CN114920239B - Two-dimensional material transferring or stacking method based on water vapor - Google Patents
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
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- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
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Abstract
The embodiment of the invention discloses a two-dimensional material transferring or stacking method based on water vapor, which comprises the following steps: treating the substrate by adopting oxygen plasma, and generating a layered two-dimensional material on the surface of the pretreated substrate to obtain a prefabricated composite substrate; spin-coating a transfer medium on the surface of the prefabricated composite substrate, and then drying the surface of the prefabricated composite substrate, and covering support gel on the surface of the prefabricated composite substrate to obtain the prefabricated transfer substrate; fumigating the prefabricated transfer substrate in a steam environment to obtain a transfer substrate; stripping the pretreated substrate on the transfer base material to obtain a transfer base; and transferring the transfer substrate to a target substrate, baking, and eluting the transfer medium to finish the transfer of the two-dimensional material. Through the mode, the method is used for simply, efficiently and low-pollution transferring of mechanical cleavage or various two-dimensional materials prepared by CVD growth, sample pollution caused by wet transfer in scientific research and danger caused by shielding using strong acid/alkaline solution are reduced, so that scientific research cost is reduced, and scientific research efficiency is improved.
Description
Technical Field
The embodiment of the invention relates to the technical field of layered material preparation, in particular to a two-dimensional material transferring or stacking method based on water vapor.
Background
The field of two-dimensional materials with graphene as a enlightenment has become a hot spot today. The two-dimensional material with nano-scale shows remarkable physicochemical properties, has great potential in the research of sensors, detectors, optoelectronic devices and the like, and has important significance in the important front technical fields of circuit electronics, energy storage and the like.
In particular, stacking and assembling different two-dimensional materials creates more novel structural and physical properties. Van der waals heterojunction exhibits surprising properties in studies of superconductivity, topological insulation, energy valley, and the like. These special structures are also of absolute advantage in the fields of electricity, optics, energy harvesting and storage, etc. In recent years, researchers have developed the research field of corner double-layer two-dimensional materials, and found that moire fringes can be prepared by changing the rotation angle of two-dimensional material stacking, so that the electrical or photoelectric properties of the materials are affected. Research shows that rare superconducting phenomena exist in the three-layer graphene material with the magic angle, and the superconducting behavior can be effectively proved to be derived from strong interaction between electrons. In addition, characteristics such as multi-body correlation spectrum signals, three-quarter filling state ferromagnetism and the like are also gradually found in various magic angle structures.
The preparation of two-dimensional van der waals heterojunction is often independent of the sample transfer and stacking process. Through the transfer of the two-dimensional material, the experimental purposes of integrating various functional substrates, passivating the air-sensitive material, preparing a corner structure, preparing a multi-dimensional hybrid device and the like can be realized. Therefore, from the aspect of basic research, the transfer technology is a necessary procedure for preparing a special structure, has an irreplaceable role in basic material performance research, and can help people to find new functional devices by constructing various structures. Therefore, transfer is an important technical approach to study the properties of two-dimensional materials and their hetero/homogeneous structures. The transfer method of the two-dimensional material can be broadly divided into two modes, wet transfer and dry transfer:
wet transfer:
(1) Take Chemical Vapor Deposition (CVD) grown graphene wet transfer techniques as an example. The process includes spin coating polymethyl methacrylate (PMMA), using ferric trichloride (FeCl) 3 ) Or ammonium disulfate ((NH) 4 ) 2 S 2 O 8 ) Removing copper from the solution, baking, removing photoresist from acetone, cleaning and the like. Because the transfer flow is longer, the operation proficiency has a certain influence on the quality of the transferred graphene. In addition to that, feCl 3 The introduction of the solution and the incomplete removal of the copper metal substrate have great influence on the quality of the transferred graphene film.
(2) And transferring graphene by an electrochemical method. And (3) taking the graphene/copper foil which is spin-coated with PMMA as a cathode, taking a carbon rod as an anode, decomposing water by using direct current in an electrolytic cell, and separating the PMMA/graphene layer by utilizing bubbles between the graphene and the copper foil. Finally, the PMMA was washed off with acetone. In the experimental process, bubbles generated by the cathode of the electrolytic cell can damage the integrity of the graphene film, and impurities are introduced into the solution more easily by placing a carbon rod in the solution and electrifying, so that a graphene sample is polluted.
