Black phosphorus controllable transportation preparation method based on thermal field induced convection
By combining a multi-temperature zone well furnace and a sealed metal reactor, and utilizing the temperature field-induced convection effect, efficient and uniform preparation of black phosphorus was achieved, solving the problems of low yield and poor controllability in existing technologies, and laying the foundation for the industrialization of black phosphorus.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- HUBEI XINGFA CHEM GRP CO LTD
- Filing Date
- 2025-12-18
- Publication Date
- 2026-04-14
AI Technical Summary
Existing black phosphorus preparation processes suffer from low yield, unstable quality, and poor controllability. In particular, uneven temperature distribution in traditional tube furnaces leads to the generation of byproducts, making it difficult to achieve large-scale preparation.
By combining a multi-temperature zone well furnace and a sealed metal reactor with internal and external heating sources, a precise temperature field is constructed and the convection effect induced by the temperature field is utilized to achieve efficient heat treatment of red phosphorus, mineralizing agent and transport agent, and prepare high-quality black phosphorus crystals.
By precisely controlling the temperature field and utilizing directional convection effects, the uniformity and purity of black phosphorus crystals were improved, significantly increasing the yield and providing a feasible path for the industrialization of black phosphorus from the laboratory.
Smart Images
Figure CN121849869A_ABST
Abstract
Description
Technical Field
[0001] This application relates to the field of novel optoelectronic semiconductor material preparation technology, and in particular to a method for preparing black phosphorus based on temperature field-induced convection controllable transport. Background Technology
[0002] Two-dimensional black phosphorus, as a novel semiconductor material with an adjustable direct bandgap (0.3 eV ~ 2.0 eV) based on the number of layers, high carrier mobility, and significant in-plane anisotropy, has shown great application potential in nanoelectronics, optoelectronic devices, and other fields. However, due to limitations in current black phosphorus preparation processes, large-scale industrial production still faces challenges.
[0003] Currently, chemical vapor transport (CVT) is one of the most mainstream methods for preparing black phosphorus. Its core principle is to convert precursors such as red phosphorus into black phosphorus crystals through gas-phase transport reactions at a specific temperature field. However, existing CVT technologies face several critical technical bottlenecks: the limited temperature range of traditional tubular furnaces makes it difficult to construct a precise, stable, and complex temperature gradient within the reactor that conforms to the nucleation and growth kinetics of black phosphorus. Slight fluctuations or inhomogeneities in the temperature field can lead to the formation of byproducts (such as white phosphorus and fibrous phosphorus), significantly reducing the purity and crystal quality of black phosphorus. Furthermore, the reaction relies on a simple radial or axial temperature gradient provided by the furnace body, lacking proactive and precise means to control the transport path and rate of phosphorus vapor. This results in low reactant utilization, random crystal growth locations, and non-uniform crystal sizes, making it difficult to achieve controllable black phosphorus preparation. Simultaneously, traditional black phosphorus preparation methods require high-performance reaction vessels and have small reaction chambers, further hindering the large-scale preparation of black phosphorus.
[0004] Therefore, there is an urgent need in this field for a novel preparation system and method that can accurately construct the internal temperature field, achieve active control of convection transport, and simplify the complexity of the preparation process, in order to solve the problems of low yield, unstable quality, and poor controllability in the preparation of black phosphorus in the existing technology. Summary of the Invention
[0005] This application provides a method for preparing black phosphorus based on temperature-induced convection with controlled transport, in order to solve the problems of low yield, unstable quality, and poor controllability in the preparation of black phosphorus in the prior art.
[0006] To address the aforementioned technical problems, this application provides a method for preparing black phosphorus based on temperature-induced convection. This method employs a black phosphorus preparation system based on temperature-induced convection to prepare black phosphorus. The preparation system includes a multi-temperature zone well furnace, a sealed metal reactor, and a heating device disposed within the sealed metal reactor. The method comprises: using red phosphorus, a mineralizing agent, and a transporting agent as raw materials, feeding them into the sealed metal reactor, and performing multi-temperature zone heat treatment in the multi-temperature zone well furnace under dual internal and external heating sources to prepare black phosphorus.
