Preparation method of boron arsenide film
By using a substrate covered with two-dimensional van der Waals material and high-temperature hot melt treatment in the quartz tube, the problem of boron arsenide film growth control is solved, and high-quality and low-defect film preparation is achieved, which is suitable for high-efficiency energy conversion of electronic devices.
Patent Information
- Application Number
- CN202411103847.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-08-13
- Publication Date
- 2024-12-27
AI Technical Summary
The prior art is difficult to effectively prepare boron arsenide films, which leads to limited application in electronic devices, because boron arsenide has few nucleation sites on the substrate surface and is difficult to nucleate uniformly, which in turn affects the growth control and quality of the film.
Using high-temperature hot melting and annealing treatment methods in quartz tubes, a substrate covered by two-dimensional van der Waals material is used to grow boron arsenide films through Van der Waals epitaxial technology, and the growth of the film is controlled by adjusting the argon pressure in the quartz tubes to ensure the formation of Uniformity of nuclear sites and film quality.
The uniform nucleation and high-quality growth of boron arsenide film are achieved, and the problems of unstable film thickness and crystal quality are overcome. They are suitable for the preparation of flexible materials, reduce the weight of the equipment, and improve the energy conversion efficiency.
Smart Images
Figure CN119194595A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of boron arsenide semiconductor materials, and in particular relates to a method for preparing a boron arsenide film. Background Art
[0002] With the development of new energy electric vehicles and communication technology, the demand for high-power and fast-response electronic devices in modern electronic devices has increased dramatically. At the same time, due to the large-scale integration and continuous reduction in size of semiconductor devices, the power density of electronic devices has increased significantly, and heat dissipation has become an increasingly urgent problem in modern electronic devices.
[0003] Boron arsenide is a semiconductor material with both high thermal conductivity and high bipolar mobility. On the one hand, its high thermal conductivity gives it a unique advantage in the application of integrated circuit thermal management, which can ensure that the device can quickly dissipate heat while operating at high power and high speed, effectively reduce the device temperature, and improve the performance of the device. Compared with materials such as diamond with high thermal conductivity, boron arsenide materials have lower requirements for manufacturing equipment, simple preparation methods, and low costs. On the other hand, boron arsenide has high carrier mobility, which makes it show great application potential in high-speed semiconductor devices. In addition, the thermal expansion coefficient of boron arsenide also matches that of conventional semiconductor materials, so that when the temperature changes, there will be no problems of structural or component damage caused by thermal expansion differences.
[0004] It can be seen that boron arsenide materials have broad application prospects in the field of modern electronic devices. They are expected to become a new type of semiconductor material that can achieve device-level heat dissipation, providing the best solution to the technical bottleneck of heat dissipation of semiconductor devices and optoelectronic devices in modern electronic equipment. The current reports on the preparation of boron arsenide are all about the preparation of boron arsenide single crystals. Compared with boron arsenide single crystals, boron arsenide thin films have greater advantages in both preparation and application. However, because boron arsenide has few nucleation sites on the substrate surface and cannot nucleate uniformly, it is difficult to grow thin films effectively. Therefore, there is still a technical gap in the technical field of rapid preparation of boron arsenide thin films. Summary of the invention
[0005] The purpose of this section is to summarize some aspects of embodiments of the present invention and briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section and the specification abstract and the invention title of this application to avoid blurring the purpose of this section, the specification abstract and the invention title, and such simplifications or omissions cannot be used to limit the scope of the present invention.
[0006] In view of the above problems and / or the problems existing in the prior art, the present invention is proposed.
[0007] Therefore, the object of the present invention is to overcome the deficiencies in the prior art and provide a method for preparing a boron arsenide film.
