A black phosphorus arsenic material, a preparation method thereof and application thereof in a semiconductor device

Abstract

The application provides a preparation method of black phosphorus arsenic material, comprising the following steps: mixing gray arsenic, red phosphorus and an additive, and then placing the mixture in a high-temperature area to react in a closed container in a protective atmosphere or vacuum, and synchronously depositing in a low-temperature area to crystallize, so as to obtain black phosphorus arsenic material; wherein the additive comprises tellurium iodide; the temperature of the high-temperature area is not lower than 550 DEG C, and the temperature of the low-temperature area is 450-530 DEG C; and the black phosphorus arsenic material is black phosphorus arsenic single crystal. The application realizes controllable synthesis of flaky black phosphorus arsenic single crystal, and has excellent applicability in semiconductor devices.

Description

Technical Field

[0001] The present invention relates to the preparation of semiconductor materials, and particularly to a black phosphorus arsenide material, a preparation method thereof, and an application thereof in semiconductor devices. Background Art

[0002] Black phosphorus arsenide has an orthorhombic lattice with a wrinkled honeycomb structure, and has strong in-plane covalent bonds and weak interlayer van der Waals interactions; arsenic atoms and phosphorus atoms are distributed therein, and the content of arsenic atoms is 0 < As ≤ 0.83. The unit cell volume of the black phosphorus arsenide molecule is proportional to the ratio of arsenic atoms, and its lattice constants are usually b > c > a, where a, b, and c are the lattice constants along the zigzag, stacking, and armchair directions, respectively. Its moderately adjustable bandgap structure (0.15 - 0.3 eV) can fill the spectral gap between the zero bandgap of graphene and the relatively large bandgap (5 - 6 eV) of hexagonal boron nitride, realizing the response in the mid- to long-wave infrared region. At the same time, black phosphorus arsenide has anisotropic optoelectronic properties and a higher theoretical carrier mobility (~14000 cm 2 V -1 s -1 ) than transition metal disulfides.

[0003] Based on the above characteristics, black phosphorus arsenide materials have excellent application prospects in field-effect transistors, photoconductors, mid-wave infrared photodetectors, silicon photon microheaters, lithium-ion batteries, solar exciton batteries and lasers, mid-wave infrared photodetection, etc.

[0004] However, the prior art has not yet achieved the direct preparation of few-layer or even single-layer large-area black phosphorus arsenide thin films. The top-down method is currently the mainstream method for preparing black phosphorus arsenide two-dimensional materials, that is, synthesizing bulk black phosphorus arsenide crystals by chemical vapor transport method, and then obtaining black phosphorus arsenide two-dimensional materials by various peeling methods. Therefore, black phosphorus arsenide crystals with single crystal characteristics are the only precursors for obtaining two-dimensional single crystal black phosphorus arsenide. Before obtaining two-dimensional single crystal black phosphorus arsenide materials, black phosphorus arsenide single crystal materials need to be synthesized first.

[0005] Since the synthesis of black phosphorus arsenide crystals directly affects the quality and performance of two-dimensional black phosphorus arsenide materials, and there is no synthesis method for black phosphorus arsenide single crystals in the prior art, the application of black phosphorus arsenide materials has not been fully exerted, restricting the wide application of black phosphorus arsenide materials in semiconductor devices and other aspects.

[0006] In view of this, it is necessary to provide a black phosphorus arsenide material, a preparation method thereof, and an application thereof in semiconductor devices to solve or at least alleviate the technical defect that black phosphorus arsenide single crystals cannot be synthesized in the above prior art. Summary of the Invention

[0007] The main objective of this invention is to provide a black phosphorus arsenic material, its preparation method, and its application in semiconductor devices, aiming to solve the technical problem that the prior art cannot synthesize black phosphorus arsenic single crystals.

[0008] To achieve the above objectives, the present invention provides a method for preparing black phosphorus arsenic material, comprising: mixing gray arsenic, red phosphorus and additives in a sealed container under a protective atmosphere or vacuum, and then placing the mixture in a high-temperature region for reaction, while simultaneously crystallizing and depositing it in a low-temperature region to obtain black phosphorus arsenic material;

[0009] The additives include tellurium iodide; the temperature of the high-temperature region is not lower than 550°C, and the temperature of the low-temperature region is 450-530°C; the black phosphorus arsenic material is a single crystal of black phosphorus arsenic.

[0010] Furthermore, the reaction duration is less than 20 hours.