[0007] In some exemplary embodiments, the mass ratio of red phosphorus, mineralizer and transporter is (100~500):(1~100):(1~100).
[0008] In some exemplary embodiments, the multi-temperature zone pit furnace includes three independently temperature-controlled zones: a bottom zone, a lower zone, and an upper zone; the multi-temperature zone pit furnace is equipped with insulation baffles to ensure the temperature field and maintain insulation.
[0009] In some exemplary embodiments, the sealed metal reactor is made of 310s stainless steel and adopts a single flange cover sealing design; the ratio of the height to the diameter of the cavity of the sealed metal reactor is 1:(0.3~3).
[0010] In some exemplary embodiments, the heating device is fixed to the flange cover of the sealed metal reactor, and the heating device has an integrated independent temperature-sensing thermocouple.
[0011] In some exemplary embodiments, when a multi-temperature zone well furnace is used to perform multi-temperature zone heat treatment under dual internal and external heating sources, the external heating source heats the furnace from room temperature to 500~600°C for 60~240 min; the holding time is 1000~3000 min; and then the furnace is cooled to room temperature for 60~1000 min.
[0012] In some exemplary embodiments, when a multi-temperature zone well furnace is used to perform multi-temperature zone heat treatment under dual internal and external heating sources, the internal heating source heats the furnace from room temperature to 500~600°C for 60~240 min, holds the furnace for 1000~3000 min, and then cools the furnace to room temperature for 60~1000 min.
[0013] In some exemplary embodiments, the red phosphorus is in the form of powder or granules.
[0014] In some exemplary embodiments, the mineralizer comprises one or more of tin, bismuth, and antimony; the mineralizer is in the form of powder or granules.
[0015] In some exemplary embodiments, the transport agent comprises one or more of iodine, bismuth iodide, antimony iodide, tin tetraiodide, or stannous iodide; the transport agent is in particulate or powder form.
[0016] The technical solution provided in this application has at least the following advantages: This application provides a method for preparing black phosphorus based on temperature-induced convection controllable transport. The method uses a black phosphorus preparation system based on temperature-induced convection controllable transport to prepare black phosphorus. The preparation system includes a multi-temperature zone well furnace, a sealed metal reactor, and a heating device disposed within the sealed metal reactor. The method includes: using red phosphorus, a mineralizing agent, and a transporting agent as raw materials, feeding them into the sealed metal reactor, and using a multi-temperature zone well furnace to perform internal and external multi-temperature zone heat treatment under dual internal and external heating sources to prepare black phosphorus.
[0017] This application provides a method for the controlled transport of black phosphorus based on temperature-induced convection. This method employs a preparation system primarily composed of a multi-temperature zone well furnace, a metal reactor, and a built-in heating device. These three components work together to form a composite heating and temperature control system. Through a composite heating mode combining external field (multi-temperature zone well furnace) and internal source (built-in heater), along with insulation technology, an extremely precise and stable complex temperature field can be constructed within the reactor, perfectly matching the thermodynamic requirements of different growth stages of black phosphorus. Simultaneously, the active convection effect induced by the temperature field drives mass transport, resulting in faster and more directional transport compared to traditional diffusion mechanisms. Combined with a reactor design of a specific aspect ratio, "short-distance, rapid, and directional" transport of phosphorus vapor is achieved, significantly improving reaction efficiency and product uniformity. Precise temperature field control and efficient convective transport effectively suppress the formation of amorphous phosphorus or other phosphorus allotropes, promoting uniform nucleation and preferential growth of black phosphorus crystals, thereby obtaining two-dimensional black phosphorus materials with complete crystal morphology, uniform size, and higher purity. Furthermore, this system employs a high-temperature resistant, corrosion-resistant, and high-strength 310s stainless steel metal reactor, which is larger in size, significantly improving the synthesis quality and yield of black phosphorus. This technical solution provides a compact and highly feasible reliable path to solve the core bottleneck in the process of moving black phosphorus from the laboratory to industrialization, and its technical characteristics significantly meet the needs of large-scale manufacturing. Attached Figure Description
[0018] One or more embodiments are illustrated by way of example with reference to the accompanying drawings. These illustrations do not constitute a limitation on the embodiments, and unless otherwise stated, the figures in the drawings are not to be limited by scale.
