CN112159970B - Preparation method of wafer-level high-quality boron nitride/graphene heterojunction film - Google Patents
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- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 229910052582 BN Inorganic materials 0.000 title claims abstract description 80
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 55
- 239000002184 metal Substances 0.000 claims abstract description 49
- 229910052751 metal Inorganic materials 0.000 claims abstract description 49
- 238000009792 diffusion process Methods 0.000 claims abstract description 18
- 239000011888 foil Substances 0.000 claims abstract description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 17
- 238000007789 sealing Methods 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 14
- 125000004429 atom Chemical group 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 230000003197 catalytic effect Effects 0.000 claims abstract description 6
- 238000005516 engineering process Methods 0.000 claims abstract description 6
- 238000001020 plasma etching Methods 0.000 claims abstract description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 238000012546 transfer Methods 0.000 claims description 14
- 238000005530 etching Methods 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 13
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 238000000137 annealing Methods 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 229910000085 borane Inorganic materials 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 230000005587 bubbling Effects 0.000 claims description 5
- 238000005229 chemical vapour deposition Methods 0.000 claims description 5
- 239000011229 interlayer Substances 0.000 claims description 5
- 239000010410 layer Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- BGECDVWSWDRFSP-UHFFFAOYSA-N borazine Chemical group B1NBNBN1 BGECDVWSWDRFSP-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000012159 carrier gas Substances 0.000 claims description 2
- 230000001276 controlling effect Effects 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- 229910001325 element alloy Inorganic materials 0.000 claims 2
- GPVMAMPCGCPARN-UHFFFAOYSA-N N.CB(C)C Chemical compound N.CB(C)C GPVMAMPCGCPARN-UHFFFAOYSA-N 0.000 claims 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims 1
- 239000004202 carbamide Substances 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- 239000012535 impurity Substances 0.000 claims 1
- 150000002739 metals Chemical class 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 229910052755 nonmetal Inorganic materials 0.000 claims 1
- 150000002843 nonmetals Chemical class 0.000 claims 1
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- 238000006243 chemical reaction Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- 238000005204 segregation Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000005669 field effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 229910000570 Cupronickel Inorganic materials 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 102000020897 Formins Human genes 0.000 description 2
- 108091022623 Formins Proteins 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000002457 bidirectional effect Effects 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 238000005255 carburizing Methods 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000011978 dissolution method Methods 0.000 description 2
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- 229920006280 packaging film Polymers 0.000 description 2
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- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- UORVGPXVDQYIDP-BJUDXGSMSA-N borane Chemical group [10BH3] UORVGPXVDQYIDP-BJUDXGSMSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 1
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/01—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes on temporary substrates, e.g. substrates subsequently removed by etching
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
- C23C16/342—Boron nitride
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- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
The invention discloses a preparation method of a wafer-level high-quality boron nitride/graphene heterojunction film; the preparation method comprises the following steps: step one: preparing a continuous hexagonal boron nitride film on the surface of the metal by a surface catalytic growth method; step two: removing the hexagonal boron nitride film on one side surface of the metal foil by a plasma etching technology; step three: folding the metal foil into a bag shape for sealing; step four: placing the metal bag in a tube furnace, raising the temperature to a certain level, and introducing high-concentration carbon-containing gas to realize the diffusion of carbon atoms from the outer surface to the inner surface, and separating out the carbon atoms in the cooling process, so as to generate graphene at the interface of the metal and hexagonal boron nitride; step five: and cutting off the metal bag, horizontally spreading the metal bag, and transferring the metal bag to the surface of a target substrate to obtain the hexagonal boron nitride/graphene vertical heterojunction film. The preparation process of the invention has high applicability and wider process parameter window; compared with the traditional method for preparing the heterojunction by an epitaxial or diffusion mode, the method effectively avoids the doping phenomenon among atoms, and meanwhile, the wafer-level high-quality vertical boron nitride/graphene heterojunction film can be obtained.
Description
Technical Field
The invention relates to a preparation method of a wafer-level high-quality boron nitride/graphene heterojunction film, and belongs to the field of film materials.
