Silicon-doped black phosphorus and preparation method thereof
By using a silicon-doped black phosphorus preparation method, the instability of black phosphorus in humid and oxygen environments was solved, improving its structural stability and charge transport performance, and thus enhancing the performance of the photodetector.
Patent Information
- Application Number
- CN202511336979.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-18
- Publication Date
- 2025-11-18
AI Technical Summary
Black phosphorus is unstable in humid and oxygen-rich environments, leading to performance degradation and affecting device performance research.
A method for preparing silicon-doped black phosphorus was adopted, using amorphous red phosphorus, tin powder, iodine and silicon powder as raw materials, and heating treatment was carried out by a liquid bath isothermal method of chemical vapor transport to form silicon-doped black phosphorus (BP-Si), thereby improving the lattice stability.
This significantly improves the structural stability and charge transport performance of black phosphorus, thereby enhancing the performance of photodetectors.
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Figure CN120964744A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of semiconductor materials technology, specifically to silicon-doped black phosphorus and its preparation method. Background Technology
[0002] Two-dimensional nanomaterials have attracted widespread attention in basic research and practical applications due to their excellent mechanical, optical, and electrical properties. Since the breakthrough discovery of graphene and its successful applications in multiple fields, other types of two-dimensional materials have also gained increasing attention. Black phosphorus (BP) is an emerging two-dimensional nanomaterial in which each phosphorus atom is covalently bonded to three adjacent atoms to form a honeycomb structure. Compared with gapless graphene, BP has a layer-dependent band gap of 0.3 eV to 2.2 eV and a higher hole mobility. These properties have led to the widespread research and application of BP-based materials in many fields such as optoelectronic devices, energy storage, field-effect transistors, and catalysis. However, when exposed to an atmospheric environment containing moisture and oxygen, BP reacts with O2 to generate phosphorus (P). x O y And P x O y It then reacts with H2O to form phosphoric acid. Therefore, this instability of BP negatively impacts its performance and hinders research into the device's fundamental properties. To address this issue, this invention provides a method that can reduce the negative impact of instability on BP performance and promote research into device performance, which is of great significance. Summary of the Invention
[0003] To address the shortcomings of existing technologies, the present invention aims to provide a silicon-doped black phosphorus and its preparation method. The silicon-doped black phosphorus prepared by this method significantly improves the structural stability of the black phosphorus lattice, enabling the doped black phosphorus to exist stably in the air environment for a long time.
[0004] To solve the above-mentioned technical problems, the present invention provides a method for preparing silicon-doped black phosphorus, comprising the following steps: Amorphous red phosphorus, tin powder, iodine and silicon powder were weighed and mixed according to the mass ratio of amorphous red phosphorus: tin powder: iodine: silicon powder of 40:4:2:0.3 and then loaded into a quartz tube. After the quartz tube was vacuum sealed, it was heated by the liquid bath constant temperature method of chemical vapor transport to obtain the dopant. After heating, the quartz tube containing the dopant to be obtained is cooled to room temperature. The quartz tube is then shaken to spread the raw material evenly. The quartz tube is then placed in a muffle furnace and heated according to the set heating and cooling program. After the reaction is completed, silicon-doped black phosphorus (BP-Si) is obtained.
[0005] Preferably, the average particle size of the silicon powder is 20nm~50nm.
[0006] The average particle size of the silicon powder is limited to 20-50 nm because the silicon powder in the range of 20-50 nm is in the nanometer scale and has a large specific surface area. More silicon atoms are exposed on the surface, which can more effectively react with the black phosphorus precursor.
[0007] Preferably, the quartz tube is placed in glass powder with a melting point of 500-550°C for heating.
[0008] The quartz tube is placed in glass powder with a melting point of 500-550°C for heating, which is to help the quartz tube to be heated uniformly after the glass powder is melted when the temperature is raised.
[0009] Preferably, the mass ratio of SiO2:PbO5:Na2O:Al2O3:B2O3 in the glass powder is 12%-14%:50%-60%:15%-20%:6%-7%:2.5%-3.5%.