[0019] Figure 1This is a schematic diagram of the black phosphorus controllable transport preparation system based on temperature field-induced convection designed in Example 1 of this application.
[0020] Figure 2 This is a design drawing of the metal reactor and built-in heating device designed in Embodiment 1 of this application.
[0021] Figure 3 This is a photograph of the black phosphorus obtained in Example 1 of this application.
[0022] Figure 4 This is the X-ray diffraction pattern of black phosphorus obtained in Example 1 of this application.
[0023] Figure 5 This is the Raman spectrum of black phosphorus obtained in Example 1 of this application.
[0024] Figure 6 This is a photograph of the black phosphorus obtained in Example 2 of this application. Detailed Implementation
[0025] As can be seen from the background technology, the existing technology has problems such as low yield, unstable quality and poor controllability in black phosphorus preparation.
[0026] To address the aforementioned technical problems, this application provides a method for the controlled transport preparation of black phosphorus based on temperature-induced convection. This method employs a black phosphorus preparation system based on temperature-induced convection to prepare black phosphorus. The preparation system includes a multi-temperature zone well furnace, a sealed metal reactor, and a heating device disposed within the sealed metal reactor. The method comprises: using red phosphorus, a mineralizing agent, and a transporting agent as raw materials, adding them to the sealed metal reactor, and performing multi-temperature zone heat treatment in the multi-temperature zone well furnace under dual internal and external heating sources to prepare black phosphorus. This preparation system aims to actively construct a stable and controllable dynamic temperature field within the reaction chamber through a unique configuration of synergistic heating inside and outside the reactor. Utilizing the resulting directional convection effect, it precisely drives the transport and deposition of phosphorus vapor, ultimately achieving the controllable preparation of high-quality, high-yield black phosphorus crystals.
[0027] The embodiments of this application will now be described in detail with reference to the accompanying drawings. However, those skilled in the art will understand that many technical details have been provided in the embodiments of this application to facilitate a better understanding of the application. However, the technical solutions claimed in this application can be implemented even without these technical details and various variations and modifications based on the following embodiments.
[0028] See Figure 1This application provides a method for preparing black phosphorus based on temperature-induced convection controllable transport. The method employs a black phosphorus preparation system based on temperature-induced convection controllable transport. The preparation system includes a multi-temperature zone well furnace 2, a sealed metal reactor 3, and a heating device 5 disposed within the sealed metal reactor 3. The multi-temperature zone well furnace 2 is equipped with an insulation baffle 1 to ensure the temperature field and maintain the temperature. The method includes: using red phosphorus, a mineralizing agent, and a transporting agent as raw materials, adding them to the sealed metal reactor 3, and performing multi-temperature zone heat treatment in the multi-temperature zone well furnace 2 under dual internal and external heating sources to achieve black phosphorus preparation.
[0029] like Figure 1 As shown, the preparation system mainly consists of three parts: a multi-temperature zone well furnace 2, a sealed metal reactor 3, and a heating device 5. The multi-temperature zone well furnace 2 provides the basic temperature field, the sealed metal reactor 3 serves as the core reaction chamber, and the heating device 5 acts as a local heat source, forming a composite heating mode with the furnace body. By controlling the temperature distribution of this composite temperature field, a precise temperature gradient field is established inside the sealed metal reactor 3, and the resulting thermal convection effect is used to directionally drive the transport process of the reaction precursors. The method includes the following steps: using red phosphorus, a mineralizing agent, and a transporting agent as preparation raw materials, they are added to the sealed metal reactor 3, and high-quality black phosphorus is prepared under certain high-temperature heat treatment conditions through the multi-temperature zone well furnace 2. This system achieves precise control of the nucleation and growth stages in the black phosphorus synthesis process, effectively solving the problems of uneven temperature field distribution and uncontrollable reaction paths in traditional methods, significantly improving the crystallization quality and preparation efficiency of black phosphorus crystals, and providing a reliable technical solution for the large-scale controllable preparation of black phosphorus.