Background
Microelectronics is the core technology of the high-tech and information industry and we can call the information-based armed device's fairy. With the continuous progress of technology, from the fields of household appliances, mobile communication, computers, satellite navigation, deep sea exploration and the like to the hot unmanned operation in the current society, intelligent manufacturing, quantum communication and the like depend on the development of microelectronic devices. In recent years, two-dimensional electronic materials which are rapidly developed show a series of new physical phenomena and unique electronic transport characteristics, and a new way is provided for realizing novel high-performance electronic devices. The graphene is a micro-nano electronic device material with great potential.
One of the biggest challenges faced by two-dimensional materials represented by graphene in device field applications is the interface problem with dielectric materials. The specific surface area of the graphene is large, and the surface state and the carrier trap center are easily introduced in various process stages of preparation, transfer, device processing and the like, so that the device performance of the graphene is greatly reduced. Hexagonal boron nitride has higher dielectric strength, atom-level flatness and excellent heat conducting capacity. Graphene may be an ideal dielectric material for graphene. The controlled growth of high quality, large area hexagonal boron nitride/graphene vertical heterojunction structures is a critical scientific issue that is now urgently needed to be studied.
However, the current method for directly preparing the hexagonal boron nitride/graphene heterojunction with clean interface, no doping and high quality has certain problems. For example, 1) a method for constructing a vertical heterojunction by means of micro-mechanical stripping and micro-transfer has high process randomness, poor repeatability and very limited heterojunction sample size; 2) Graphene is directly grown on the surface of hexagonal boron nitride by a CVD epitaxial method, uniformity and continuity of the graphene in a large area range in the obtained heterojunction are poor, and adverse interlayer etching and doping phenomena in a heterojunction sample can be caused by a higher epitaxial growth temperature. 3) Through a pre-dissolution and segregation method, carbon atoms are pre-dissolved in the metal, and a graphene/boron nitride heterojunction is generated in the cooling process. Patent CN201610895790.3 "a method for preparing graphene and hexagonal boron nitride composite film material" describes a one-step growth method. Preparing h-BN on the surface of a metal substrate in which carbon atoms with a certain concentration are dissolved in advance by a chemical vapor deposition method, controlling the dissolution and precipitation of carbon in the metal substrate in the cooling process, and growing graphene between the h-BN and the metal substrate to obtain the h-BN/graphene/metal substrate. In patent CN201610652002.8, "a preparation method of a graphene-based two-dimensional layered heterojunction", a gaseous carbon source is also used to pre-dissolve into a metal substrate. The Peng Hailin teaching of Beijing university et al adopts a co-segregation method to dissolve carbon atoms and B, N atoms into the metal Ni in advance to form a sandwich structure, and the dissolved atoms gradually precipitate in the annealing process to form an h-BN/graphene heterojunction structure. (C.H.Zhang et al, "Direct growth of large-area graphene and boron nitrideheterostructures by a co-segregation method". Nature Communications,2015, 6:6519). The pre-dissolution and segregation methods used in the above patents and literature have the problem that carbon atoms pre-dissolved in metal easily enter the boron nitride interlayer during the growth of the boron nitride film, and atomic doping is generated.
Disclosure of Invention
Aiming at the problems, the preparation method adopts an effective mode to realize the preparation of the graphene/hexagonal boron nitride vertical heterojunction film with large area, high quality and high uniformity.
The invention relates to a preparation method of a wafer-level high-quality boron nitride/graphene heterojunction film, which comprises the following steps:
step one: preparing a continuous hexagonal boron nitride film on the surface of the metal by a surface catalytic growth method;
step two: removing the hexagonal boron nitride film on one side surface of the metal foil by a plasma etching technology;
step three: folding the metal foil into a bag shape for sealing, wherein a boron nitride film grows on the inner surface of the sealing bag, and the outer surface of the sealing bag is free of the boron nitride film;
step four: the metal bag is placed in a tube furnace, the temperature is raised to a certain level, and high-concentration carbon-containing gas is introduced, so that the diffusion of carbon atoms from the outer surface to the inner surface is realized. Slowly cooling, slowly separating out carbon atoms, and generating graphene at the interface of the metal and the hexagonal boron nitride;
step five: the metal bag is sheared and spread, and the hexagonal boron nitride/graphene vertical heterojunction film can be obtained on the surface of the target substrate through wet transfer, bubbling transfer, dry transfer and other methods.