[0010] The glass powder with the mass ratio can form a stable, uniform, and safe liquid bath environment in a specific temperature range, which is conducive to promoting the growth of BP-Si. That is, the liquid bath environment can ensure uniform temperature distribution in the quartz tube and has good heat preservation effect, which is conducive to the uniform growth of long-size BP-Si fibers; at the same time, it also provides good buffering effect outside the quartz tube, effectively absorbs and relieves part of the stress generated in the reaction process, and avoids the danger of explosion of the quartz tube.
[0011] Preferably, the heating time of the quartz tube is 200-240 min, and then the cooling time to room temperature is 800-840 min.
[0012] The heating time is 200-240 min to prevent the quartz tube from exploding due to thermal stress and to ensure the smooth start of the reactants. The slow cooling for 800-840 min provides sufficient time for the further growth of the crystal grains and the repair of the crystal lattice defects, thereby ensuring that the obtained BP-Si has good crystallinity and millimeter-level macro size.
[0013] Preferably, the quartz tube is vacuumed to <10 -3 Pa.
[0014] Preferably, the temperature rising and falling program is as follows: Heating from room temperature to 600℃~620℃, heating time is 200min~250min, holding time is 270min~300min; then cooling to 485℃~500℃, cooling time is 450min~480min, holding time is 200min~240min; continue to cool to 120℃~140℃, cooling time is 300min~360min, then cool to room temperature.
[0015] The first stage heating to 620℃ is to create sufficient and uniform gas phase reactant atmosphere and prepare for subsequent growth. The second stage cooling to 485℃ realizes the preferred growth of one-dimensional BP fibers and silicon doping at the best supersaturation.
[0016] Preferably, the raw materials need to be weighed under the atmosphere of inert gas.
[0017] Preferably, the quartz glass tube to be loaded with raw materials is cleaned with acetone, ethanol and deionized water respectively before use.
[0018] The application also provides a silicon-doped black phosphorus prepared by the preparation method.
[0019] Compared with the prior art, the application has the beneficial effects that: The application is to use amorphous red phosphorus as phosphorus source, tin and iodine as transport agent, and silicon powder as silicon source, mix uniformly according to the mass ratio of amorphous red phosphorus, tin powder, iodine and silicon powder, and vacuum packaging to avoid the contact of raw materials with moisture and oxygen in the atmosphere (the mixed uniformity can be loaded into a quartz tube, and the vacuum packaging is to vacuum package the quartz tube), and the liquid bath constant temperature method is used to heat the mixed amorphous red phosphorus, tin powder, iodine and silicon powder, which is beneficial to the uniform growth of long-size BP-Si fibers (that is, the packaged quartz tube is heated to ensure uniform temperature distribution in the quartz tube, and good heat preservation effect is achieved, and the quartz tube also provides good buffering effect, effectively absorbs and relieves part of the stress generated in the reaction process, and avoids the danger of explosion of the quartz tube), and then the obtained doping object (the quartz tube loaded with the obtained doping object) is placed into a muffle furnace for heating treatment, so that the controllable preparation of millimeter-level two-dimensional BP-Si fibers is successfully realized, and the in-situ doping of Si is also completed, the doping significantly improves the structural stability of the BP lattice, and makes it exist stably in the air environment for a long time. The reason is that: Si doping can effectively regulate the electronic structure of BP, improve its charge transport performance, carrier mobility, chemical stability and structural stability; in addition to lattice doping, Si nanoparticles can also be stably loaded on the surface of BP fibers to form BP / Si heterojunction, and the built-in electric field is used to efficiently separate photo-generated carriers and promote transport. The synergistic effect of these material properties finally significantly improves the performance of the photodetector based on the BP-Si fibers. BRIEF DESCRIPTION OF DRAWINGS
[0020] Figure 1 Typical SEM images and XRD patterns of BP and BP-Si samples in Example 1 and Comparative Example 1 of the present application, wherein (a) is the SEM image of BP, (b) is the typical SEM image of BP-Si sample, (c) is the typical SEM image of BP-Si sample, (d) is the typical SEM image of BP-Si sample (e) is the XRD pattern of BP and BP-Si.