[0030] In some embodiments, the mass ratio of red phosphorus, mineralizer and transporter is (100~500):(1~100):(1~100).
[0031] In some embodiments, the multi-temperature zone well furnace 2 includes three independently temperature-controlled zones, namely the bottom temperature zone, the lower temperature zone, and the upper temperature zone; the multi-temperature zone well furnace 2 is provided with a heat-insulating baffle 1 to ensure the temperature field and heat preservation.
[0032] In some embodiments, the sealed metal reactor 3 in the preparation system is made of stainless steel, preferably grade 310s, with a length-to-diameter ratio of 1:(0.3~3), preferably 1:1.
[0033] In some embodiments, the heating device 5 is fixed to the flange cover of the sealed metal reactor 3, and the heating device 5 has an independent temperature sensing thermocouple built in.
[0034] In some embodiments, when a multi-temperature zone well furnace is used for heat treatment in both internal and external heating sources, the external heating source heats the furnace from room temperature to 500~600°C for 60~240 min; the holding time is 1000~3000 min; and then the furnace is cooled to room temperature for 60~1000 min.
[0035] In some embodiments, when a multi-temperature zone well furnace is used for heat treatment in both internal and external heating sources, the internal heating source heats the furnace from room temperature to 500~600°C for 60~240 min, holds the temperature for 1000~3000 min, and then cools the furnace to room temperature for 60~1000 min.
[0036] In some embodiments, red phosphorus is in the form of powder or granules.
[0037] In some embodiments, the mineralizer comprises one or more of tin, bismuth, and antimony; the mineralizer is in the form of powder or granules.
[0038] In some embodiments, the transport agent comprises one or more of iodine, bismuth iodide, antimony iodide, tin tetraiodide, or stannous iodide; the transport agent is in particulate or powder form.
[0039] The following detailed embodiments illustrate the controllable transport method for black phosphorus preparation based on temperature-induced convection provided in this application.
[0040] Unless otherwise specified, the experimental methods used in the embodiments of this application are all conventional methods.
[0041] In the following examples and comparative examples, unless otherwise specified, all raw materials can be obtained commercially or prepared by conventional methods.
[0042] Example 1 like Figure 1 In this paper, a controllable transport preparation system for black phosphorus based on temperature-induced convection is disclosed. The preparation system includes a multi-temperature zone well furnace 2, a sealed metal reactor 3, and a reactor-embedded heating device 5. The design diagram of the sealed metal reactor 3 is shown in the figure below. Figure 2 As shown, the single flange cover design has a heater and matching thermocouple 4 installed on the cover; The reactor is entirely within several different temperature zones of the three-zone well furnace, and a preset gradient temperature field can be constructed for the reactor by setting parameters. The specific steps for preparing black phosphorus crystals using the above-described preparation system are as follows: Red phosphorus, tin, and iodine are mixed in a mass ratio of 100:10:5 and added to a reactor. The reactor is then sealed directly without ventilation. The reactor is placed at the bottom of a heating furnace, and an insulation layer is added before heating begins. The external temperature field is raised to 530 / 510 / 500℃ at a rate of 5℃ / min, held for 1440 min, and then cooled to room temperature for 240 min. Simultaneously, the internal temperature field is raised to 550℃ at a rate of 5℃ / min, held for 1440 min, and then cooled to room temperature for 240 min. This process yields cyclic black phosphorus crystals within the reactor. Figure 3 As shown.
[0043] Figure 4 The X-ray diffraction pattern of the black phosphorus crystals prepared in Example 1 of this application is shown. Compared with the corresponding standard card, there are no extra impurity peaks, and the characteristic peaks at positions (020), (040), (060), and (080) are sharp and have high intensity, which proves that the black phosphorus crystal material has high crystallinity and good quality.