[0011] Furthermore, the reaction duration is 6–12 hours.

[0012] Furthermore, after the reaction is completed, the high-temperature region and the low-temperature region are simultaneously cooled down, and the cooling method is rapid cooling.

[0013] Furthermore, the mass of the tellurium iodide is 1 to 10% of the total mass of the gray arsenic, the red phosphorus, and the additives.

[0014] Furthermore, the mass of the tellurium iodide is 2-7% of the total mass of the gray arsenic, the red phosphorus, and the additives.

[0015] Furthermore, the atomic ratio of the gray arsenic to the red phosphorus is 4:1 to 1:2.

[0016] Furthermore, once the temperatures of the high-temperature region and the low-temperature region stabilize, the temperature of the high-temperature region is 550–600°C; and the temperature of the low-temperature region is 480–520°C.

[0017] The present invention also provides a black phosphorus arsenic material, which is prepared by any of the preparation methods described above.

[0018] The present invention also provides an application of the black phosphorus arsenic material as described in any one of the above claims in semiconductor devices.

[0019] Compared with the prior art, the present invention has at least the following advantages:

[0020] This invention achieves the controllable synthesis of sheet-like black phosphorus arsenic single crystals by adding tellurium iodide (TeI4) as an additive to raw materials gray arsenic (As) and red phosphorus (P), making it a transport agent and crystal form regulator, and by strictly controlling the reaction conditions such as the temperature in the high-temperature reaction zone and the low-temperature deposition zone.

[0021] Existing technologies typically produce black phosphorus arsenic materials with disordered crystal growth patterns, making it impossible to achieve directional growth of the (010) crystal plane. In contrast, the black phosphorus arsenic material of this invention has typical plate-like single-crystal characteristics, achieving preferential growth of the (010) crystal plane.

[0022] Furthermore, the sheet-like black phosphorus arsenic single crystals obtained by this invention have low impurities, superior crystal form, and exhibit obvious consistency in macroscopic and microscopic growth. Attached Figure Description

[0023] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the structures shown in these drawings without creative effort.

[0024] Figure 1 This is a physical image of the black phosphorus arsenic material in Example 1 of the present invention;

[0025] Figure 2 This is a scanning electron microscope (SEM) image of the black phosphorus arsenic material in Example 1 of the present invention;

[0026] Figure 3 The image shows the X-ray diffraction (XRD) pattern of the black phosphorus arsenic material in Example 1 of this invention.

[0027] Figure 4 This is the Raman spectrum of the black phosphorus arsenic material in Example 1 of the present invention;

[0028] Figure 5 This is a high-resolution transmission electron microscope (HRTEM) image of the black phosphorus arsenic material in Example 1 of the present invention;

[0029] Figure 6 This is the selected area electron diffraction (SAED) pattern of the black phosphorus arsenic material in Example 1 of the present invention;

[0030] Figure 7 This is a graph showing the current variation with gate voltage of the single-crystal black phosphorus arsenic-based field-effect transistor in Embodiment 2 of the present invention under different bias voltages (0.1~0.5V);

[0031] Figure 8 This is a graph showing the current variation with bias voltage of the single-crystal black phosphorus arsenic-based field-effect transistor in Embodiment 2 of the present invention under different gate voltages (0-20V);

[0032] Figure 9 The image shows the X-ray diffraction (XRD) pattern of the black phosphorus arsenic material in Example 3 of this invention.

[0033] Figure 10 This is the selected area electron diffraction (SAED) pattern of the black phosphorus arsenic material in Example 3 of the present invention;

[0034] Figure 11 The image shows the X-ray diffraction (XRD) pattern of the black phosphorus arsenic material in Example 4 of this invention.

[0035] Figure 12 The selected area electron diffraction (SAED) pattern of the black phosphorus arsenic material in Example 4 of this invention is shown below.

[0036] Figure 13 The image shows the X-ray diffraction (XRD) pattern of the gray arsenic crystal in Comparative Example 1 of this invention.

[0037] Figure 14 The image shows the X-ray diffraction (XRD) pattern of the black phosphorus arsenic material in Comparative Example 2 of this invention.

[0038] Figure 15 The selected area electron diffraction (SAED) pattern of the black phosphorus arsenic material in Comparative Example 2 of this invention is shown below.

[0039] Figure 16 The X-ray diffraction (XRD) pattern of the black phosphorus arsenic material in Comparative Example 3 of this invention is shown below.

