CN112159970A - Preparation method of wafer-level high-quality boron nitride/graphene heterojunction film - Google Patents
Preparation method of wafer-level high-quality boron nitride/graphene heterojunction film Download PDFInfo
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- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910052582 BN Inorganic materials 0.000 title claims abstract description 74
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 57
- 229910052751 metal Inorganic materials 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 56
- 238000009792 diffusion process Methods 0.000 claims abstract description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 18
- 239000011888 foil Substances 0.000 claims abstract description 17
- 239000000758 substrate Substances 0.000 claims abstract description 16
- 238000007789 sealing Methods 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000005516 engineering process Methods 0.000 claims abstract description 8
- 125000004429 atom Chemical group 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 230000003197 catalytic effect Effects 0.000 claims abstract description 7
- 238000001020 plasma etching Methods 0.000 claims abstract description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 238000012546 transfer Methods 0.000 claims description 14
- 238000005530 etching Methods 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 12
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- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 238000000137 annealing Methods 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 7
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- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- 239000010410 layer Substances 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 230000005587 bubbling Effects 0.000 claims description 5
- 238000005229 chemical vapour deposition Methods 0.000 claims description 5
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- 229910052796 boron Inorganic materials 0.000 claims description 4
- 239000011229 interlayer Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
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- 239000002243 precursor Substances 0.000 claims description 4
- BGECDVWSWDRFSP-UHFFFAOYSA-N borazine Chemical compound B1NBNBN1 BGECDVWSWDRFSP-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 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
- 229920001577 copolymer Polymers 0.000 claims description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 2
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 238000004806 packaging method and process Methods 0.000 claims description 2
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims 1
- -1 boraneamine Chemical compound 0.000 claims 1
- 239000004202 carbamide Substances 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- 230000001419 dependent effect Effects 0.000 claims 1
- 229910052732 germanium Inorganic materials 0.000 claims 1
- 239000012535 impurity Substances 0.000 claims 1
- 229910052741 iridium Inorganic materials 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- BORTXUKGEOWSPS-UHFFFAOYSA-N n-dimethylboranylmethanamine Chemical compound CNB(C)C BORTXUKGEOWSPS-UHFFFAOYSA-N 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 229910052755 nonmetal Inorganic materials 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 229910052697 platinum Inorganic materials 0.000 claims 1
- 229910052703 rhodium Inorganic materials 0.000 claims 1
- 229910052707 ruthenium Inorganic materials 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010408 film Substances 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 8
- 239000010453 quartz Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000010409 thin film Substances 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 5
- 238000005204 segregation Methods 0.000 description 5
- 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
- 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
- 238000004090 dissolution Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 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
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 229920006280 packaging film Polymers 0.000 description 2
- 239000012785 packaging film Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 1
- 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
- 230000001276 controlling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000003746 surface roughness Effects 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
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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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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: the method comprises the following steps: 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 the surface of one side 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 tubular furnace, raising the temperature to a certain temperature, introducing high-concentration carbon-containing gas, realizing the diffusion of carbon atoms from the outer surface to the inner surface, separating out the carbon atoms in the cooling process, and generating graphene at the interface of metal and hexagonal boron nitride; step five: and cutting 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 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 can obtain the vertical boron nitride/graphene heterojunction film with wafer level and high quality.
Description
The technical field is as follows:
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 art:
the microelectronic technology is the core technology of high technology and information industry, and we can refer to the genius of the equipment of the informatization martial arts. With the continuous progress of science and technology, the fields of household appliances, mobile communication, computers, satellite navigation, deep sea detection and the like to the modern society can be well mastered by unmanned driving, and intelligent manufacturing, quantum communication and the like all depend on the development of microelectronic devices. Two-dimensional electronic materials rapidly developed in recent years show a series of new physical phenomena and unique electronic transport characteristics, and provide a new approach for realizing novel high-performance electronic devices. The graphene is a micro-nano electronic device material with great potential.