[0044] Figure 5 The image shows the Raman spectrum of the black phosphorus crystals prepared in Example 1 of this application. The three distinct and sharp characteristic peaks demonstrate its high purity and high crystal quality.
[0045] Example 2 This embodiment uses the same reaction system as Example 1. The black phosphorus preparation process in this embodiment is as follows: Red phosphorus, bismuth, and iodine are mixed in a mass ratio of 100:30:10 and added to a metal reactor. No aeration is required; the reactor is then sealed directly. The reactor is placed at the bottom of a heating furnace, and an insulation layer is placed inside. Heating is then initiated. The external temperature field is raised to 480℃~525℃ at a rate of 5℃ / min, held for 1440 min, and cooled to room temperature for 240 min. Simultaneously, the internal temperature field is raised to 540℃ at a rate of 5℃ / min, held for 1440 min, and cooled to room temperature for 240 min. Ring-shaped black phosphorus crystals are then obtained within the reactor. Figure 6 As shown.
[0046] Comparative Example 1 Red phosphorus, tin, and iodine were mixed evenly in a mass ratio of 600:1:1 and added to a reactor, which was then sealed. The reactor was placed at the bottom of a heating furnace, an insulation layer was placed on top, and heating was then initiated. The temperature was increased to 470℃~520℃ at a rate of 5℃ / min, held at that temperature for 1440min, and then cooled to room temperature for 240min. The built-in heating device was not activated. Upon opening the lid, no obvious black phosphorus was produced; only clumps of red phosphorus were present.
[0047] Comparative Example 2 Red phosphorus, bismuth, and bismuth iodide were mixed evenly in a mass ratio of 100:100:100 and added to a reactor, which was then sealed. The reactor was placed at the bottom of a heating furnace, an insulation layer was placed on top, and heating was then initiated. The temperature was increased to 490℃~530℃ at a rate of 5℃ / min, held for 1440min, and then cooled to room temperature for 240min. The built-in heating device was not activated. Upon opening the lid, no obvious black phosphorus was produced; only clumps of red phosphorus were present.
[0048] In summary, the temperature-induced convection-based controllable transport preparation system and method for black phosphorus employed in this application utilizes a unique configuration of coordinated heating inside and outside the reactor to actively construct a stable and controllable dynamic temperature field within the reaction chamber. The resulting directional convection effect precisely drives the transport and deposition of phosphorus vapor, ultimately achieving the controllable preparation of high-quality, high-yield black phosphorus crystals. The temperature-induced convection transport system constructed in this invention features a simple process route, outstanding efficiency, and excellent potential for large-scale scaling, providing a highly feasible technical solution for overcoming the bottlenecks in the industrial application of black phosphorus.
[0049] This application provides a method for preparing black phosphorus based on temperature-induced convection controllable transport. The method uses a black phosphorus preparation system based on temperature-induced convection controllable transport to prepare black phosphorus. The preparation system includes a multi-temperature zone well furnace, a sealed metal reactor, and a heating device disposed within the sealed metal reactor. The method includes: using red phosphorus, a mineralizing agent, and a transporting agent as raw materials, feeding them into the sealed metal reactor, and using a multi-temperature zone well furnace to perform internal and external multi-temperature zone heat treatment under dual internal and external heating sources to prepare black phosphorus.