[0040] Figure 17 The selected area electron diffraction (SAED) pattern of the black phosphorus arsenic material in Comparative Example 3 of this invention is shown below.

[0041] Figure 18 The X-ray diffraction (XRD) pattern of the black phosphorus arsenic material in Comparative Example 4 of this invention is shown below.

[0042] Figure 19 The selected area electron diffraction (SAED) pattern of the black phosphorus arsenic material in Comparative Example 4 of this invention is shown below.

[0043] Figure 20 The X-ray diffraction (XRD) pattern of the black phosphorus arsenic material in Comparative Example 5 of this invention is shown below.

[0044] Figure 21 The selected area electron diffraction (SAED) pattern of the black phosphorus arsenic material in Comparative Example 5 of this invention is shown below.

[0045] Figure 22 The X-ray diffraction (XRD) pattern of the black phosphorus arsenic material in Comparative Example 6 of this invention is shown below.

[0046] Figure 23 The selected area electron diffraction (SAED) pattern of the black phosphorus arsenic material in Comparative Example 6 of this invention is shown below.

[0047] Figure 24 The X-ray diffraction (XRD) pattern of the black phosphorus arsenic material in Comparative Example 7 of this invention is shown below.

[0048] Figure 25 The selected area electron diffraction (SAED) pattern of the black phosphorus arsenic material in Comparative Example 7 of this invention is shown below.

[0049] Figure 26 The X-ray diffraction (XRD) pattern of the black phosphorus arsenic material in Comparative Example 8 of this invention is shown below.

[0050] Figure 27 The selected area electron diffraction (SAED) pattern of the black phosphorus arsenic material in Comparative Example 8 of this invention is shown below.

[0051] Figure 28 The X-ray diffraction (XRD) pattern of the black phosphorus arsenic material in Comparative Example 9 of this invention is shown.

[0052] Figure 29 The selected area electron diffraction (SAED) pattern of the black phosphorus arsenic material in Comparative Example 9 of this invention is shown below.

[0053] Figure 30 The X-ray diffraction (XRD) pattern of the black phosphorus arsenic material in Comparative Example 10 of this invention is shown.

[0054] Figure 31 This is the selected area electron diffraction (SAED) pattern of the black phosphorus arsenic material in Comparative Example 10 of the present invention.

[0055] The realization of the objective, functional characteristics and advantages of the present invention will be further explained in conjunction with the embodiments and with reference to the accompanying drawings. Detailed Implementation

[0056] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0057] Furthermore, the technical solutions of the various embodiments of the present invention can be combined with each other, but only if they are based on the ability of those skilled in the art to implement them. When the combination of technical solutions is contradictory or cannot be implemented, it should be considered that such combination of technical solutions does not exist and is not within the scope of protection claimed by the present invention.

[0058] When numerical ranges are given in the embodiments, it should be understood that, unless otherwise stated in the present invention, both endpoints of each numerical range and any value between the two endpoints may be selected. Unless otherwise defined, all technical and scientific terms used in this invention, as well as the prior art known to those skilled in the art and the description of the invention, may be implemented using any prior art methods, devices, and materials similar to or equivalent to the methods, devices, and materials in the embodiments of the present invention.

[0059] It should be noted that the existing gas-phase synthesis methods lack systematic exploration of the synthesis of bulk black phosphorus arsenic crystals. They mainly use tin (Sn) plus tin iodide (SnI4) or iodine (I2) as mineralizers. The unexamined types of additives result in poor crystal shape, many metal impurities, and low microscopic growth consistency in the synthesized black phosphorus arsenic, showing a chaotic crystal growth direction and unable to grow preferentially along the (010) crystal plane direction.

[0060] Research has shown that if black arsenic phosphorus crystals are grown strictly along the (010) crystal plane, they will eventually grow into a single black arsenic phosphorus crystal due to their natural layered structure. However, the lack of existing strategies for synthesizing single black arsenic phosphorus crystals is attributed to insufficient systematic exploration of the gas-phase synthesis process and the failure to find suitable conditions for the directional growth of the (010) crystal plane of black arsenic phosphorus.