[0021] Figure 2 Band structure diagrams of black phosphorus crystal and silicon-doped black phosphorus in Example 1 and Comparative Example 1 of the present application, wherein the left diagram is the band structure diagram of undoped black phosphorus crystal, the middle diagram is the band structure diagram of black phosphorus crystal doped with two silicon, and the right diagram is the band structure diagram of black phosphorus crystal doped with one silicon. DETAILED DESCRIPTION
[0022] In order to make the above objectives, features and advantages of the embodiments of the present application more obvious and easy to understand, the technical solutions in the embodiments of the present application will be described clearly and completely below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by a person of ordinary skill in the art without creative work fall within the protection scope of the present application.
[0023] It should be noted that when numerical ranges are involved in the present application, both endpoints of each numerical range and any number between the two endpoints can be selected. Since the steps and methods used are the same as those in Example 1 to Example 12, in order to avoid redundancy, the present application describes preferred embodiments, but the present application is not limited thereto, but can also be embodied in other ways within the scope of the technical solutions defined in the appended claims.
[0024] The technical solutions of the present application will be further illustrated in the form of specific examples as follows.
[0025] In each of the following embodiments, the method is a conventional method unless otherwise specified, and the reagent is commercially available unless otherwise specified.
[0026] In the prior art, black phosphorus (BP) is exposed to air, and BP reacts with O2 in the air to form P x O y , and then P x O ySubsequently, the reaction with H2O forms phosphoric acid. This instability of BP has a negative impact on the performance of BP, hindering the study of the basic performance of the device. In order to solve this problem, the strategy adopted by the present application is to dope heteroatoms (silicon atoms) in BP, which can realize the regulation of the electronic structure without sacrificing its unique two-dimensional structure, and is a very promising method to regulate the physical and chemical properties of BP.
[0027] The silicon-doped black phosphorus prepared by the preparation method of silicon-doped black phosphorus based on black phosphorus and silicon-doped black phosphorus provided by the present application significantly improves the structural stability of the black phosphorus lattice, so that the doped black phosphorus can exist stably in the air environment for a long time.
[0028] The following gives a specific embodiment of the silicon-doped black phosphorus prepared by the preparation method of silicon-doped black phosphorus.
[0029] Example 1 A preparation method of silicon-doped black phosphorus includes the following steps: A 20cm-long and 1cm-diameter quartz glass tube is cleaned with acetone, ethanol and deionized water for 15 minutes each by ultrasonic cleaning, and then dried for standby use; In an inert gas atmosphere, amorphous red phosphorus 400mg, tin powder 40mg, iodine 20mg and silicon powder 3mg are weighed according to the mass ratio of amorphous red phosphorus:tin powder:iodine:silicon powder 40:4:2:0.3, mixed and then loaded into the quartz tube, and the quartz tube is vacuum heated and sealed by a hydrogen flame sealing machine at a heating temperature of 2200℃-2800℃, the vacuum pressure is <10 -3 Pa, and the tube length of the sealing area after sealing is 10cm, wherein the average particle size of the silicon powder is 20nm; The vacuum-sealed quartz tube is completely immersed in a glass powder stainless steel device with a ratio of SiO2:PbO5:Na2O:Al2O3:B2O3 of 12:50:15:6:2.5%, and the glass powder is heated to 500℃ to become liquid, and the heating time is 200min, then cooled to room temperature within 840min, (the heating process of the quartz tube is realized by liquid bath constant temperature method based on chemical vapor transport (CVT)); After heating and shaking, the quartz tube is placed in a muffle furnace and heated from room temperature to 620℃, the heating time is 200min, and the holding time is 300min; then the temperature is lowered to 485℃, the cooling time is 480min, and the holding time is 240min; the temperature is further lowered to 120℃, the cooling time is 360min, and then the temperature is cooled to room temperature, after the reaction is completed, the silicon-doped black phosphorus BP-Si is obtained.