Preferably, the preparation process of the hexagonal boron nitride film in the first step is a chemical vapor deposition method, the metal substrate used for growth is a metal foil, the surface roughness of the foil is less than 5nm, the raw material adopts borazine or borane ammonia complex, the evaporation temperature is room temperature to 120 ℃, the evaporation device adopts a bubbling method, a water bath heating method or a heating belt direct heating method, the growth temperature is 400 to 1200 ℃, the growth time is 5 to 120min, the carrier gas is argon gas mixture containing a certain proportion of hydrogen, and the hydrogen volume content is 2.5 to 50 percent.
Preferably, the plasma etching process in the second step is as follows; the etching gas is argon, hydrogen or oxygen plasma, and the power of the radio frequency power supply is 100W-250W. In the etching process, the metal foil is horizontally arranged on the surface of the quartz plate, and four sides are encapsulated by polymers such as polyvinyl alcohol (PVA), polymethyl methacrylate (PDMS), ethylene-octene copolymer (POE) and the like, so that the hexagonal boron nitride film on the other side is prevented from being etched by plasma.
Preferably, the metal bag in the third step is in a completely sealed state. When in manufacture, the three opening edges are folded for 2-3 times, and certain pressure is applied. The metal strip should be heated to 800-1050 ℃ for annealing for 5-30min to ensure complete sealing of the metal bag.
Preferably, the conditions in the fourth step are that the diffusion process temperature is 500-850 ℃, so that the inter-layer atomic doping is avoided under the condition of higher temperature, and the generated heterojunction structure interface doping is caused. The diffusion process is carried out under normal pressure, the concentration of carbon atoms is 1% -25%, the diffusion time is 0.5-25h, and the cooling rate is 0.1-25 ℃/min.
The invention relates to a preparation method of a wafer-level high-quality boron nitride/graphene heterojunction film, which divides the growth of boron nitride and the growth of graphene into two mutually independent paths, and the sealed metal bag structure and the lower diffusion temperature greatly reduce the interlayer atom doping effect and ensure the purity of a vertical heterojunction structure interface.
Compared with the prior art, the invention has the beneficial effects that:
1. in step one, the metal is not subjected to any pre-dissolution of carbon atoms while growing the boron nitride film. The boron nitride prepared at this time is a pure film.
2. In step four, by adopting a sealed metal bag structure, carbon atoms diffuse from the outer surface of the metal bag and enter the inner surface, segregate on the inner surface and form graphene between the boron nitride and the inner surface of the metal. In this process, carbon atoms are always in a low concentration state at the inner surface covered with boron nitride, reducing the probability of interatomic doping.
3. In the fourth step, the diffusion temperature is always lower than 850 ℃ in the process that carbon atoms diffuse from the outer surface of the metal bag and enter the inner surface. At this time, the boron nitride which has completed growing is in a chemically stable state, and the doping phenomenon between heterojunction layers promoted by high temperature is effectively inhibited.
4. Boron nitride in the heterojunction prepared by the method is obtained by surface catalytic growth, and graphene is obtained by carbon atom diffusion and segregation growth; the two synthesis paths are independent of each other and do not affect each other. The thicknesses of the boron nitride layer and the graphene layer in the heterojunction can be independently regulated and controlled.
5. Graphene in the heterojunction prepared by the method is obtained through carbon atom diffusion and segregation growth, and graphene is generated through slow precipitation by reducing the cooling rate, so that the graphene has higher uniformity compared with an island-shaped growth mode in the epitaxial growth process.