[0061] Based on this, the present invention provides a method for preparing black phosphorus arsenic material, comprising: mixing gray arsenic, red phosphorus and additives in a sealed container under a protective atmosphere or vacuum, and then placing the mixture in a high-temperature region for reaction, while simultaneously crystallizing and depositing it in a low-temperature region to obtain black phosphorus arsenic material; the black phosphorus arsenic material provided by the present invention is a single crystal of black phosphorus arsenic, which is macroscopically plate-like, has extremely high crystal quality, large grain size and macroscopic and microscopic growth consistency, and exhibits excellent and consistent physicochemical properties in any region.

[0062] To ensure that the black phosphorus arsenic material is a single crystal, the additives must include or be tellurium iodide. It should be understood that when the additives are tantalum iodide (TaI5), antimony iodide (SbI3), tin iodide (SnI4), lead iodide (PbI2), bismuth iodide (BiI3), iodine (I2), etc., the black phosphorus arsenic single crystal described in this application cannot be obtained.

[0063] The reaction method in this invention is a gas-phase transport method, i.e., a gas-phase synthesis reaction. To ensure the reaction proceeds, before the reaction, gray arsenic, red phosphorus, and additives can be placed in a quartz tube, and the quartz tube is vacuum sealed and placed in a dual-temperature zone tube furnace. Then, both the high-temperature zone and the low-temperature zone are heated to their respective set temperatures so that the gray arsenic, red phosphorus, and additives are calcined under the set temperature field.

[0064] The high-temperature region can be understood as the high-temperature reaction region, and the low-temperature region can be understood as the low-temperature deposition region. The temperature field is composed of the high-temperature region and the low-temperature region. During the reaction, when the temperatures of the high-temperature region and the low-temperature region stabilize, the temperature of the high-temperature region is not lower than 550°C, and the temperature of the low-temperature region is 450-530°C. For example, the temperature of the high-temperature region can be 550-600°C, and the temperature of the low-temperature region can be 480-520°C.

[0065] To ensure the synthesis of black phosphorus arsenic single crystals, the reaction time must be less than 20 hours. Further, the reaction time can be 6–12 hours; the reaction time includes the heating time and the holding time. The heating time is the time before the temperatures in the high-temperature and low-temperature regions stabilize, and it is typically 1–4 hours. The holding time is the time after the temperatures in the high-temperature and low-temperature regions stabilize, and it can be 4–10 hours.

[0066] To further ensure the acquisition of black phosphorus arsenic single crystals, after the reaction is complete, both the high-temperature and low-temperature regions can be cooled simultaneously using quenching. Quenching can be achieved by placing the reaction vessel in a room-temperature environment, thereby rapidly cooling the reaction products to room temperature.

[0067] As an optional embodiment, in this invention, the mass of tellurium iodide can be 1 to 10% of the total mass of gray arsenic, red phosphorus, and additives; further, the mass of tellurium iodide can be 2 to 7% of the total mass of gray arsenic, red phosphorus, and additives. The atomic ratio of gray arsenic to red phosphorus can be 4:1 to 1:2; further, the atomic ratio of gray arsenic to red phosphorus can be 2:1 to 1:1.

[0068] It should be understood that in this invention, gray arsenic (As), red phosphorus (P), and tellurium iodide (TeI4) as an additive are vaporized at the temperature of the high-temperature reaction zone. The gaseous products formed are transferred to the low-temperature zone under the driving force of the temperature difference gradient. Arsenic and phosphorus crystallize and deposit at the temperature of the low-temperature deposition zone to obtain black phosphorus arsenic products. The gaseous iodide returns to the high-temperature reaction zone under the driving force of the concentration difference, so that the transport process continues. The low-doped tellurium iodide (TeI4) dissociates into tellurium iodide sub-iodide (TeI2) and gaseous I atoms at this temperature. Among them, the gaseous I atoms act as a transport agent and TeI2 acts as a crystal form regulator, so as to achieve the controllable synthesis of plate-like black phosphorus arsenic single crystals.

[0069] It should be noted that although the black phosphorus arsenic crystal provided by the Chinese invention with authorization announcement number CN113737279B has the trend of preferential growth of the (010) single crystal plane family, it has failed to achieve completely uniform growth in each region. That is, there will still be some defects, grain boundaries or atomic vacancies, which will affect the overall performance of the crystal and the uniform performance of each region.

[0070] In the reaction process of this invention, the black phosphorus arsenic crystal grows strictly according to the (010) crystal plane. Due to its natural layered structure, it will eventually grow into a single black phosphorus arsenic crystal. Therefore, unlike other black phosphorus arsenic materials, the black phosphorus arsenic material provided by this invention is a single black phosphorus arsenic crystal grown strictly according to the (010) crystal plane, which can be used as a precursor for two-dimensional single-crystal black phosphorus arsenic.