[0030] Example 2 A preparation method of silicon-doped black phosphorus includes the following steps: A quartz glass tube with a length of 20 cm and a diameter of 1 cm was cleaned with acetone, ethanol, and deionized water for 15 minutes each by ultrasonic cleaning, and then dried for standby use; Under an inert gas atmosphere, amorphous red phosphorus 400 mg, tin powder 40 mg, iodine 18 mg, and silicon powder 3 mg were mixed according to the mass ratio of amorphous red phosphorus:tin powder:iodine:silicon powder 40:4:1.8:0.3, and then loaded into a quartz tube. The quartz tube was sealed by a hydrogen flame sealing machine under vacuum heating at a heating temperature of 2200℃-2800℃, and the vacuum pressure was <10 -3 Pa. After sealing, the tube length of the sealed area was 10 cm, and the average particle size of the silicon powder was 20 nm; The vacuum-sealed quartz tube was completely immersed in a glass powder stainless steel device with a ratio of SiO2:PbO5:Na2O:Al2O3:B2O3 of 12%:50%:15%:6%:2.5%. The glass powder was heated to 500℃ and became liquid. The heating time was 200 min, and then cooled to room temperature within 840 min. The heating process of the quartz tube was realized by a liquid bath constant temperature method based on chemical vapor transport (CVT). After heating and shaking, the quartz tube was placed in a muffle furnace and heated from room temperature to 620℃, with a heating time of 200 min and a holding time of 300 min. Then it was cooled to 485℃, with a cooling time of 480 min and a holding time of 240 min. It was further cooled to 120℃, with a cooling time of 360 min, and then cooled to room temperature. After the reaction was completed, silicon-doped black phosphorus BP-Si was obtained.
[0031] Example 3 A method for preparing silicon-doped black phosphorus, comprising the following steps: A quartz glass tube with a length of 20 cm and a diameter of 1 cm was cleaned with acetone, ethanol, and deionized water for 15 minutes each by ultrasonic cleaning, and then dried for standby use; Under an inert gas atmosphere, amorphous red phosphorus 400 mg, tin powder 40 mg, iodine 18 mg, and silicon powder 3 mg were mixed according to the mass ratio of amorphous red phosphorus:tin powder:iodine:silicon powder 40:4:1.8:0.3, and then loaded into a quartz tube. The quartz tube was sealed by a hydrogen flame sealing machine under vacuum heating at a heating temperature of 2200℃-2800℃, and the vacuum pressure was <10 -3 Pa. After sealing, the tube length of the sealed area was 10 cm, and the average particle size of the silicon powder was 20 nm; The quartz tube after vacuum sealing is completely immersed in a glass powder stainless steel device with a proportion of SiO2:PbO5:Na2O:Al2O3:B2O3 being 12%:50%:15%:6%:2.5%, the glass powder is heated to a liquid state at 500°C, the heating time is 200 min, and then cooled to room temperature within 840 min. The heating process of the quartz tube is realized by the liquid bath constant temperature method based on chemical vapor transport (CVT). After heating, the quartz tube is shaken to evenly lay the raw materials, and then the quartz tube is placed in a muffle furnace and heated from room temperature to 620°C, the heating time is 200 min, and the holding time is 300 min; then cooled to 485°C, the cooling time is 480 min, and the holding time is 240 min; continue to cool to 120°C, the cooling time is 360 min, and then cool to room temperature, after the reaction is completed, silicon-doped black phosphorus BP-Si is obtained.