6. The size of the heterojunction prepared by the method is completely dependent on the size of the metal bag and the pipe diameter of the high-temperature furnace pipe, so that the wafer-level vertical heterojunction film can be prepared.
Drawings
For ease of illustration, the invention is described in detail by the following detailed description and the accompanying drawings.
FIG. 1 is a schematic diagram of a growth process according to the present invention;
FIG. 2 is a digital photograph of a wafer level boron nitride/graphene vertical heterojunction film prepared in example 1 of the present invention;
FIG. 3 shows the Raman spectrum and the UV-visible absorption spectrum of the boron nitride/graphene vertical heterojunction film prepared in example 1 of the present invention;
fig. 4 is a comparison of the bidirectional transfer curves of the field effect crystals of the pure graphene and the boron nitride/graphene vertical heterojunction film prepared in comparative example 1 and example 1.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the present invention is described below by means of specific embodiments shown in the accompanying drawings. It should be understood that the description is only illustrative and is not intended to limit the scope of the invention. In addition, in the following description, descriptions of well-known structures and techniques are omitted so as not to unnecessarily obscure the present invention.
Example 1
Surface catalytic growth of boron nitride films: the growth of hexagonal boron nitride is performed in a chemical vapor deposition system, and the precursor is borane ammonia complex. Cut about 5X 5cm before reaction 2 The copper-nickel alloy foil with the size is placed at the center of a quartz tube, about 10mg of borane ammonia complex is weighed and placed at the front end of a tube furnace at a position 30-60cm away from the central region of the furnace temperature. Before heating, the system is vacuumized, inert protective gas is introduced to normal pressure, and the operation is repeated for 2 times, so that the air in the pipeline is exhausted. Maintaining the flow of inert protective gas at 500sccm, the pressure at normal pressure, and the temperature rising rate at 5-50deg.C for min -1 . When the furnace temperature is raised to the reaction temperature, the raw materials are thermally decomposed by using a heating belt device, and the growth time is 30-60min. After the reaction, the heating belt is closed, and the system is slowly cooled.
Removing the boron nitride film on one side surface: and after the first step of reaction is finished, firstly removing the hexagonal boron nitride film on one side of the surface of the copper-nickel alloy foil. Firstly, the sample obtained by the previous growth step is horizontally placed on the surface of a quartz plate, and four sides of the sample are packaged by adopting a polyvinyl alcohol film. And etching the surface by using argon plasma, wherein the power is 100W and the time is 30min.
Preparing a sealing bag structure: and slowly lifting the polyvinyl alcohol packaging film after etching is finished, and sealing the copper-nickel alloy foil. In the sealing, the side subjected to etching treatment is set as the outer side, and the side which is not subjected to etching treatment and remains with the hexagonal boron nitride film is set as the inner side. To ensure the airtight properties of the sealed bag, the open three sides should be folded, pressed and the edges of the foil fused during the high temperature annealing process. The annealing temperature was 1050℃for 20min.
Diffusion of carbon atoms and precipitation of graphene: the carburizing process is carried out at 800 ℃ in the atmosphere of CH 4 The volume fraction is 5-25%, the hydrogen volume fraction is 1-25% of argon gas mixture, and the diffusion time is generally 0.5-2.5h. After the process is finished, the methane raw material is cut off, and the system is slowly cooled to room temperature.
Transfer of heterojunction: after the reaction, the metal bag is cut and spread, and transferred onto a target substrate by a conventional wet transfer or hydrogen bubbling method. The boron nitride/graphene heterojunction structure can be obtained on the target substrate, the thickness is between 1 and 25nm, and the size is about 4.5X4.5 cm 2 。
Fig. 2 is a digital picture of a wafer level boron nitride/graphene vertical heterojunction obtained in this example.