Dry transfer:
(3) Taking hexagonal boron nitride (h-BN) as an example for assisted dry transfer of graphene. The preparation method comprises the steps of spin-coating polypropylene carbonate (PPC) on a standby silicon wafer, stripping h-BN and graphene on the PPC and the silicon wafer, adhering the PPC by using a Scotch tape, aligning the h-BN sample, and adhering the sample on PDMS on a glass slide to form a conveying frame. And then aligning and tightly attaching the h-BN and the graphene sample below, heating the sample stage to a temperature above the glass transition temperature of PCC, and cooling back to room temperature, wherein the h-BN sticks the graphene sample. And transferred to the target substrate on the premise that realignment is required if the heterostructure is constructed. Finally, the PPC film is released by heating and placed in acetone. The secondary transfer process requires high skill from the operator and requires multiple targeting.
(4) Liquid embedding is an example. This method is mainly to cover the sample and substrate surfaces with a hydrophobic layer of l-polylactic acid (PLLA), transfer is achieved by hydrophobicity of PLLA and melting PLLA onto the desired substrate, and finally PLLA is removed with Dichloromethane (DCM). This method, while easy to operate, increases the cost of the experiment using PLLA and DCM solvents.
The above schemes can realize the transfer of two-dimensional materials, but are undeniable: unnecessary solution is introduced in the wet transfer process, so that the transfer difficulty and sample pollution are increased, and even strong acid and alkali solution which can cause serious injury to human bodies is involved; the dry transfer technique often requires the use of new adhesive materials (PPC, PLLA, h-BN, etc.), which, while greatly improving the cleanliness during sample transfer, increases the cost of experimentation and cumbersome handling steps. The wet transfer technology and the dry transfer technology related at present are to be improved in cleanliness and operation flow, and the processing difficulty is high.
Disclosure of Invention
To this end, embodiments of the present invention provide a two-dimensional material transfer or stacking method based on water vapor, which is specific to existing layered materials (such as graphene, moS 2 ，WSe 2 Etc.), the method has the advantages of simple, efficient and low-pollution realization, can transfer a plurality of two-dimensional materials prepared by mechanical cleavage or CVD growth in a positioning way, reduces sample pollution caused by wet transfer in scientific research and shields the dangers caused by using strong acid/alkaline solution, thereby reducing the scientific research cost and improving the scientific research efficiency.
In order to achieve the above object, the embodiments of the present invention provide the following technical solutions:
in one aspect of an embodiment of the present invention, there is provided a method of two-dimensional material transfer or stacking based on water vapor, comprising:
s100, treating the substrate by oxygen plasma to obtain a pretreated substrate;
s200, generating a layered two-dimensional material on the surface of the pretreated substrate to obtain a prefabricated composite substrate;
s300, spin-coating a transfer medium on the surface of the prefabricated composite substrate, drying, and covering support gel on the surface of the dried transfer medium to obtain the prefabricated transfer substrate;
s400, fumigating the prefabricated transfer substrate in a steam environment to obtain a transfer substrate;
s500, stripping the pretreated substrate on the transfer substrate to obtain a transfer substrate;
s600, transferring the transfer substrate to a target substrate, baking, and eluting the transfer medium to finish transfer or stacking of the two-dimensional material.
As a preferred embodiment of the present invention, the material of the substrate is selected from one or more of silicon, sapphire and mica.
As a preferred embodiment of the present invention, the layered two-dimensional material is provided by graphite or a metal chalcogenide;
preferably, the metal chalcogenide has the formula MX 2 Wherein M is selected from Mo, W, sn, ta, nb, pt or Ga, and X is selected from S, se or Te.
As a preferable mode of the present invention, the graphite is pyrolytic graphite crystal or natural graphite crystal with high orientation.
As a preferred embodiment of the present invention, the method of forming the layered two-dimensional material in step S200 may employ mechanical cleavage or chemical vapor deposition.
As a preferred embodiment of the present invention, the transfer medium in step S300 is selected from one or more of polymethyl methacrylate, polystyrene, and rosin;
preferably, the spin-coated transfer medium has a thickness of 200nm to 10 μm after baking.
As a preferable scheme of the invention, the temperature of the drying process in the step S300 is 100-140 ℃ and the time is 2-10min.