[0032] Example 4 A method for preparing silicon-doped black phosphorus, comprising the following steps: A quartz glass tube with a length of 20 cm and a diameter of 1 cm is ultrasonically cleaned with acetone, ethanol and deionized water for 15 minutes respectively, and then dried for standby use; Under an inert gas atmosphere, amorphous red phosphorus 400 mg, tin powder 40 mg, iodine 19 mg and silicon powder 4 mg are weighed according to the mass ratio of amorphous red phosphorus:tin powder:iodine:silicon powder being 40:4:1.9:0.4, mixed and loaded into the quartz tube, and the quartz tube is vacuum heated and sealed at a heating temperature of 2200°C-2800°C by a hydrogen flame sealing machine, the vacuum pressure is <10 -3 Pa, the tube length of the sealing area after sealing is 10 cm, and the average particle size of the silicon powder is 20 nm; The quartz tube after vacuum sealing is completely immersed in a glass powder stainless steel device with a proportion of SiO2:PbO5:Na2O:Al2O3:B2O3 being 12%:50%:15%:6%:2.5%, the glass powder is heated to a liquid state at 500°C, the heating time is 200 min, and then cooled to room temperature within 840 min. The heating process of the quartz tube is realized by the liquid bath constant temperature method based on chemical vapor transport (CVT). After heating, the quartz tube is shaken to evenly lay the raw materials, and then the quartz tube is placed in a muffle furnace and heated from room temperature to 620°C, the heating time is 200 min, and the holding time is 300 min; then cooled to 485°C, the cooling time is 480 min, and the holding time is 240 min; continue to cool to 120°C, the cooling time is 360 min, and then cool to room temperature, after the reaction is completed, silicon-doped black phosphorus BP-Si is obtained.
[0033] Example 5 A preparation method of silicon-doped black phosphorus, comprising the following steps: A quartz glass tube with a length of 20 cm and a diameter of 1 cm is ultrasonically cleaned with acetone, ethanol and deionized water for 15 minutes respectively, and then dried for standby use; Under an inert gas atmosphere, amorphous red phosphorus 400 mg, tin powder 40 mg, iodine 19 mg and silicon powder 3 mg are weighed according to the mass ratio of amorphous red phosphorus:tin powder:iodine:silicon powder 40:4:1.9:0.3, mixed and loaded into the quartz tube, and the quartz tube is vacuum heated and sealed by a hydrogen flame sealing machine at a heating temperature of 2200℃-2800℃, the vacuum pressure is <10 -3 Pa, and the tube length of the sealing area after sealing is 10 cm, wherein the average particle size of the silicon powder is 20 nm; The vacuum-sealed quartz tube is completely immersed in a stainless steel device with a glass powder ratio of SiO2:PbO5:Na2O:Al2O3:B2O3 being 12%:50%:15%:6%:2.5%, and the glass powder is heated to 500℃ to become liquid, and the heating time is 200 min, then cooled to room temperature within 840 min; After heating and shaking, the quartz tube is lowered to make the raw materials evenly flat, and then the quartz tube is placed in a muffle furnace and heated from room temperature to 620℃, the heating time is 200 min, and the holding time is 300 min; then cooled to 485℃, the cooling time is 480 min, and the holding time is 240 min; continue to cool to 120℃, the cooling time is 360 min, and then cool to room temperature, after the reaction is completed, the silicon-doped black phosphorus BP-Si is obtained.
[0034] Example 6 A preparation method of silicon-doped black phosphorus, comprising the following steps: A quartz glass tube with a length of 20 cm and a diameter of 1 cm is ultrasonically cleaned with acetone, ethanol and deionized water for 15 minutes respectively, and then dried for standby use; Under an inert gas atmosphere, amorphous red phosphorus 400 mg, tin powder 40 mg, iodine 19 mg and silicon powder 3 mg are weighed according to the mass ratio of amorphous red phosphorus:tin powder:iodine:silicon powder 40:4:1.9:0.3, mixed and loaded into the quartz tube, and the quartz tube is vacuum heated and sealed by a hydrogen flame sealing machine at a heating temperature of 2200℃-2800℃, the vacuum pressure is <10 -3 Pa, and the tube length of the sealing area after sealing is 10 cm, wherein the average particle size of the silicon powder is 20 nm; The vacuum-sealed quartz tube is completely immersed in a glass powder stainless steel device with a proportion of SiO2:PbO5:Na2O:Al2O3:B2O3 being 12%:50%:15%:6%:2.5%, the glass powder is heated to be liquid at 500°C, the heating time is 200 min, and then cooled to room temperature within 840 min; After the heating, the quartz tube is shaken to make the raw materials evenly flat, and then the quartz tube is placed in a muffle furnace and heated from room temperature to 620°C, the heating time is 200 min, the holding time is 300 min; then cooled to 485°C, the cooling time is 480 min, the holding time is 240 min; continue to cool to 120°C, the cooling time is 360 min, and then cooled to room temperature, after the reaction is completed, the silicon-doped black phosphorus BP-Si is obtained.