[0008] In order to solve the above technical problems, the present invention provides the following technical solutions: comprising:
[0009] The raw materials are placed into one end of a container that is resistant to high temperatures and does not participate in the reaction, and then a substrate material covered with a two-dimensional van der Waals material on one side is placed into a quartz tube;
[0010] Wherein, the raw materials are boron powder and arsenic particles with a purity of >99%, and the side of the substrate material covered with the two-dimensional van der Waals material faces the raw materials;
[0011] After the quartz tube is evacuated to a vacuum, argon gas is introduced to adjust the pressure inside the tube, and the quartz tube is sealed by heat melting treatment. The end of the sealed quartz tube containing the raw material is the high-temperature end, and the position of the substrate material is the low-temperature end. Heating treatment and annealing treatment are performed in sequence to obtain a boron arsenide film.
[0012] As a preferred solution of the method for preparing the boron arsenide film of the present invention, the molar ratio of the boron powder to the arsenic particles in the raw materials is 55:1 to 8:1.
[0013] As a preferred scheme of the preparation method of the boron arsenide film described in the present invention, wherein: the substrate covered with a two-dimensional van der Waals material, wherein the two-dimensional van der Waals material includes a single-layer boron nitride, a multilayer boron nitride with 2 to 5 layers, a single-layer graphene, a multilayer graphene, molybdenum disulfide, tungsten sulfide, molybdenum selenide, and tungsten selenide.
[0014] As a preferred solution of the method for preparing the boron arsenide film of the present invention, the substrate comprises silicon wafer, quartz, aluminum oxide, calcium fluoride, magnesium oxide, magnesium fluoride, and silicon carbide.
[0015] As a preferred solution of the method for preparing the boron arsenide film of the present invention, wherein: the pressure in the tube is adjusted by introducing argon gas to adjust the pressure in the tube to 10 mTorr to 200 Torr.
[0016] As a preferred solution of the method for preparing the boron arsenide film of the present invention, wherein: the heating treatment, wherein the heating temperature at the high temperature end is 800-890°C, and the heating temperature at the low temperature end is 600-790°C.
[0017] As a preferred solution of the method for preparing the boron arsenide film of the present invention, the heat treatment is carried out for a holding time of 3 to 7 hours.
[0018] As a preferred solution of the method for preparing the boron arsenide film of the present invention, the annealing treatment is carried out under vacuum conditions, the treatment temperature is 500-700° C., and the treatment time is 20 min-60 min.
[0019] Another object of the present invention is to provide a boron arsenide film.
[0020] Another object of the present invention is to provide a boron arsenide film for use as a semiconductor material in the preparation of modern electronic devices.
[0021] Beneficial effects of the present invention:
[0022] The present invention grows a cubic boron arsenide thin film material on the surface of a two-dimensional van der Waals material (single layer or multilayer) by van der Waals epitaxy, so that the nucleation sites are uniform and controllable, boron arsenide can be uniformly filmed on the two-dimensional van der Waals material, and a high-quality, low-defect boron arsenide film can be prepared in a short time.
[0023] The present application introduces argon gas into a quartz tube and adjusts the gas pressure in the tube. By adjusting the gas pressure in the tube, the partial pressures of different gas phase components can be controlled, thereby accelerating the growth of the boron arsenide film and optimizing the film quality.
[0024] Compared with the preparation of boron arsenide single crystals, the preparation method of the present application can effectively overcome technical obstacles such as the difficulty in controlling the thickness and uniformity of boron arsenide film growth, crystal quality, and performance stability. The prepared boron arsenide film is suitable for the preparation of flexible materials, reduces the weight of equipment, and can achieve efficient energy conversion. BRIEF DESCRIPTION OF THE DRAWINGS
[0025] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for describing the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative labor. Among them:
[0026] Figure 1 This is a schematic diagram of preparing a boron arsenide film according to the present invention.
[0027] Figure 2 This is the XRD diffraction pattern of the boron arsenide film prepared in Example 1 of the present invention.
[0028] Figure 3 This is the XRD diffraction pattern of the boron arsenide film prepared in Example 2 of the present invention.