As a preferred embodiment of the present invention, the transfer medium is selected from polymethyl methacrylate and rosin, and the spin coating process specifically includes:
s301, spin-coating rosin on the surface of a prefabricated composite substrate, lightly touching the surface of the rosin by adopting a rough surface, and then placing the substrate in a first temperature condition for drying for 1-2min to obtain a substrate young body;
s302, spin-coating polymethyl methacrylate on the surface of the rosin layer on the obtained substrate young body, and then drying for 1-9min at a second temperature; wherein,,
the temperature value of the first temperature is smaller than the temperature value of the second temperature;
preferably, the surface area of the spin-coated rosin in step S301 is smaller than the area of the spin-coated polymethyl methacrylate in step S302, and the spin-coated polymethyl methacrylate has a rim formed on the outer edge of the spin-coated rosin.
As a preferred embodiment of the present invention, the support gel is polydimethylsiloxane and/or silica gel;
preferably, the thickness of the support gel is 200 μm-2mm.
As a preferable scheme of the invention, the fumigation time in the step S400 is 10-30min;
preferably, the baking process in step S600 is performed at a temperature of 120-150 ℃ for a time of 1-3min.
Embodiments of the present invention have the following advantages:
1) Based on pretreatment of the surface of the substrate by oxygen plasma, the corrosion operation on the substrate in the conventional transfer process is avoided, the damage to the surface of the two-dimensional material is effectively avoided, and the defects generated by the damage are greatly reduced; meanwhile, the surface of the substrate pretreated in the mode generates interface strain to form an oxygen-philic interface, and the whole transfer or stacking can be completed more simply, rapidly and effectively by introducing water vapor on the basis. The mode can be widely suitable for mechanical cleavage or transfer of two-dimensional layered materials formed by CVD growth, and the application range is greatly improved.
2) The preparation method can be based on the selection of the substrate, and is matched with the support gel to realize the integral transparent visualization, thereby being more convenient for preparing the accurate positioning transfer of the functional structures such as the heterojunction and the like.
3) The invention is mainly based on the interface change of the surface of the substrate after oxygen plasma treatment, has lower influence on the sample, thus obtaining higher crystal quality and being beneficial to researching the properties of high-quality two-dimensional material films and heterostructures thereof.
4) The invention provides a more convenient, clean, rapid and pollution-free transfer or stacking method for the research of preparing special structures by two-dimensional layered materials. The heterojunction structure with high quality performance is facilitated, and research and future development of next-generation multifunctional devices and integrated circuits prepared based on two-dimensional materials are facilitated.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It will be apparent to those skilled in the art from this disclosure that the drawings described below are merely exemplary and that other embodiments may be derived from the drawings provided without undue effort.
The structures, proportions, sizes, etc. shown in the present specification are shown only for the purposes of illustration and description, and are not intended to limit the scope of the invention, which is defined by the claims, so that any structural modifications, changes in proportions, or adjustments of sizes, which do not affect the efficacy or the achievement of the present invention, should fall within the ambit of the technical disclosure.
FIG. 1 is a flow chart of a two-dimensional material transfer or stacking method provided by an embodiment of the present invention;
FIG. 2 (a) is an optical photograph of a substrate before oxygen plasma treatment according to an embodiment of the present invention;
FIG. 2 (b) is an optical photograph of a substrate after oxygen plasma treatment according to an embodiment of the present invention;
fig. 3 (a) is a physical diagram of the substrate obtained in step (2) in embodiment 2 of the present invention to obtain a large-area single-layer graphene;
fig. 3 (b) is a physical diagram of the graphene-PMMA-PDMS sample obtained in step (3) in example 2 of the present invention;
FIG. 3 (c) is a partial enlarged view of PMMA on the graphene-PMMA-PDMS sample obtained in step (3) of example 2 of the present invention;
FIG. 3 (d) shows a single-layer MoS obtained in example 2 of the present invention 2 -a single layer graphene thin film structure;
fig. 4 (a) is a silver pattern structure covered with a graphene film prepared in example 1 of the present invention;
fig. 4 (b) is a heterostructure of a large-area monolayer Bi2212 and a monolayer graphene stack prepared in inventive example 3;
FIG. 4 (c) shows a multilayer WSe obtained in inventive example 4 2 And a heterostructure of single layer graphene stacks;
fig. 4 (d) shows a substrate structure with suspended graphene film prepared in embodiment 5 of the present invention;
FIG. 4 (e) shows a thin layer MoTe obtained in example 6 of the present invention 2 Heterostructure stacked with single layer graphene
FIG. 4 (f) shows a sheet WSe obtained in inventive example 7 2 -Bi 2 O 2 Heterostructure of Se stacks.