[0050] Based on the above technical solutions, this application provides a method for the controllable transport of black phosphorus based on temperature-induced convection. This method is implemented using a preparation system, which mainly consists of three parts: a multi-temperature zone well furnace, a metal reactor, and a built-in heating device. These three components work together to form a composite heating and temperature control system. Through a composite heating mode combining external field (multi-temperature zone well furnace) and internal source (built-in heater), combined with insulation technology, an extremely precise and stable complex temperature field can be constructed inside the reactor, perfectly matching the thermodynamic requirements of different growth stages of black phosphorus. Simultaneously, the active convection effect induced by the temperature field drives mass transport, resulting in a faster transport rate and stronger directionality compared to traditional diffusion mechanisms. Combined with a reactor design with a specific aspect ratio, "short-distance, rapid, and directional" transport of phosphorus vapor is achieved, significantly improving reaction efficiency and product uniformity. Precise temperature field control and efficient convective transport effectively suppress the formation of amorphous phosphorus or other phosphorus allotropes, promoting uniform nucleation and preferential growth of black phosphorus crystals, thereby obtaining two-dimensional black phosphorus materials with complete crystal morphology, uniform size, and higher purity. Furthermore, this system employs a high-temperature resistant, corrosion-resistant, and high-strength 310s stainless steel metal reactor, which is larger in size, significantly improving the synthesis quality and yield of black phosphorus. This technical solution provides a compact and highly feasible reliable path to solve the core bottleneck in the process of moving black phosphorus from the laboratory to industrialization, and its technical characteristics significantly meet the needs of large-scale manufacturing.
[0051] Those skilled in the art will understand that the above-described embodiments are specific examples of implementing this application, and in practical applications, various changes in form and detail may be made without departing from the spirit and scope of this application. Any person skilled in the art can make their own modifications and alterations without departing from the spirit and scope of this application; therefore, the scope of protection of this application should be determined by the scope defined in the claims.
Claims
1. A method for preparing black phosphorus based on temperature-induced convection with controlled transport, characterized in that, This method employs a temperature-induced convection-based controlled transport system for black phosphorus preparation. The preparation system includes a multi-temperature zone well furnace, a sealed metal reactor, and a heating device disposed within the sealed metal reactor; The method includes: using red phosphorus, mineralizing agent and transporting agent as raw materials, putting them into a sealed metal reactor, and using a multi-temperature zone well furnace to carry out internal and external multi-temperature zone heat treatment under dual internal and external heating sources to achieve black phosphorus preparation.
2. The method for preparing black phosphorus based on temperature-induced convection according to claim 1, characterized in that, The mass ratio of red phosphorus, mineralizer and transporter is (100~500):(1~100):(1~100).
3. The method for preparing black phosphorus based on temperature-induced convection according to claim 1, characterized in that, The multi-temperature zone pit furnace includes three independently temperature-controlled zones: a bottom zone, a lower zone, and an upper zone. The multi-temperature zone well furnace is equipped with heat-insulating baffles to ensure the temperature field and heat preservation.
4. The method for preparing black phosphorus based on temperature-induced convection according to claim 1, characterized in that, The sealed metal reactor is made of 310s stainless steel and adopts a single flange cover sealing design; the ratio of the height to the diameter of the chamber of the sealed metal reactor is 1:(0.3~3).
5. The method for preparing black phosphorus based on temperature-induced convection according to claim 1, characterized in that, The heating device is fixed to the flange cover of the sealed metal reactor, and the heating device has an independent temperature sensing thermocouple built in.
6. The method for preparing black phosphorus based on temperature-induced convection according to claim 1, characterized in that, When using a multi-temperature zone well furnace for heat treatment with internal and external dual heating sources, the external heating source heats the temperature from room temperature to 500~600℃ for 60~240min; the holding time is 1000~3000min; and then the temperature is cooled to room temperature for 60~1000min.
7. The method for preparing black phosphorus based on temperature-induced convection according to claim 6, characterized in that, When using a multi-temperature zone well furnace for heat treatment with internal and external dual heating sources, the internal heating source heats the furnace from room temperature to 500~600℃ for 60~240min, holds the temperature for 1000~3000min, and then cools it to room temperature for 60~1000min.
8. The method for preparing black phosphorus based on temperature-induced convection according to claim 1, characterized in that, The red phosphorus is in the form of powder or granules.
9. The method for preparing black phosphorus based on temperature-induced convection according to claim 1, characterized in that, The mineralizing agent comprises one or more of tin, bismuth, and antimony; the mineralizing agent is in the form of powder or granules.
10. The method for preparing black phosphorus based on temperature-induced convection according to claim 1, characterized in that, The transport agent comprises one or more of iodine, bismuth iodide, antimony iodide, tin tetraiodide, or stannous iodide; the transport agent is in granular or powder form.