Fig. 3 is a raman spectrum and an ultraviolet-visible absorption spectrum of the boron nitride/graphene vertical heterojunction obtained in this example. Raman spectra showed typical D, G and 2D peaks of graphene and E2G vibrational peaks of hexagonal boron nitride. The ultraviolet-visible absorption spectrum shows the absorption peak (270 cm) -1 ) Absorption peak with boron nitride (210 cm) -1 )。
Example 2
Surface catalytic growth of boron nitride films: the growth chemical vapor deposition system of hexagonal boron nitride is performed, and the precursor is borazine. Cut about 5X 9cm before reaction 2 A large Ni foil was placed at the center of the quartz tube. Firstly, collecting before heatingThe inert gas is used for washing, and the air in the quartz tube is exhausted as much as possible. The flow rate of the inert protective gas is maintained to be 500sccm, the pressure is normal pressure, and the temperature of the reaction furnace body is raised. The temperature rising rate is 25 ℃ for min -1 . When the furnace temperature is increased to the reaction temperature, the raw materials are introduced into the reaction system by using a bubbling device, and the growth time is 30-60min. And slowly cooling the system after the reaction.
Removing the boron nitride film on one side surface: after the first step of reaction is finished, firstly removing the hexagonal boron nitride film on one side of the surface of the Ni foil. Firstly, the sample obtained in the previous step is horizontally placed on the surface of a quartz plate, and the four sides of the sample are packaged by adopting a polymethyl methacrylate film. And etching the surface by utilizing hydrogen plasma, wherein the power is 125W and the time is 60min.
Preparing a sealing bag structure: and slowly lifting the polymethyl methacrylate packaging film after etching is finished, and sealing the Ni foil. In the sealing, the side subjected to etching treatment is set as the outer side, and the side which is not subjected to etching treatment and remains with the hexagonal boron nitride film is set as the inner side. To ensure the airtight properties of the sealed bag, the open three sides should be folded, pressed and the edges of the foil fused during the high temperature annealing process. The annealing temperature was 1065℃for 10min.
Diffusion of carbon atoms and precipitation of graphene: the carburizing process is carried out at 650 ℃ in the atmosphere of CH 4 The volume fraction is 5-25%, the hydrogen volume fraction is 1-25% of argon gas mixture, and the diffusion time is generally 0.5-2.5h. After the process is finished, the methane raw material is cut off, and the system is slowly cooled to room temperature.
Transfer of heterojunction: after the reaction, the metal bag was cut and spread, and transferred onto a target substrate by a dry transfer method. The boron nitride/graphene heterojunction structure can be obtained on the target substrate, the thickness is between 1 and 50nm, and the size is about 4 multiplied by 8cm 2 。
Comparative example 1
In this comparative example, the first step and the second step of example 1 were omitted, and the remaining methods were the same as those of example 1, thereby obtaining a pure graphene film. A field effect transistor consisting solely of graphene was prepared and compared to the performance of the field effect transistor of the boron nitride/graphene vertical heterojunction shown in the examples of the present invention.
As shown in fig. 4, it is a bidirectional transfer curve of the field effect transistor simply composed of graphene shown in comparative example 1: as can be seen from the figure, the transistor shows remarkable hysteresis in the process of reverse sweeping back of the gate voltage, and the dirac point is far away from the central point. And the field effect transistor of the boron nitride/graphene vertical heterojunction has almost no hysteresis, and the dirac point tends to the center point more. It is demonstrated that the electrical properties of the graphene in comparative example 1 are much lower than those of the boron nitride/graphene vertical heterojunction in example 1.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (9)
1. A preparation method of a wafer-level high-quality boron nitride/graphene heterojunction film is characterized by comprising the following steps of: the preparation method comprises the following steps:
step one: preparing a continuous hexagonal boron nitride film on the surface of the metal by adopting a chemical vapor deposition technology through a surface catalytic growth method;
step two: removing the hexagonal boron nitride film on one side surface of the metal foil by a plasma etching technology;
step three: folding the metal foil into a bag shape for sealing, wherein a boron nitride film grows on the inner surface of the sealing bag, and the outer surface of the sealing bag is free of the boron nitride film;
step four: placing the sealed bag in a tube furnace, raising the temperature to a certain level, introducing high-concentration carbon-containing gas, realizing diffusion of carbon atoms from the outer surface to the inner surface, slowly cooling, slowly separating out carbon atoms, and generating graphene at the interface of metal and hexagonal boron nitride;
step five: the sealing bag is sheared and spread, and the hexagonal boron nitride/graphene vertical heterojunction film can be obtained on the surface of the target substrate through a wet transfer, bubbling transfer or dry transfer method;
the temperature of the diffusion process is 200-850 ℃, the interface impurity of the generated heterojunction structure is avoided due to the inter-layer atomic doping under the higher temperature condition, the diffusion process is carried out under normal pressure, and the atmosphere is CH 4 The volume fraction is 5-25%, the hydrogen volume fraction is 1-25% of argon gas mixture, and the diffusion time is 0.5-2.5h.