[0071] Based on this, the present invention provides a black phosphorus arsenic material, which is prepared by the preparation method as described in any of the above embodiments.

[0072] Since the black phosphorus arsenic material provided by the present invention is a single crystal of black phosphorus arsenic and has excellent semiconductor properties, the present invention also provides an application of the black phosphorus arsenic material as described in any of the above embodiments in semiconductor devices.

[0073] The following are specific examples of the present invention:

[0074] Example 1

[0075] Step 1: Soak the quartz tube in 3% hydrofluoric acid for 10 hours, then rinse it 3-5 times with deionized water, 15-20% dilute nitric acid solution and anhydrous ethanol respectively, and dry it in a far-infrared drying oven for later use; grind the raw materials gray arsenic (As) and red phosphorus (P) into powder for later use.

[0076] Step 2: Under the inert atmosphere of the glove box, weigh 0.4380g of gray arsenic (As) and 0.1840g of red phosphorus (P) as raw materials using a 0.001g electronic balance and add them into the quartz tube; wherein, the atomic weight of gray arsenic is 0.0058mol and the atomic weight of red phosphorus is also 0.0058mol.

[0077] Step 3: Under the inert atmosphere of the glove box, weigh 0.0155g of tellurium iodide (TeI4) as an additive using a 0.0001g electronic balance and add it into the quartz tube; wherein, the tellurium iodide provides 0.0001mol of iodine atoms.

[0078] Step 4: Seal one end of the quartz tube with a plug, then seal the quartz tube with a vacuum valve, and then take the quartz tube out of the glove box.

[0079] Step 5: Use a tube sealing machine to evacuate the inside of the quartz tube to a vacuum, and then use a hydrogen-oxygen generator to seal the quartz tube.

[0080] Step 6: Place the sealed quartz tube horizontally into the dual-temperature zone tube furnace, set the dual-temperature zone temperature, and carry out the gas-phase synthesis reaction.

[0081] The process involves heating the high-temperature zone from room temperature to 550℃ at a rate of 4.38℃ / min and the low-temperature zone from room temperature to 500℃ at a rate of 3.96℃ / min for 2 hours. After heating, the temperature is maintained for 4 hours. Then, the quartz tube is placed in a room temperature environment, which rapidly cools both the high-temperature and low-temperature zones to room temperature (which can be understood as scald cooling) to obtain black phosphorus arsenic material.

[0082] The black phosphorus arsenic material obtained in this embodiment is a single crystal material of black phosphorus arsenic.

[0083] Reference Figure 1 As shown, the black phosphorus arsenic material obtained in this embodiment is macroscopically sheet-like, with a size of approximately 2mm*3mm and a thickness of approximately 50μm.

[0084] See Figure 2 As shown, the scanning electron microscope image of the black phosphorus arsenic material obtained in this embodiment shows a clear layered stacking morphology at the microscopic level, with a complete sheet-like structure and a very large lateral dimension.

[0085] See Figure 3 As shown, the X-ray diffraction pattern of the black phosphorus arsenic material obtained in this embodiment exhibits obvious single-crystal characteristics, with only diffraction peaks representing the (020), (040), (060), and (080) crystal planes appearing, while the diffraction peaks representing other crystal planes disappear, indicating its excellent single-crystal properties.

[0086] See Figure 4 As shown, the Raman spectrum of the black phosphorus arsenic material obtained in this embodiment exhibits vibrational peaks corresponding to As, As-P, and P from the low-frequency region to the high-frequency region, which are consistent with the characteristics of black phosphorus arsenic material.

[0087] See Figure 5 As shown, the high-resolution transmission electron microscopy (TEM) image of the black phosphorus arsenic material obtained in this embodiment exhibits a highly consistent lattice image, indicating a high degree of consistency in crystal plane growth.

[0088] See Figure 6 As shown, the selected area electron diffraction pattern of the black phosphorus arsenic material obtained in this embodiment exhibits a distinct set of lattice features, demonstrating the material's excellent single-crystal properties.

[0089] Example 2

[0090] The black phosphorus arsenic material prepared in Example 1 was applied to semiconductor devices. The specific application process was as follows: the black phosphorus arsenic single crystal material prepared in Example 1 was prepared into a black phosphorus arsenic stripping sheet with a thickness of nanometers by mechanical exfoliation. A single crystal black phosphorus arsenic-based field-effect transistor was made according to the standard field-effect transistor preparation method, and its electrical transport characteristics were tested.