Detailed Description
Other advantages and advantages of the present invention will become apparent to those skilled in the art from the following detailed description, which, by way of illustration, is to be read in connection with certain specific embodiments, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a two-dimensional material transferring or stacking method based on water vapor, which concretely comprises the following steps:
1. treating a substrate (i.e., a substrate) by oxygen plasma, mechanically cleaving or CVD growing a two-dimensional layered material onto the surface of the substrate to obtain a substrate-layered material;
2. spin-coating the surface of the obtained substrate-layered material with an organic solution, and then placing the substrate-layered material into a constant temperature box or on a hot table for drying for 2-10min to obtain a substrate-layered material-organic film;
3. covering the substrate-layered material-organic film with support gel, placing into a water container, heating to steam generation without contacting water, and fumigating for 10-30min;
4. removing the self-supporting gel layer of the substrate-layered material-organic film covered with the supporting gel, so that the substrate is separated from the layered material-organic film to obtain layered material-organic film-supporting gel;
5. transferring the obtained layered material-organic film-support gel onto a required substrate (namely a target substrate) and baking again for 1-3min so as to tightly attach a new substrate to a sample;
6. and (3) desorbing the organic film layer in the new substrate-layered material-organic film-supporting gel by using acetone or acetone steam to obtain a transferred functional structure, namely the new substrate-layered material.
The substrate type herein may be selected from any type of material that would be conventionally understood and used by those skilled in the art, e.g., silicon, sapphire, mica, etc., in a preferred embodiment.
In another preferred embodiment, the two-dimensional layered material herein may be derived from graphite or metal chalcogenides, and preferably, the graphite herein may be selected from highly oriented pyrolytic graphite crystals or natural graphite crystals. Further, when graphite is selected here, the resulting substrate-layered material is a substrate-graphene thin film material. Meanwhile, the metal chalcogenides herein are further selected as MX 2 Wherein M is Mo, W, sn, ta, nb, pt or Ga and X is S, se or Te.
The organic film is preferably a polymethyl methacrylate film or a polystyrene film, and has a thickness of 200nm to 10 μm. In a preferred embodiment, the support gel is a polydimethylsiloxane film or a silicone film and has a thickness of 200 microns to 2 millimeters.
Further details of the method of specifically producing a pleat of a layered material are described below in conjunction with the accompanying drawings.
A. As shown in fig. 1 (a), oxygen plasma-treated single polished silicon/silicon oxide (300 nm in thickness) was used as a substrate; as shown in fig. 1 (b), mechanically cleaving graphite (where graphite may be selected from highly oriented pyrolytic graphite crystals or natural graphite crystals) with a 3M tape to the treated substrate surface to obtain a substrate-graphene thin film material as shown in fig. 1 (c);
B. as shown in fig. 1 (d), spin-coating a polymethyl methacrylate (PMMA) solution on the surface of the substrate-graphene film material obtained in the step a, and then placing the substrate-graphene film material into an incubator or on a hot table for drying for 2-10min to obtain a substrate-graphene film material-PMMA film (the thickness of the PMMA film is not more than 2 μm);
C. covering PDMS (polydimethylsiloxane) with the substrate-graphene film material-PMMA film obtained in the step B, wherein the thickness of the PDMS film is not more than 500 mu m, placing the substrate-graphene film material-PMMA film into a water container, heating the substrate-graphene film material-PMMA film into steam without contacting with water, and fumigating the substrate-PMMA film material and the PDMS film for 10-30min, wherein fig. 1 (e) is a schematic diagram of a fumigating process;
D. and (3) removing the PDMS layer in the step C. As can be seen from fig. 1 (f), the substrate is separated from the graphene film material-PMMA film, so as to obtain the graphene film material-PMMA film-PDMS film;
E. transferring the graphene film material-PMMA film-PDMS film obtained in the step D onto a new substrate with a silver pattern (BIT letters, silver layer thickness 10 nm) prepared in advance and baking for 1-3min again, wherein a process diagram is shown in FIG. 1 (g);
F. and (3) eluting the PMMA film layer in the new substrate-graphene film material-PMMA film-PDMS film in the step E by using acetone or acetone steam, wherein the structural schematic diagram and the physical diagram of the obtained transferred substance are shown in fig. 1 (h) and fig. 4 (a), respectively.