[0029] Figure 4 This is the XRD diffraction pattern of the boron arsenide film prepared in Example 3 of the present invention.
[0030] Figure 5 This is the XRD diffraction pattern of the boron arsenide film prepared in Example 4 of the present invention.
[0031] Figure 6 This is the XRD diffraction pattern of the boron arsenide film prepared in Example 5 of the present invention.
[0032] Figure 7 This is the XRD diffraction pattern of the boron arsenide film prepared in Example 6 of the present invention.
[0033] Figure 8 This is the XRD diffraction pattern of the boron arsenide film prepared in Example 7 of the present invention.
[0034] Fig. 9 This is the XRD diffraction pattern of the boron arsenide film prepared in Example 8 of the present invention.
[0035] Fig.10 This is a substrate sample diagram prepared in Comparative Example 1 of the present invention.
[0036] Fig.11 This is a microscopic picture of the sample prepared in Comparative Example 2 of the present invention. DETAILED DESCRIPTION
[0037] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the specific implementation methods of the present invention are described in detail below in conjunction with the embodiments of the specification.
[0038] In the following description, many specific details are set forth to facilitate a full understanding of the present invention, but the present invention may also be implemented in other ways different from those described herein, and those skilled in the art may make similar generalizations without violating the connotation of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.
[0039] Secondly, the term "one embodiment" or "embodiment" as used herein refers to a specific feature, structure, or characteristic that may be included in at least one implementation of the present invention. The term "in one embodiment" that appears in different places in this specification does not necessarily refer to the same embodiment, nor does it refer to a separate or selective embodiment that is mutually exclusive with other embodiments.
[0040] The quartz tube used in the present invention has a diameter of 20 mm, a length of 300 mm, and a wall thickness of 1 mm;
[0041] The substrate holder used in the present invention has a diameter of 17 mm, a length of 10 mm, and a wall thickness of 2 mm. A micro electric grinder is used to cut a 15 mm long and 2 mm wide incision 5 mm away from one end of the substrate holder so that the incision can vertically insert a 10 mm×10 mm×0.5 mm substrate;
[0042] The quartz tube and substrate support used in the present invention need to be pretreated before use, including:
[0043] Deionized water, isopropanol with a purity greater than 99.5%, anhydrous ethanol with a purity of 99.99%, and deionized water were used in an ultrasonic cleaning machine for cleaning for 10 minutes each. After cleaning, a high-pressure air gun was used to blow away the residual water on the quartz tube and the substrate holder;
[0044] A small-caliber flame spray gun is used to heat the tube 50 mm away from the bottom. During heating, the quartz tube rotates continuously and is heated evenly, so that the tube diameter at this point is slightly smaller than the substrate holder, which can prevent the substrate from directly contacting the raw materials and avoid contamination of the substrate surface.
[0045] The raw materials used in the present invention are all commercially available in the art unless otherwise specified, wherein the purity of boron powder (Aladdin) and arsenic particles is 99.9% to 99.999% (3A materials).
[0046] Example 1
[0047] Reference Figure 1 , is a schematic diagram of preparing a boron arsenide film according to the present invention. This embodiment provides a method for preparing a boron arsenide film, specifically:
[0048] 1) 0.8 g of boron powder and 0.5 g of arsenic particles (molar ratio of 11:1) were weighed and loaded into one end of a quartz tube, and a silicon dioxide substrate material covered with a single layer of boron nitride (h-BN) film on one side was inserted into a substrate holder and then placed into the quartz tube. The substrate was positioned about 105 mm from the bottom of the tube, and the side of the substrate material covered with the two-dimensional van der Waals material faced the raw material;
[0049] 2) After the quartz tube is evacuated to a vacuum, argon gas is introduced to adjust the pressure in the tube to 150 mTorr, and the quartz tube is sealed by heat melting treatment. The end of the sealed quartz tube containing the raw material is the high-temperature end, and the position of the substrate material is the low-temperature end. The high-temperature end is heated to 890° C., and the low-temperature end is heated to 780° C., and the heat treatment is carried out for 3 hours. At this time, the thickness of the film obtained is about 500 nm. Then, an annealing operation is performed in a vacuum environment at a temperature of 600° C. for 20 minutes to obtain the boron arsenide film of this embodiment, and its XRD diffraction pattern is as shown in the figure. Figure 2 shown.