One of the biggest challenges facing the application of two-dimensional materials represented by graphene in the device field is the interface problem between the two-dimensional materials and dielectric materials. The graphene has a large specific surface area, and a surface state and a carrier trap center are easily introduced in each process stage of preparation, transfer, device processing and the like, so that the device performance of the graphene is greatly reduced. The hexagonal boron nitride has high dielectric strength, atomic-level flatness and excellent heat conductivity. Graphene is an ideal dielectric material. The controlled growth of a high-quality large-area hexagonal boron nitride/graphene vertical heterojunction structure is a key scientific problem which needs to be researched urgently at present.
However, the existing method for directly preparing the hexagonal boron nitride/graphene heterojunction with clean interface, no doping and high quality has certain problems. For example, 1) the method for constructing the vertical heterojunction by means of micro-mechanical stripping and micro-transfer has high process randomness, poor repeatability and very limited size of a heterojunction sample; 2) graphene is directly grown on the surface of hexagonal boron nitride by a CVD epitaxial method, the uniformity and continuity of the graphene in the obtained heterojunction in a large-area range are poor, and unfavorable interlayer etching and doping phenomena occur in a heterojunction sample due to the high epitaxial growth temperature. 3) Carbon atoms are dissolved in the metal in advance by a method of pre-dissolving and segregation, 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 thin film material" describes a one-step growth method. Preparing h-BN on the surface of a metal substrate dissolved with carbon atoms with certain concentration in advance by a chemical vapor deposition method, then 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 the patent CN201610652002.8, "a method for preparing a two-dimensional layered heterojunction based on graphene", a gaseous carbon source is also pre-dissolved in a metal substrate. By adopting a co-segregation method, carbon atoms and B, N atoms are dissolved into metal Ni in advance to form a sandwich structure, and the atoms dissolved in the annealing process are gradually separated out to form an h-BN/graphene heterojunction structure. (C.H.Zhang et al, "Direct growth of large-area graphene and boron nitride heterojunction methods". Nature Communications,2015,6: 6519). The pre-dissolution + segregation method used in the above patent and literature is a method in which carbon atoms pre-dissolved in a metal easily enter between boron nitride layers during the growth of a boron nitride thin film, thereby causing atomic doping.
The invention content is as follows:
aiming at the problems, the invention 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:
the method comprises the following steps: 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 the surface of one side 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 boron nitride film does not exist on the outer surface of the sealing bag;
step four: the metal bag is put in a tube furnace, the temperature is raised to a certain temperature, and high-concentration carbon-containing gas is introduced to realize the diffusion of carbon atoms from the outer surface to the inner surface. Slowly cooling, slowly separating out carbon atoms, and generating graphene on the interface of the metal and the hexagonal boron nitride;
step five: the metal bag is cut and spread, and the hexagonal boron nitride/graphene vertical heterojunction film can be obtained on the surface of the target substrate by methods such as wet transfer, bubbling transfer, dry transfer and the like.
Preferably, the preparation process of the hexagonal boron nitride film in the step one 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 introduction method, a water bath heating method or a heating belt direct heating method, the growth temperature is 400-1200 ℃, the growth time is 5-120 min, the carrier gas is argon gas mixed gas containing hydrogen in a certain proportion, and the volume content of the hydrogen is 2.5-50%.
Preferably, the plasma etching process in the second step is; the etching gas is argon, hydrogen or oxygen plasma, and the power of the radio frequency power supply is between 100W and 250W. In the etching process, the metal foil is horizontally arranged on the surface of the quartz plate, and polymers such as polyvinyl alcohol (PVA), polymethyl methacrylate (PDMS), ethylene-octene copolymer (POE) and the like are used for packaging four sides, so that the hexagonal boron nitride film on the other side is prevented from being etched by plasma.
Preferably, the metal bag described in the third step is in a completely sealed state. When in manufacture, the three open edges are firstly folded for 2-3 times, and certain pressure is applied. The metal strip should be heated to 800-1050 ℃ for annealing for 5-30 min to ensure the metal bag to be completely sealed.