In the operation mode, the single polished silicon/silicon oxide treated by oxygen plasma is taken as a substrate, and the 3M adhesive tape is used for cleaving high-orientation pyrolytic graphite (HOPG) crystals or natural graphite crystals on the surface of the substrate, so that large-area thin-layer graphene can be effectively prepared. The PMMA solution was spin coated on the prepared sample surface and the PMMA layer was dried in a hot stage or oven. In order to support a PMMA film layer with extremely high flexibility, PDMS is selected as a supporting layer, the PMMA film layer is adhered to the PDMS film layer, then the PMMA film layer is placed into a container containing water (a heightening object is arranged in the container), a sample does not touch water, the temperature is raised until steam is generated, fumigation is carried out for 10-30 minutes, and the steam fully enters between a substrate and graphene film-PMMA. The oxygen ions are on the surface of the substrate, so that the substrate and the graphene are not tightly attached, the substrate is very hydrophilic due to the existence of the oxygen ions, and water molecules can enter between the graphene and the substrate conveniently, so that the graphene film-PMMA and the substrate interface are the main driving force for separating. Due to the weakening of the acting force of the graphene film-PMMA and the substrate, the PMMA film tightly adhered to the PDMS of the supporting layer can be removed at the moment, so that the graphene film can be efficiently peeled off from the surface of the substrate. The power, the oxygen flow and the time of the oxygen plasma treatment base have no obvious influence on the transfer of the two-dimensional material from the substrate, but the insertion of water molecules is easier to realize under the conditions of long time, high power and stable oxygen amount, and the transfer is easier. The oxygen amount can stabilize the visible plasma white light in the power range of 40-100mW for 30-360 seconds, the transfer can be realized by meeting the requirements, and the substrate after the oxygen plasma treatment can realize the large-area cleavage of the sample more easily. PDMS is a thin film layer that serves as a support and adhesion, and PDMS with a thickness ranging from 200 micrometers to 2 millimeters can be used, as can other adhesive rigid organic films, such as silicone, plastic, and the like.
The integrity of the sample during transfer is extremely high, and the area is related to the size of the two-dimensional material prepared by the most original cleavage. The realization of the transfer has no correlation with the number of layers of the sample, the transfer can be realized by using a steam-assisted quasi-dry method from single-layer graphene to thick-layer graphite, the structure quality of a device prepared by the transfer is high, and in the whole process, the sample only contacts with PMMA (polymethyl methacrylate) as an organic solvent. Meanwhile, in order to better facilitate the removal of PMMA, reduce the roughness of the surface of the structure after transfer or stacking, further reduce the influence of impurities introduced in the transfer or stacking process, a layer of rosin can be further spin-coated before spin-coating the PMMA, and a drying operation is performed after spin-coating the rosin, and of course, the temperature and time of the primary drying operation are smaller than those of the spin-coating the PMMA, so that the interface is easier to elute later, and the overall cleanliness is improved. For example, in a specific embodiment, the temperature of drying after spin-coating rosin may be 95-105 ℃, the time may be selected to be 1-2min, the temperature of drying after spin-coating PMMA may be selected to be 100-140 ℃ and the time may be selected to be 2-10min, and of course, the present invention is not limited to this specific example, and any suitable time and temperature range may be selected, so long as the temperature and time of the rosin drying process are less than the temperature and time of the PMMA drying process. The setting mode can be based on the progressive drying process of the two spin-coating layers layer by layer when the overall drying effect is further effectively achieved, so that the sectional adhesion of the spin-coating layers to the substrate is achieved pertinently, and subsequent elution is facilitated better. Meanwhile, the surface area of the rosin spin-coated in step S301 may be smaller than the area of the polymethyl methacrylate spin-coated in step S302, and the spin-coated polymethyl methacrylate may have a rim formed on the outer edge of the spin-coated rosin. Namely, polymethyl methacrylate at the center is overlapped on the surface layer of rosin, and polymethyl methacrylate at the periphery is coated on the substrate, so that the arrangement mode can avoid overflow problems such as softening of the rosin layer and the like caused by relatively high temperature in the second-step drying process, and the temperature performance of the whole preparation process is better improved.
