system black phosphorus single crystal
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  • Method for preparing orthorhombic crystal system black phosphorus single crystal

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preparation example Construction

[0016] The invention provides a method for preparing black phosphorus single crystal, wherein the method comprises: mixing phosphorus raw materials and a catalyst, placing them in a reactor, removing oxygen from the reactor and then closing the reactor, and preparing black phosphorus through programmed heating and cooling processes. The catalyst is a three-way catalyst of phosphorus, tin and iodine, including Sn 24 P 19.3 I 8 ;Exhausting oxygen can be achieved by vacuuming or exhausting air with inert gas; 1 Warming up to the sublimation temperature T 1 , after time t 2 down to the initial crystallization temperature T 2 , the elapsed time t 3 reaches the crystallization termination temperature T 3 . where time t 1 , t 2 Not limited, T 1 Greater than or equal to 450°C, preferably T 1 Greater than or equal to 535°C; time t 3 Relatively long, greater than 4 hours, T 3 Greater than or equal to 416°C, preferably, T 3 Greater than or equal to 450°C; T 3 The process o...

Embodiment 1

[0020] Catalyst preparation:

[0021] 12mmol Sn, 2mmol I 2 , 9.65mmol red phosphorus is added in the glass quartz tube, then the quartz tube (1cm inner diameter, 10cm long) is vacuumized, and when the vacuum degree reaches 1Pa, the quartz tube is packaged. Raise the temperature to 500°C, keep it for 72 hours, cool down to room temperature, grind the product evenly with an agate mortar and set aside.

[0022] Preparation of black phosphorus:

[0023] Take 40 mg of catalyst and 300 mg of red phosphorus, put them into a glass quartz tube, then vacuumize the quartz tube (inner diameter 1 cm, length 10 cm), and seal the quartz tube when the vacuum reaches 1 Pa. React according to the following heating procedure: room temperature-60min-650°C-60min-650°C-480min-500°C-room temperature, the conversion rate of the obtained black phosphorus is 91%, and it is block.

Embodiment 2

[0025] Catalyst preparation:

[0026] 12mmol Sn, 2mmol I 2 , 9.65mmol red phosphorus is added in the glass quartz tube, then the quartz tube (1cm inner diameter, 10cm long) is vacuumized, and when the vacuum degree reaches 1Pa, the quartz tube is packaged. Raise the temperature to 500°C, keep it for 72 hours, cool down to room temperature, grind the product evenly with an agate mortar and set aside.

[0027] Preparation of black phosphorus:

[0028] Take 20 mg of catalyst and 300 mg of red phosphorus, put them into a glass quartz tube, then vacuumize the quartz tube (inner diameter 1 cm, length 10 cm), and seal the quartz tube when the vacuum reaches 1 Pa. React according to the following heating procedure: room temperature-60min-650°C-60min-650°C-480min-500°C-room temperature, the conversion rate of the obtained black phosphorus is 99%, and it is block.

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Abstract

The invention relates to a preparation method of an orthorhombic crystal system black phosphorus single crystal. The preparation method comprises the following specific steps: mixing a ternary phosphorus-tin-iodine catalyst and red phosphorus; putting a mixture into a reactor; after discharging air and sealing, preparing black phosphorus through programmed temperature rising and temperature reduction. Mass production of the ternary phosphorus-tin-iodine catalyst can be realized in advance; the black phosphorus obtained by the catalyst has good crystallization performance and high purity; the yield reaches 99 percent and the catalyst can be repeatedly utilized; extremely great convenience is provide for subsequent application and development of the black phosphorus.

Description

technical field [0001] The invention belongs to the field of photoelectric semiconductor two-dimensional materials, and in particular relates to a preparation method of orthorhombic black phosphorus material. Background technique [0002] The rapid development of the semiconductor electronics industry has put forward higher requirements for the development of materials. Graphene has ushered in the era of two-dimensional materials, with its ultra-high carrier mobility (15000cm 2 / V*s) and other superior physical and chemical properties make it considered the most likely material to replace silicon, but the zero band gap limit the development of graphene. Similar to graphene, black phosphorus is a single-element two-dimensional material with van der Waals force between layers, and flake crystals with different layers can be obtained by exfoliation. Black phosphorus not only has graphene-like ultra-high carrier mobility (200~50000cm 2 / V*s), and its bandgap can be adjusted b...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C01B25/02C30B23/00C30B29/02
CPCC30B23/00C30B29/02C01B25/02C01P2002/72C01P2002/82
Inventor 闾敏王东亚谢小吉黄岭黄维
Owner NANJING UNIV OF TECH
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