Preferably, the condition in the fourth step is that the diffusion process temperature according to claim 1 is 500-850 ℃, and interlayer atom doping is avoided under a higher temperature condition, so that the interface doping of the generated heterojunction structure is caused. The diffusion process is carried out under normal pressure, the concentration of carbon atoms is 1-25%, the diffusion time is 0.5-25 h, 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, greatly reduces the interlayer atom doping effect by a sealed metal bag structure and a lower diffusion temperature, and ensures 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 does not undergo any pre-dissolution of carbon atoms when growing the boron nitride film. The boron nitride produced at this time was a pure film.
2. In step four, by adopting the sealed metal bag structure, carbon atoms diffuse from the outer surface of the metal bag and enter the inner surface, segregate at the inner surface and form graphene between boron nitride and the inner surface of the metal. In the process, carbon atoms are always in a low concentration state at the inner surface covered with boron nitride, so that the probability of doping among atoms is reduced.
3. In step four, the diffusion temperature is always lower than 850 ℃ during the diffusion of carbon atoms from the outer surface of the metal bag and into the inner surface. The boron nitride which has finished growing at this time is in a chemically stable state, and the phenomenon of doping 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 and do not influence each other. The thicknesses of the boron nitride layer and the graphene layer in the heterojunction can be independently regulated and controlled.
5. The graphene in the heterojunction prepared by the method is obtained through carbon atom diffusion and segregation growth, and is slowly precipitated to generate the graphene 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 completely depends 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.
Description of the 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 view of the growth process of the present invention;
fig. 2 is a digital picture of a wafer-level boron nitride/graphene vertical heterojunction thin film prepared in example 1 of the present invention;
fig. 3 is a raman spectrum and an ultraviolet-visible absorption spectrum of the boron nitride/graphene vertical heterojunction thin film prepared in example 1 of the present invention;
fig. 4 is a comparison of the bidirectional transfer curves of field effect crystals of simple graphene and boron nitride/graphene vertical heterojunction thin films prepared in comparative example 1 and example 1 of the present invention.
The specific implementation mode is as follows:
in order that the objects, aspects and advantages of the invention will become more apparent, the invention will be described by way of example only, and in connection with the accompanying drawings. It is to be understood that such description is merely illustrative and not intended to limit the scope of the present invention. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present invention.
Example 1:
surface catalytic growth of boron nitride film: the growth of hexagonal boron nitride is carried out in a chemical vapor deposition system, and the precursor is borane ammonia complex. Shearing about 5X 5cm before reaction2Copper nickel alloy of sizeThe gold foil is placed in the center of the quartz tube, and about 10mg of borane ammonia complex is weighed and placed at the front end of the tube furnace 30-60 cm away from the central area of the furnace temperature. Before heating, the system is vacuumized and inert protective gas is introduced to the normal pressure, and the process is repeated for 2 times, so that the air in the pipeline is emptied. Maintaining inert shielding gas flow at 500sccm, normal pressure, and temperature rise rate of 5-50 deg.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 30-60 min. After the reaction, the heating belt is closed, and the system is slowly cooled.
Removing the boron nitride film on one side surface: after the first-step reaction is finished, firstly removing the hexagonal boron nitride film on one side of the surface of the copper-nickel alloy foil. Firstly, a sample obtained by the last step of growth is flatly 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 of the substrate by using argon plasma, wherein the power is 100W, and the time is 30 min.
Preparing a sealing bag structure: and after the etching is finished, slowly uncovering the polyvinyl alcohol packaging film, and sealing the copper-nickel alloy foil. And during sealing, setting the side subjected to etching treatment as the outer side, and setting the side which is not subjected to etching treatment and is reserved with the hexagonal boron nitride film as the inner side. To ensure the air tightness of the sealed bag, the three open sides of the sealed bag are folded, extruded and the edges of the foil are fused in a high-temperature annealing process. The annealing temperature is 1050 ℃ and the annealing time is 20 min.