The method of the invention has the following advantages:
(1) From the preparation principle, the transfer process is easier and cleaner than other transfer or stacking methods, and the materials involved are all required for the transfer and preparation of traditional two-dimensional materials. The experiment used only conventional transfer solvents, PMMA solvents. Although the PMMA solvent can be removed quickly by using solvents such as acetone, the previous use of PMMA to transfer samples from a silicon oxide substrate requires the use of a strong acid/alkaline solution to etch away the silicon oxide layer, which inevitably damages the surface of the sample and damages the surface of the two-dimensional material, causing defects. We can solve this problem well by oxygen plasma treated substrate interfaces. First, an oxygen plasma treated substrate will facilitate cleavage of two-dimensional materials such as graphene. Secondly, as can be seen from fig. 2 (a) and (b), the substrate becoming an oxygen-philic interface attracts water molecules, and the introduction of a large amount of water molecules can rapidly reduce the effect of the two-dimensional material and the substrate, so that the two-dimensional material is conveniently carried away from the substrate by the conventional organic transfer solvent such as PMMA. The use of steam transfer is clearly different from wet transfer. In wet transfer, the solution often has many micro-nano particles that are invisible to the naked eye, which is a fatal problem for transfer processes with high cleanliness. However, the water molecules in the steam are hardly carried with particles, so that the amount of pollutants at the transfer interface can be reduced. In general, the whole preparation process of the water vapor assisted transfer method is simple, convenient, rapid and effective, and the obtained graphene has low cost and high quality, and is an environment-friendly, safe and reliable preparation method. This method is proven to be widely suitable for the transfer of cleaved or CVD grown layered materials on oxygen plasma treated substrates.
(2) The transfer method can obtain a sample of a pure transparent medium-two-dimensional material, has the protection of supporting gel, and is more convenient for preparing the positioning transfer of the functional structures such as heterojunction and the like. In the past, when PMMA is used as a transfer organic medium, most of the methods are to soak PMMA and two-dimensional materials into a solution together by means of a wet transfer technology and drag out the two-dimensional materials, so that the transfer position of a sample is difficult to grasp, and a heterostructure is difficult to obtain. Our transfer does not require more steps than the dry transfer technique, for example, it is necessary to prepare a boron nitride (h-BN) film and find the location of the transferred sample (sample attached to the boron nitride surface and sample transferred to the corresponding location) multiple times. Based on the above two points, our transfer technique does not require any solution effect and does not require multiple alignments to achieve positional transfer. In general, by our quasi-dry transfer technique, large area two-dimensional materials can be transferred efficiently, achieving clean heterojunction stacking.
(3) The fabrication of high quality heterostructures and functional devices has become a prime prerequisite for high performance devices. Because defects can bring a plurality of performance influences to sample testing, the high-quality film has important significance for researching physical and chemical properties of the material. The two-dimensional material obtained by mechanical cleavage has fewer defects and higher crystal quality. The technology mainly depends on the substrate treated by oxygen plasma, has extremely low influence on the sample, so that the obtained crystal has higher quality, and is beneficial to researching the properties of the high-quality two-dimensional material film and the heterostructure thereof.
(4) CVD grown layered materials tend to have regular structural features, which play an essential role in studying the structural properties of two-dimensional materials. The method is also suitable for transferring the two-dimensional material grown by CVD, and only needs to grow on the substrate after oxygen plasma treatment, and the technical method can be used.
(5) The invention provides a more convenient, clean, rapid and pollution-free transfer method for the research of preparing special structures by the layered material. The heterojunction structure with high quality performance is facilitated, and research and future development of next-generation multifunctional devices and integrated circuits prepared based on two-dimensional materials are facilitated.
The preparation method of the present invention is described below with reference to several specific examples.
Example 1
(1) At 1X 1cm 2 The silicon/silicon oxide of (2) was used as a substrate, and the surface of the substrate was treated with oxygen plasma at a power of 80mW for 3 minutes.
(2) High-orientation pyrolytic graphite (HOPG) crystals purchased from Nanjing Xianfeng nano company are clamped by tweezers, adhered to the surface of a 3M adhesive tape, repeatedly cleaved, attached to the surface of the silicon/silicon oxide substrate in step (1), pressed on a heat table at 110 ℃, and mechanically dissociated graphite in the cooling process, so that large-area single-layer graphene is obtained on the substrate.