[0091] Test results:

[0092] See Figure 7 The figure shows the current variation with gate voltage of the above-mentioned single-crystal black phosphorus arsenic-based field-effect transistor under different bias voltages (0.1~0.5V), demonstrating its good electron cutoff characteristics.

[0093] See Figure 8 The figure shows the current variation with bias voltage of the above-mentioned single-crystal black phosphorus arsenic-based field-effect transistor under different gate voltages (0-20V), demonstrating its excellent electron transport characteristics.

[0094] Example 3

[0095] Compared to Example 1, this embodiment only adjusts the amount of tellurium iodide added to 0.0310g, while other conditions remain the same as in Example 1; in this embodiment, the atomic weight of iodine (derived from tellurium iodide) is 0.0002mol.

[0096] This embodiment yielded black phosphorus arsenic single crystal material.

[0097] See Figure 9 As shown, the X-ray diffraction pattern of the black phosphorus arsenic material obtained in this embodiment exhibits obvious single-crystal characteristics, with only diffraction peaks representing the (020), (040), (060), and (080) crystal planes appearing, while the diffraction peaks representing other crystal planes disappear, indicating its excellent single-crystal properties.

[0098] See Figure 10 As shown, the selected area electron diffraction pattern of the black phosphorus arsenic material obtained in this embodiment exhibits a distinct set of lattice features, demonstrating the material's excellent single-crystal properties.

[0099] Example 4

[0100] Compared to Example 1, this embodiment differs only in that the amount of tellurium iodide added is adjusted to 0.0465 g, while all other conditions remain the same as in Example 1. In this embodiment, the atomic weight of iodine (derived from tellurium iodide) is 0.0003 mol.

[0101] This embodiment yielded black phosphorus arsenic single crystal material.

[0102] See Figure 11 As shown, the X-ray diffraction pattern of the black phosphorus arsenic material obtained in this embodiment exhibits obvious single-crystal characteristics, with only diffraction peaks representing the (020), (040), (060), and (080) crystal planes appearing, while the diffraction peaks representing other crystal planes disappear, indicating its excellent single-crystal properties.

[0103] See Figure 12 As shown, the selected area electron diffraction pattern of the black phosphorus arsenic material obtained in this embodiment exhibits a distinct set of lattice features, demonstrating the material's excellent single-crystal properties.

[0104] Comparative Example 1

[0105] Compared to Example 1, this comparative example differs only in that the amount of tellurium iodide added is adjusted to 0, while all other conditions remain the same as in Example 1. In this example, the atomic weight of iodine is 0.

[0106] No black phosphorus arsenic single crystal material was obtained in this comparative example.

[0107] See Figure 13 As shown, the X-ray diffraction pattern of the material obtained in this comparative example shows obvious gray arsenic characteristic peaks, indicating that the product is gray arsenic crystals without the addition of exogenous additives.

[0108] Comparative Example 2

[0109] Compared to Example 1, this comparative example replaces tellurium iodide with tin (Sn) and tin iodide (SnI4). In this comparative example, the amount of tin (Sn) added is 0.0746 g, and the amount of tin iodide (SnI4) added is 0.0153 g. All other conditions remain the same as in Example 1. The atomic weight of iodine (derived from tin iodide) in this comparative example is 0.0001 mol.

[0110] No black phosphorus arsenic single crystal material was obtained in this comparative example.

[0111] See Figure 14 As shown, the X-ray diffraction pattern of the black phosphorus arsenic material obtained in this comparative example shows obvious diffraction peaks. In addition to the main (020), (040), (060), and (080) crystal planes, there are still diffraction peaks representing other crystal planes, such as (021) and (041), indicating the polymorphism of the product.

[0112] See Figure 15 As shown, the selected area electron diffraction pattern of the black phosphorus arsenic material obtained in this comparative example exhibits obvious crystal ring characteristics, indicating the polymorphism of the product.

[0113] Comparative Example 3

[0114] Compared to Example 1, this comparative example replaces tellurium iodide with tin iodide (SnI4), with an addition amount of 0.0153 g. All other conditions remain the same as in Example 1. The atomic weight of iodine (derived from tin iodide) in this comparative example is 0.0001 mol.