[0035] Example 7 The difference between example 7 and example 1 is that the average particle size of the silicon powder is 50 nm.
[0036] Example 8 The difference between example 8 and example 1 is that the average particle size of the silicon powder is 30 nm.
[0037] Example 9 The difference between example 9 and example 1 is that the vacuum-sealed quartz tube is completely immersed in a glass powder stainless steel device with a proportion of SiO2:PbO5:Na2O:Al2O3:B2O3 being 14%:60%:20%:7%:3.5%, the glass powder is heated to be liquid at 550°C, the heating time is 240 min, and then cooled to room temperature within 800 min.
[0038] Example 10 The difference between example 10 and example 1 is that the vacuum-sealed quartz tube is completely immersed in a glass powder stainless steel device with a proportion of SiO2:PbO5:Na2O:Al2O3:B2O3 being 13%:55%:18%:6.5%:3%, the glass powder is heated to be liquid at 520°C, the heating time is 210 min, and then cooled to room temperature within 820 min.
[0039] Example 11 The difference between example 11 and example 1 is that the quartz tube is placed in a muffle furnace and heated from room temperature to 600°C, the heating time is 250 min, the holding time is 270 min; then cooled to 500°C, the cooling time is 450 min, the holding time is 200 min; continue to cool to 140°C, the cooling time is 300 min, and then cooled to room temperature.
[0040] Example 12 Example 12 differs from Example 1 in that the quartz tube is placed in a muffle furnace and heated from room temperature to 610°C, the heating time is 230 min, and the holding time is 280 min; then cooled to 490°C, the cooling time is 470 min, and the holding time is 220 min; continue to cool to 130°C, the cooling time is 330 min, and then cool to room temperature.
[0041] Comparative Example 1 A method for preparing black phosphorus, comprising the following steps: A quartz glass tube with a length of 20 cm and a diameter of 1 cm is cleaned with acetone, ethanol, and deionized water for 15 minutes each by ultrasonic cleaning, and then dried for use; Under an inert gas atmosphere, amorphous red phosphorus 400 mg, tin powder 40 mg, and iodine 20 mg are weighed according to the mass ratio of amorphous red phosphorus:tin powder:iodine of 20:2:1, mixed, and then loaded into the quartz tube. The quartz tube is sealed by vacuum heating sealing at a heating temperature of 2200°C-2800°C using a hydrogen flame sealing machine. The vacuum pressure is <10 -3 Pa, and the tube length of the sealed area is 10 cm after sealing. The average particle size of the silicon powder is 50 nm; When the sealed quartz tube is placed in a muffle furnace for heat treatment, the heat treatment is performed from room temperature to 620°C, the heating time is 200 min, and the holding time is 300 min; then cooled to 485°C, the cooling time is 480 min, and the holding time is 240 min; continue to cool to 120°C, the cooling time is 360 min, and then cool to room temperature. The product is washed and dried to obtain BP.
[0042] The preparation methods of black phosphorus and silicon-doped black phosphorus based on the above-mentioned Examples 1-12 can all prepare silicon-doped black phosphorus. Now, the silicon-doped black phosphorus prepared by Example 1 and the black phosphorus prepared by Comparative Example 1 are used for experimental verification.
[0043] (1) SEM and XRD As Figure 1 Typical SEM images and XRD of BP-Si and BP samples in Example 1 and Comparative Example 1 are given, wherein Figure 1 (a) and Figure 1 (b) show typical SEM images of BP and BP-Si samples, respectively, by Figure 1 (a) and Figure 1 (b) can be obtained that BP-Si has excellent crystallinity with good rectangular grain morphology. It shows that the surface morphology of BP-Si has changed significantly, and the silicon doping process causes it to exhibit better crystallinity and regularity. As Figure 1(c) and (d) show that the surface of BP-Si is arranged with very regular and obvious atomic particles, and the change in morphology further emphasizes that silicon is successfully combined into the BP structure.