2. The method of claim 1, wherein the metal is a metal having a certain carbon-dissolving capacity and its alloy, including a binary or multi-element alloy of a high carbon-dissolving metal Fe, co, ni, rh, ru, ir, a low carbon-dissolving metal Cu, pt, au, ga, ge and the high carbon-dissolving metal, and a multi-element alloy of non-metals B, si, and P and the low carbon-dissolving and high carbon-dissolving metals.
3. The method for preparing a wafer-level, high-quality boron nitride/graphene heterojunction film according to claim 1, wherein the conditions for surface-catalyzed growth of the boron nitride film are as follows: the raw material is a mixture precursor of a compound containing B atoms and a compound containing N atoms or a compound precursor containing both B atoms and N atoms, the growth temperature is 400-1200 ℃, and the carrier gas is a mixed gas of hydrogen and argon, wherein the volume content of the hydrogen is 2.5-50%.
4. The method for preparing a wafer-level, high-quality boron nitride/graphene heterojunction film according to claim 3, wherein,
the B atom-containing compound is boron powder, borane or organoborane BR 3 ；
The compound containing N atoms is nitrogen, ammonia or urea;
the compound containing B atom and N atom is borazine, borane ammonia complex, trimethylborane ammonia or B 3 N 3 Cl 6 。
5. The method for preparing a wafer-level, high-quality boron nitride/graphene heterojunction film as claimed in claim 4, wherein said borane has a formula of B n H n+4 N is a positive integer.
6. The method for preparing the wafer-level high-quality boron nitride/graphene heterojunction film according to claim 1, wherein the condition for etching the hexagonal boron nitride film on the surface of one side of the metal is a plasma atmosphere of one gas of argon, oxygen and hydrogen and a mixed gas thereof, the power is 25W-250W, the metal foil is horizontally arranged on the surface of a horizontal substrate in the etching process, and four sides are encapsulated by polyvinyl alcohol, polymethyl methacrylate or ethylene-octene copolymer polymer, so that the hexagonal boron nitride film on the other side is prevented from being etched by the plasma.
7. The method for preparing the wafer-level high-quality boron nitride/graphene heterojunction film according to claim 1, wherein the method comprises the following steps: the bag is completely sealed and airtight, wherein a boron nitride film grows on the inner surface of the bag, and the outer surface of the bag is free of the boron nitride film; when in manufacture, the three opening edges are folded for 2-3 times, and certain pressure is applied, the sealed bag is heated to 800-1050 ℃ for annealing, and the annealing time is 5-30min, so as to ensure that the sealed bag is completely sealed.
8. The method for preparing the wafer-level high-quality boron nitride/graphene heterojunction film according to claim 1, wherein the thickness of the boron nitride/graphene vertical heterojunction film is between 0.5 and 50nm, and the method can be used for independently regulating and controlling the thickness of the upper layer boron nitride and the thickness of the lower layer graphene.
9. The method for preparing a wafer-level high-quality boron nitride/graphene heterojunction film according to claim 1, wherein the planar area of the boron nitride/graphene vertical heterojunction structure is 0.01-200cm 2 And the area of the device only depends on the size of the sealing bag and the volume of the tube furnace, and in the actual preparation process, the growth device can be correspondingly modified, so that the plane area of the device is further increased.
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