[0115] No black phosphorus arsenic single crystal material was obtained in this comparative example.

[0116] See Figure 16As shown, although the X-ray diffraction pattern of the black phosphorus arsenic material obtained in this comparative example shows obvious preferential growth of the (010) crystal plane family, diffraction peaks representing other crystal planes still exist, such as (041) and (042), indicating that the product is still polycrystalline.

[0117] See Figure 17 As shown, the selected area electron diffraction pattern of the black phosphorus arsenic material obtained in this comparative example reveals a lattice of multiple crystal planes, indicating the polymorphism of the product.

[0118] Comparative Example 4

[0119] Compared to Example 1, this comparative example replaces tellurium iodide with iodine (I2), and the amount of iodine (I2) added is 0.0124 g. All other conditions remain the same as in Example 1. The atomic weight of the iodine (derived from iodine) in this comparative example is 0.0001 mol.

[0120] No black phosphorus arsenic single crystal material was obtained in this comparative example.

[0121] See Figure 18 As shown, the X-ray diffraction pattern of the black phosphorus arsenic material obtained in this comparative example shows obvious diffraction peaks. In addition to the main (020), (040), (060), and (080) crystal planes, there are still diffraction peaks representing other crystal planes, such as (021) and (041), indicating the polymorphism of the product.

[0122] See Figure 19 As shown, the selected area electron diffraction pattern of the black phosphorus arsenic material obtained in this comparative example exhibits obvious crystal ring characteristics, indicating the polymorphism of the product.

[0123] Comparative Example 5

[0124] Compared to Example 1, this comparative example replaces tellurium iodide with tantalum iodide (TaI5), with an addition amount of 0.0159 g. All other conditions remain the same as in Example 1. The atomic weight of iodine (derived from tantalum iodide) in this comparative example is 0.0001 mol.

[0125] No black phosphorus arsenic single crystal material was obtained in this comparative example.

[0126] See Figure 20 As shown, the X-ray diffraction pattern of the black phosphorus arsenic material obtained in this comparative example shows obvious diffraction peaks. In addition to the main (020), (040), (060), and (080) crystal planes, there are still diffraction peaks representing other crystal planes, such as (021) and (041), indicating the polymorphism of the product.

[0127] See Figure 21As shown, the selected area electron diffraction pattern of the black phosphorus arsenic material obtained in this comparative example reveals a lattice of multiple crystal planes, indicating the polymorphism of the product.

[0128] Comparative Example 6

[0129] Compared to Example 1, this comparative example replaces tellurium iodide with antimony iodide (SbI3), with an addition amount of 0.0164 g of antimony iodide (SbI3). All other conditions remain the same as in Example 1. The atomic weight of iodine (derived from antimony iodide) in this comparative example is 0.0001 mol.

[0130] No black phosphorus arsenic single crystal material was obtained in this comparative example.

[0131] See Figure 22 As shown, the X-ray diffraction pattern of the black phosphorus arsenic material obtained in this comparative example shows obvious diffraction peaks. In addition to the main (020), (040), (060), and (080) crystal planes, there are still diffraction peaks representing other crystal planes, such as (021) and (041), indicating the polymorphism of the product.

[0132] See Figure 23 As shown, the selected area electron diffraction pattern of the black phosphorus arsenic material obtained in this comparative example exhibits obvious crystal ring characteristics, indicating the polymorphism of the product.

[0133] Comparative Example 7

[0134] Compared to Example 1, this comparative example replaces tellurium iodide with lead iodide (PbI2), with an addition amount of 0.0225 g of lead iodide (PbI2). All other conditions remain the same as in Example 1. The atomic weight of iodine (derived from lead iodide) in this comparative example is 0.0001 mol.

[0135] No black phosphorus arsenic single crystal material was obtained in this comparative example.

[0136] See Figure 24 As shown, the X-ray diffraction pattern of the black phosphorus arsenic material obtained in this comparative example shows obvious diffraction peaks. In addition to the main (020), (040), (060), and (080) crystal planes, there are still diffraction peaks representing other crystal planes, such as (021) and (041), indicating the polymorphism of the product.

[0137] See Figure 25 As shown, the selected area electron diffraction pattern of the black phosphorus arsenic material obtained in this comparative example reveals a lattice of multiple crystal planes, indicating the polymorphism of the product.