(3) Spin-coating PMMA solvent on the surface of the substrate with graphene, drying, attaching PDMS as a supporting layer, placing the substrate into a container with water vapor at 80 ℃ for 20 minutes, taking out and uncovering the PDMS supporting layer, and obtaining the graphene-PMMA-PDMS sample.
(4) And (3) attaching the graphene-PMMA-PDMS sample obtained in the step (3) to a pre-prepared substrate with silver patterns (10 nm thick), and heating at a high temperature of 100 ℃ to facilitate the tight attachment of graphene and a functional substrate. After that, the PDMS support layer was lifted off after being left in acetone vapor for a period of time. Fig. 4 (a) is a single-layer graphene film-silver pattern structure prepared in example 1. As can be seen from fig. 4 (a), after the PMMA is completely removed by the acetone vapor, a silver pattern structure covered with a graphene film can be obtained.
Example 2
(1) At 1X 1cm 2 The silicon/silicon oxide of (2) was used as a substrate, and the surface of the substrate was treated with oxygen plasma at a power of 60mW for 1 minute.
(2) High-orientation pyrolytic graphite (HOPG) crystals purchased from nanjing qinfeng nano company are clamped by tweezers, adhered to the surface of a 3M adhesive tape, repeatedly cleaved, attached to the surface of a silicon/silicon oxide substrate in step (1), pressed on a hot table at 110 ℃, and mechanically dissociated in the cooling process, and as can be seen from fig. 3 (a), large-area single-layer graphene is obtained on the substrate.
(3) Spin-coating PMMA solvent on the surface of a substrate with graphene, drying, attaching PDMS as a supporting layer, placing the substrate into a container with water vapor at 90 ℃ for 30 minutes, taking out and uncovering the PDMS supporting layer, and obtaining a graphene-PMMA-PDMS sample, wherein the graphene is extremely deformed on the PMMA surface as can be seen in FIG. 3 (c).
(4) Attaching the graphene-PMMA-PDMS sample obtained in (3) to a pre-mechanically cleaved MoS 2 On a single layer substrate, heating at 100 degrees celsius, as can be seen from fig. 1 (i), graphene and MoS 2 -the substrate is tightly adhered. After that, the PDMS support layer was lifted off after being left in acetone vapor for a period of time. FIG. 3 (d) is a single-layer MoS obtained in example 2 2 -a monolayer graphene film structure. As can be seen from FIGS. 1 (j) and 3 (d), a single layer of MoS is obtained after the PMMA is completely removed by the acetone vapor 2 And heterostructures of single layer graphene stacks.
Example 3
(1) At 1X 1cm 2 The silicon/silicon oxide of (2) was used as a substrate, and the surface of the substrate was treated with oxygen plasma at a power of 60mW for 1 minute.
(2) High-orientation pyrolytic graphite (HOPG) crystals purchased from Nanjing Xianfeng nano company are clamped by tweezers, adhered to the surface of a 3M adhesive tape, repeatedly cleaved, attached to the surface of the silicon/silicon oxide substrate in step (1), pressed on a heat table at 110 ℃, and mechanically dissociated graphite in the cooling process, so that large-area single-layer graphene is obtained on the substrate.
(3) Spin-coating PMMA solvent on the surface of the substrate with graphene, drying, attaching PDMS as a supporting layer, placing the substrate into a container with water vapor at 90 ℃ for 30 minutes, taking out and uncovering the PDMS supporting layer, and obtaining the graphene-PMMA-PDMS sample.
(4) And (3) attaching the graphene-PMMA-PDMS sample obtained in the step (3) to a substrate which is mechanically cleaved with a Bi2212 monolayer in advance, and heating at 60 ℃ to facilitate the tight attachment of graphene and the substrate. After that, the PDMS support layer was lifted off after being left in acetone vapor for a period of time. Fig. 4 (b) is a single-layer Bi 2212-single-layer graphene thin film structure prepared in example 3. As can be seen from fig. 4 (b), when PMMA is completely removed by acetone vapor, a heterostructure of large-area single-layer Bi2212 and single-layer graphene stacks can be obtained.
Example 4
(1) The substrate surface was treated with oxygen plasma at a power of 80mW for 3 minutes using 1X 1cm2 of silicon/silicon oxide as substrate.