[0044] As Figure 1 (e) It can be observed that the diffraction peak position in the figure is systematically shifted, indicating that silicon atoms enter the lattice of black phosphorus, replace part of the phosphorus atoms or are located in the interstitial position, causing the lattice constant to change, thereby causing the diffraction angle (2 theta) to move. After silicon doping, the material still maintains the typical orthorhombic layered structure of black phosphorus, and no other impurity phase is formed.
[0045] (Band analysis) As Figure 2 The band structure diagram of black phosphorus crystals and silicon-doped black phosphorus in Example 1 and Comparative Example 1 is given, as shown in Figure 2 The left graph is the band structure diagram of the undoped black phosphorus crystal, and through Figure 2 As can be seen from the left graph, black phosphorus is a direct band gap semiconductor, and by introducing silicon atoms, the direct band structure of BP after doping Si atoms can be converted into an indirect band structure; as Figure 2 The middle graph is the band structure diagram of the black phosphorus crystal doped with two silicon atoms, as shown in Figure 2 The right graph is the band structure diagram of the black phosphorus crystal doped with one silicon atom, and through Figure 2 As can be seen from the right graph, by introducing silicon atoms, the type and band gap of the semiconductor are changed, and an impurity band is introduced, thereby realizing the regulation of the properties of BP in the main semiconductor.
[0046] Obviously, those skilled in the art can make various modifications and changes to the present application without departing from the spirit and scope of the present application. Thus, if these modifications and changes of the present application fall within the scope of the claims of the present application and their equivalents, the present application also intends to include these modifications and changes.
Claims
1. A method for preparing silicon-doped black phosphorus, characterized by, The method comprises the following steps: amorphous red phosphorus, tin powder, iodine and silicon powder as raw materials, according to the mass ratio of amorphous red phosphorus:tin powder:iodine:silicon powder is 40:4:1.8~2:0.3~0.5, after weighing and mixing, the chemical vapor transport liquid bath constant temperature method is used for vacuum sealing heating, and the doped material is obtained; After the doped material is cooled to room temperature, the heating treatment is carried out again according to the set temperature rising program and temperature falling program, and the silicon doped black phosphorus is obtained after the reaction is completed.
2. The method of claim 1, wherein the silicon-doped black phosphorus is prepared by the steps of: The average particle size of the silicon powder is 20nm~50nm. 3. The method of claim 1, wherein the silicon-doped black phosphorus is prepared by the steps of: preparing a mixture of phosphorus and silicon; and heating the mixture to a temperature of 300-600 °C for 1-10 hours. The quartz tube is placed in glass powder with a melting point of 500℃~550℃ for heating.
4. The method of claim 3, wherein the black phosphorus and silicon-doped black phosphorus are prepared by the method comprising: The mass ratio of SiO2:PbO5:Na2O:Al2O3:B2O3 in the glass powder is 12%~14%:50%~60%:15%~20%:6%~7%:2.5%~3.5%.
5. The method for preparing silicon-doped black phosphorus according to claim 1, characterized in that, The heating time of the quartz tube is 200min~240min, and then the cooling time to room temperature is 800min~840min.
6. The method of claim 1, wherein the silicon-doped black phosphorus is prepared by the method comprising: preparing a mixture of phosphorus and silicon; and heating the mixture to a temperature of 300-600 °C for 1-10 hours. The quartz tube is evacuated to <10 -3 Pa.
7. The method of claim 1, wherein the silicon-doped black phosphorus is prepared by the method comprising: providing a black phosphorus; and doping the black phosphorus with silicon. The temperature rising and falling program is: heating from room temperature to 600℃~620℃, heating time is 200min~250min, holding time is 270min~300min; then cooling to 485℃~500℃, cooling time is 450min~480min, holding time is 200min~240min; continue to cool to 120℃~140℃, cooling time is 300min~360min, then cool to room temperature.
8. The method of claim 1, wherein the silicon-doped black phosphorus is prepared by the method comprising: providing a black phosphorus; and doping the black phosphorus with silicon. The quartz glass tube containing raw materials is cleaned with acetone, ethanol and deionized water respectively, and then is used.
9. The silicon doped black phosphorus prepared by the method of any one of claims 1~8.