[0138] Comparative Example 8

[0139] Compared to Example 1, this comparative example replaces tellurium iodide with bismuth iodide (BiI3), and the amount of bismuth iodide (BiI3) added is 0.0192 g. All other conditions remain the same as in Example 1. The atomic weight of iodine (derived from bismuth iodide) in this comparative example is 0.0001 mol.

[0140] No black phosphorus arsenic single crystal material was obtained in this comparative example.

[0141] See Figure 26 As shown, the X-ray diffraction pattern of the black phosphorus arsenic material obtained in this comparative example shows obvious diffraction peaks. In addition to the main (020), (040), (060), and (080) crystal planes, there are still diffraction peaks representing other crystal planes, such as (021) and (041), indicating the polymorphism of the product.

[0142] See Figure 27 As shown, the selected area electron diffraction pattern of the black phosphorus arsenic material obtained in this comparative example reveals a lattice of multiple crystal planes, indicating the polymorphism of the product.

[0143] Comparative Example 9

[0144] Compared to Example 1, this comparative example has an adjusted heat preservation time of 20 hours, while other conditions remain the same as in Example 1.

[0145] No black phosphorus arsenic single crystal material was obtained in this comparative example.

[0146] See Figure 28 As shown, the X-ray diffraction pattern of the black phosphorus arsenic material obtained in this comparative example shows obvious diffraction peaks. In addition to the main (020), (040), (060), and (080) crystal planes, there are still diffraction peaks representing other crystal planes, such as (021) and (041), indicating the polymorphism of the product.

[0147] See Figure 29 As shown, the selected area electron diffraction pattern of the black phosphorus arsenic material obtained in this comparative example reveals a lattice of multiple crystal planes, indicating the polymorphism of the product.

[0148] Comparative Example 10

[0149] Compared to Example 1, this comparative example adjusts the cooling method as follows: the high-temperature zone and the low-temperature zone are simultaneously reduced to 75°C and 25°C respectively at a rate of 3.96°C / min, and then both the high-temperature zone and the low-temperature zone are naturally cooled to room temperature; other conditions remain the same as in Example 1.

[0150] No black phosphorus arsenic single crystal material was obtained in this comparative example.

[0151] See Figure 30As shown, although the X-ray diffraction pattern of the black phosphorus arsenic material obtained in this comparative example shows obvious preferential growth of the (010) crystal plane family, diffraction peaks representing other crystal planes still exist, such as (021) and (041), indicating that the product is still polycrystalline.

[0152] See Figure 31 As shown, the selected area electron diffraction pattern of the black phosphorus arsenic material obtained in this comparative example shows a lattice of one main crystal plane, while other orientations of the lattice still exist, indicating that the product is still polycrystalline.

[0153] In summary, the above-described technical solutions of the present invention are merely preferred embodiments of the present invention and do not limit the patent scope of the present invention. All equivalent structural transformations made using the contents of the present invention's specification and drawings under the technical concept of the present invention, or direct / indirect applications in other related technical fields, are included within the patent protection scope of the present invention.

Claims

1. A method for preparing a black phosphorus arsenic material, characterized in that, include: In a sealed container under a protective atmosphere or vacuum, gray arsenic, red phosphorus, and additives are mixed and placed in a high-temperature region for reaction, while simultaneously crystallizing and depositing in a low-temperature region to obtain black phosphorus arsenic material. The additive is tellurium iodide; the temperature of the high-temperature region is not lower than 550°C, and the temperature of the low-temperature region is 450~530°C; the black phosphorus arsenic material is black phosphorus arsenic single crystal; the reaction time is less than 20 h; after the reaction is completed, the high-temperature region and the low-temperature region are cooled simultaneously, and the cooling method is rapid cooling.

2. The preparation method according to claim 1, characterized in that, The reaction lasts for 6 to 12 hours.

3. The preparation method according to claim 1, characterized in that, The mass of the tellurium iodide is 1 to 10% of the total mass of the gray arsenic, the red phosphorus, and the additives.

4. The preparation method according to claim 3, characterized in that, The mass of tellurium iodide is 2-7% of the total mass of the gray arsenic, the red phosphorus, and the additives.

5. The preparation method according to claim 1, characterized in that, The atomic ratio of the gray arsenic to the red phosphorus is 4:1 to 1:

2.

6. The preparation method according to claim 1, characterized in that, Once the temperatures of the high-temperature region and the low-temperature region stabilize, the temperature of the high-temperature region is 550~600℃; and the temperature of the low-temperature region is 480~520℃.

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