Diffusion of carbon atoms and precipitation of graphene: the carburizing process is carried out at 800 ℃ under CH atmosphere4The diffusion time of the argon gas mixture with the volume fraction of 5-25 percent and the volume fraction of 1-25 percent of hydrogen is generally 0.5-2.5 h. After the process is finished, the methane raw material is cut off, and the system is slowly cooled to the room temperature.
And (3) heterojunction transfer: after the reaction is finished, the metal bag is cut and spread, and is transferred to a target substrate by a conventional wet transfer method or a hydrogen bubbling method. Then a boron nitride/graphene heterojunction structure can be obtained on the target substrate, the thickness is between 1 and 25nm, and the size is about 4.5 multiplied by 4.5cm2。
Fig. 2 is a digital image of the wafer-level boron nitride/graphene vertical heterojunction obtained in this embodiment.
Fig. 3 is a raman spectrum and an ultraviolet-visible absorption spectrum of the boron nitride/graphene vertical heterojunction obtained in this embodiment. The Raman spectrum shows a D peak, a G peak and a 2D peak typical of graphene and E of hexagonal boron nitride2gA vibration peak. The ultraviolet-visible absorption spectrum shows the absorption peak (270 cm) of graphene-1) Absorption peak with boron nitride (210 cm)-1)。
Example 2:
surface catalytic growth of boron nitride film: the growth of hexagonal boron nitride is carried out in a chemical vapor deposition system, and the precursor is borazine. Shearing about 5X 9cm before reaction2A Ni foil of size was placed in the center of the quartz tube. Before the temperature is raised, inert gas is firstly adopted for gas washing, and the air in the quartz tube is exhausted as far as possible. And (3) maintaining the flow of the inert protective gas at 500sccm and the pressure at normal pressure, and heating the reaction furnace body. The heating rate is 25 ℃ for min-1. When the furnace temperature is raised to the reaction temperature, introducing the raw materials into the reaction system by using a bubbling device, wherein the growth time is 30-60 min. After the reaction, the system is slowly cooled.
Removing the boron nitride film on one side surface: and after the first-step reaction is finished, firstly removing the hexagonal boron nitride film on one side of the surface of the Ni foil. Firstly, a sample obtained by the last step of growth is flatly placed on the surface of a quartz plate, and four sides of the sample are packaged by adopting a polymethyl methacrylate film. And etching the surface of the substrate by using hydrogen plasma, wherein the power is 125W, and the time is 60 min.
Preparing a sealing bag structure: and after the etching is finished, slowly uncovering the polymethyl methacrylate packaging film, and sealing the Ni foil. And during sealing, setting the side subjected to etching treatment as the outer side, and setting the side which is not subjected to etching treatment and is reserved with the hexagonal boron nitride film as the inner side. To ensure the air tightness of the sealed bag, the three open sides of the sealed bag are folded, extruded and the edges of the foil are fused in a high-temperature annealing process. The annealing temperature is 1065 ℃ and the time is 10 min.
Diffusion of carbon atoms and precipitation of graphene: the carburizing process isAt a temperature of 650 ℃ in a CH atmosphere4The diffusion time of the argon gas mixture with the volume fraction of 5-25 percent and the volume fraction of 1-25 percent of hydrogen is generally 0.5-2.5 h. After the process is finished, the methane raw material is cut off, and the system is slowly cooled to the room temperature.