[0050] Example 2
[0051] The difference between this embodiment and Example 1 is that the two-dimensional van der Waals material in step 1) is adjusted to a single-layer graphene, and the remaining steps and processes are all referred to Example 1, to obtain a boron arsenide film of this embodiment, whose XRD diffraction pattern is as shown in FIG. Figure 3 shown.
[0052] Example 3
[0053] The difference between this embodiment and Example 1 is that the molar ratio of boron powder to arsenic particles in step 1) is adjusted to 8:1, and the remaining steps are all based on Example 1 to obtain a boron arsenide film of this embodiment. Its XRD diffraction pattern is as follows: Figure 4 shown.
[0054] Example 4
[0055] The difference between this embodiment and Example 1 is that the quartz tube in step 2) is evacuated to vacuum and argon gas is introduced to adjust the pressure in the tube to 10 mTorr. The remaining steps and processes are the same as those in Example 1. The boron arsenide film of this embodiment is obtained. Its XRD diffraction pattern is as follows: Figure 5 shown.
[0056] Example 5
[0057] The difference between this embodiment and Example 1 is that the heat preservation treatment time of step 2) is adjusted to 3 hours, and the remaining steps are all based on Example 1 to obtain the boron arsenide film of this embodiment, and its XRD diffraction pattern is as follows: Figure 6 shown.
[0058] from Figure 2 to Figure 6 It can be seen that the films prepared in Examples 1 to 5 of the present invention have high crystallinity - the higher the (111) peak value, the better the crystal quality of the film, and the film prepared in Example 1 is the best.
[0059] Example 6
[0060] The difference between this embodiment and Example 1 is that the molar ratio of boron powder to arsenic particles in step 1) is adjusted to 55:1, and the remaining steps are all based on Example 1 to obtain a boron arsenide film of this embodiment, whose XRD diffraction pattern is as follows: Figure 7 shown.
[0061] Example 7
[0062] The difference between this embodiment and Example 1 is that the quartz tube in step 2) is evacuated to vacuum and argon gas is introduced to adjust the pressure in the tube to 200 Torr. The remaining steps and processes are the same as those in Example 1. The boron arsenide film of this embodiment is obtained. Its XRD diffraction pattern is as follows: Figure 8 shown.
[0063] Example 8
[0064] The difference between this embodiment and Example 1 is that the heat preservation treatment time of step 2) is adjusted to 7 hours, and the remaining steps and processes are all referred to Example 1, and the boron arsenide film of this embodiment is obtained, and its XRD diffraction pattern is as follows: Fig. 9 shown.
[0065] from Figure 7 to Figure 9 It can be seen that boron arsenide thin films can still be produced under the conditions of Examples 6 to 8 of the present invention, but the crystallinity is slightly lower than that of Examples 1 to 5.
[0066] Comparative Example 1
[0067] The difference between this comparative example and Example 1 is that the substrate in the adjustment step 1) does not contain van der Waals material, and the remaining steps and processes are all based on Example 1 to obtain the sample of this example. Figure 7 shown.
[0068] from Fig.10 It can be seen that boron arsenide films cannot be grown on substrates that do not contain two-dimensional van der Waals materials.
[0069] Comparative Example 2
[0070] The difference between this comparative example and implementation 1 is that the molar ratio of boron powder to arsenic particles in step 1) is adjusted to 56:1, and the remaining steps and processes are all referred to implementation 1. The electron microscope image of the product of this comparative example is as follows: Fig.11 The results show that this comparative example cannot produce a continuous film.