And (3) heterojunction transfer: after the reaction is finished, the metal bag is cut and spread, and is transferred to a target substrate by a dry transfer method. Then a 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 8cm2。
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 in example 1, thereby obtaining a simple graphene thin film. A field effect transistor consisting solely of graphene was prepared and compared to the field effect transistor performance 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 composed of graphene alone shown in comparative example 1: it can be seen from the figure that the transistor exhibits a significant hysteresis during the reverse scan back of the gate voltage, and the dirac point is far from the center point. And the field effect transistor of the boron nitride/graphene vertical heterojunction hardly has hysteresis, and the Dirac point tends to a central point. It is shown 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 attributes 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 description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (8)
1. A preparation method of a wafer-level high-quality boron nitride/graphene heterojunction film is characterized by comprising the following steps: the preparation method comprises the following steps:
the method comprises the following steps: preparing a continuous hexagonal boron nitride film on the surface of the metal by a surface catalytic growth method and adopting a chemical vapor deposition technology;
step two: removing the hexagonal boron nitride film on the surface of one side 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 boron nitride film does not exist on the outer surface of the sealing bag;
step four: the metal bag is put in a tube furnace, the temperature is raised to a certain temperature, and high-concentration carbon-containing gas is introduced to realize the diffusion of carbon atoms from the outer surface to the inner surface. Slowly cooling, slowly separating out carbon atoms, and generating graphene on the interface of the metal and the hexagonal boron nitride;
step five: the metal bag is cut and spread, and the hexagonal boron nitride/graphene vertical heterojunction film can be obtained on the surface of the target substrate by a wet transfer method, a bubbling transfer method or a dry transfer method.
2. The metal according to claim 1 is a metal having a certain carbon-dissolving ability and an alloy thereof, and includes a binary or a multicomponent alloy of a highly carbon-soluble metal such as Fe, Co, Ni, Rh, Ru or Ir, a low carbon-soluble metal such as Cu, Pt, Au, Ga or Ge, and the highly carbon-soluble metal, and a binary or a multicomponent alloy of a nonmetal including B, Si or P, and the metal.
3. The conditions for surface catalytic growth of boron nitride films according to claim 1 are: the raw material is any compound containing B atoms such as: boron powder (B) and borane (B)nHn+4N is a positive integer), organoborane BR3Etc. and optionally N atom-containing compounds such as nitrogen (N)2) Ammonia (NH)3) Urea and compounds containing both B and N atoms, e.g. borazine, boraneamine, trimethylboraneamine, B3N3Cl6The growth temperature of the precursor and the mixture precursor is between 400 ℃ and 1200 ℃. The carrier gas is a mixed gas of hydrogen and argon, wherein the volume content of the hydrogen is 0-75%.
4. The method according to claim 1, wherein the etching conditions for the hexagonal boron nitride film on the surface of the metal side are plasma atmosphere of argon, oxygen, hydrogen and their mixture, and the power is 25W-250W. In the etching process, the metal foil is horizontally arranged on the surface of the horizontal substrate, and polymers such as polyvinyl alcohol (PVA), polymethyl methacrylate (PDMS), ethylene-octene copolymer (POE) and the like are used for packaging four sides, so that the hexagonal boron nitride film on the other side is prevented from being etched by plasma.
5. The metal bag according to claim 1, wherein: the bag is completely sealed and airtight. Wherein the inner surface of the bag is grown with a boron nitride film, and the outer surface is not provided with the boron nitride film; when in manufacture, the three open edges are firstly folded for 2-3 times, and certain pressure is applied. The metal strip should be heated to 800-1050 ℃ for annealing for 5-30 min to ensure the metal bag to be completely sealed.
6. The diffusion process as claimed in claim 1, wherein the temperature of the diffusion process is 200-850 ℃, thereby avoiding impurity at the interface of the heterojunction structure due to interlayer atom doping at higher temperature. The diffusion process is carried out under normal pressure, the concentration of carbon atoms is 1-50%, and the diffusion time is 0.5-50 h. The cooling rate is 0.1-100 deg.C/min.
7. The thickness of the boron nitride/graphene vertical heterojunction film of claim 1 is 0.5-50 nm, and the method can independently regulate and control the thickness of the upper layer boron nitride and the thickness of the lower layer graphene.
8. The boron nitride/graphene vertical heterojunction structure of claim 1, wherein the planar area of the boron nitride/graphene vertical heterojunction structure is generally 0.01-200 cm2And the area of the metal bag is only dependent on the size of the metal bag and the volume of the tube furnace, and the growth equipment can be correspondingly modified in the actual preparation process, so that the plane area of the metal bag is further increased.
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