[0071] In summary, the present application grows cubic phase boron arsenide thin film material on the surface of a two-dimensional van der Waals material (single layer or multilayer) by van der Waals epitaxy, so that the nucleation sites are uniform and controllable, boron arsenide can be uniformly film-formed on the two-dimensional van der Waals material, and high-quality, low-defect boron arsenide thin films can be prepared in a short time. In addition, only within the scope of the present invention can a thin film with excellent crystallization be prepared. If it exceeds the scope of the present invention, such as the solution of Comparative Example 2, the crystallinity of the thin film will decrease and a continuous thin film cannot be prepared.
[0072] The present application introduces argon gas into a quartz tube and adjusts the gas pressure in the tube. By adjusting the gas pressure in the tube, the partial pressures of different gas phase components can be controlled, thereby accelerating the growth of the boron arsenide film and optimizing the film quality.
[0073] Compared with the preparation of boron arsenide single crystals, the preparation method of the present application can effectively overcome technical obstacles such as the difficulty in controlling the thickness and uniformity of boron arsenide film growth, crystal quality, and performance stability. The prepared boron arsenide film is suitable for the preparation of flexible materials, reduces the weight of equipment, and can achieve efficient energy conversion.
[0074] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the spirit and scope of the technical solutions of the present invention, which should all be included in the scope of the claims of the present invention.
Claims
1. A method for preparing a boron arsenide thin film, characterized in that: include, The raw materials are placed into one end of a container that is resistant to high temperatures and does not participate in the reaction, and then a substrate material covered with a two-dimensional van der Waals material on one side is placed into a quartz tube; Wherein, the raw materials are boron powder and arsenic particles with a purity of >99%, and the side of the substrate material covered with the two-dimensional van der Waals material faces the raw materials; After the quartz tube is evacuated to a vacuum, argon gas is introduced to adjust the pressure inside the tube, and the quartz tube is sealed by heat melting treatment. The end of the sealed quartz tube containing the raw material is the high-temperature end, and the position of the substrate material is the low-temperature end. Heating treatment and annealing treatment are performed in sequence to obtain a boron arsenide film.
2. The method for preparing a boron arsenide thin film according to claim 1, characterized in that: The molar ratio of boron powder to arsenic particles in the raw materials is 55:1 to 8:
1.
3. The method for preparing a boron arsenide thin film according to claim 1, characterized in that: The substrate is covered with a two-dimensional van der Waals material, wherein the two-dimensional van der Waals material includes a single-layer boron nitride, a multilayer boron nitride with 2 to 5 layers, a single-layer graphene, a multilayer graphene, molybdenum disulfide, tungsten sulfide, molybdenum selenide, and tungsten selenide.
4. The method for preparing a boron arsenide thin film according to claim 3, characterized in that: The substrate includes one of silicon wafer, quartz, aluminum oxide, calcium fluoride, magnesium oxide, magnesium fluoride, and silicon carbide.
5. The method for preparing a boron arsenide thin film according to claim 1, wherein: The argon gas is introduced to adjust the pressure in the tube to 10 mTorr to 200 Torr.
6. The method for preparing a boron arsenide thin film according to claim 1, wherein: In the heating treatment, the heating temperature at the high temperature end is 800-890°C, and the heating temperature at the low temperature end is 600-790°C.
7. The method for preparing a boron arsenide thin film according to claim 6, characterized in that: The heat preservation time of the heating treatment is 3 to 7 hours.
8. The method for preparing a boron arsenide thin film according to claim 1, wherein: The annealing treatment is carried out under vacuum conditions, with a treatment temperature of 500-700° C. and a treatment time of 20 min-60 min.
9. The boron arsenide thin film prepared by the preparation method according to any one of claims 1 to 8.
10. Use of the boron arsenide film as claimed in claim 9 as a semiconductor material in the preparation of modern electronic devices.