(2) High-orientation pyrolytic graphite (HOPG) crystals purchased from Nanjing Xianfeng nano company are clamped by forceps, adhered to the surface of a 3M adhesive tape, repeatedly cleaved, attached to the surface of the silicon/silicon oxide substrate in step (1), pressed on a heat table at 115 ℃, and mechanically dissociated in the cooling process to obtain large-area single-layer graphene on the substrate.
(3) Spin-coating PMMA solvent on the surface of the substrate with graphene, drying, attaching PDMS as a supporting layer, placing the substrate into a container with water vapor at 90 ℃ for 10 minutes, taking out and uncovering the PDMS supporting layer, and obtaining the graphene-PMMA-PDMS sample.
(4) Attaching the graphene-PMMA-PDMS sample obtained in (3) to a pre-mechanically cleaved WSe 2 And on the substrate with multiple layers, the graphene is heated at 100 ℃ so as to be convenient for adhesion with the substrate. After that, the PDMS support layer was lifted off after being left in acetone vapor for a period of time. FIG. 4 (c) shows a multilayer WSe obtained in example 4 2 -a monolayer graphene film structure. As can be seen from FIG. 4 (c), a multilayer WSe is obtained after the PMMA is completely removed by the acetone vapor 2 And heterostructures of single layer graphene stacks.
Example 5
(1) At 1X 1cm 2 The silicon/silicon oxide of (2) was used as a substrate, and the surface of the substrate was treated with oxygen plasma at a power of 100mW for 2 minutes.
(2) High-orientation pyrolytic graphite (HOPG) crystals purchased from Nanjing Xianfeng nano company are clamped by tweezers, adhered to the surface of a 3M adhesive tape, repeatedly cleaved, attached to the surface of the silicon/silicon oxide substrate in step (1), pressed on a heat table at 110 ℃, and mechanically dissociated graphite in the cooling process, so that large-area thin-layer graphene is obtained on the substrate.
(3) Spin-coating PMMA solvent on the surface of the substrate with the thin graphene, drying, attaching PDMS as a supporting layer, placing the substrate into a container with water vapor at 90 ℃ for 10 minutes, taking out and uncovering the PDMS supporting layer, and obtaining the graphene-PMMA-PDMS sample.
(4) And (3) attaching the graphene-PMMA-PDMS sample obtained in the step (3) to a part prepared in advance, etching the substrate to form a groove, and heating at a high temperature of 70 ℃ to facilitate the tight attachment of graphene and the substrate. After that, the PDMS support layer was lifted off after being left in acetone vapor for a period of time. Fig. 4 (d) shows the structure of the suspended thin-layer graphene film prepared in example 5. As can be seen from fig. 4 (d), the substrate structure with suspended graphene film can be obtained after PMMA is completely removed by acetone vapor.
Example 6
(1) At 1X 1cm 2 The silicon/silicon oxide of (2) was used as a substrate, and the surface of the substrate was treated with oxygen plasma at a power of 100mW for 30 seconds.
(2) MoTe from hq-graphic was gripped with forceps 2 The crystal is adhered on the surface of the silica gel film and repeatedly cleaved by adopting a plurality of PDMS films with the same size, the surface of the silicon/silicon oxide substrate adhered to the silicon/silicon oxide substrate in the step (1) is pressed on a heat table at 110 ℃, and the mechanical dissociation of graphite is realized in the cooling process, namely, a thin layer MoTe is obtained on the substrate 2 。
(3) Will be provided with a thin layer of MoTe 2 Spin-coating PMMA solvent on the surface of the substrate, drying, attaching PDMS as a supporting layer, placing into a container with water vapor at 90 ℃ for 20 minutes, taking out and uncovering the PDMS supporting layer to obtain a thin layer MoTe 2 -PMMA-PDMS sample.
(4) The thin layer MoTe obtained in (3) is subjected to 2 Attachment of PMMA-PDMS sample to Pre-mechanical cleavage with Single graphene and Evaporation withHeating the gold electrode substrate at 100 ℃ to facilitate thin MoTe layer 2 The graphene is tightly attached to the substrate-single-layer graphene. After that, the PDMS support layer was lifted off after being left in acetone vapor for a period of time. FIG. 4 (e) shows a thin layer MoTe obtained in example 6 2 -a single layer graphene heterostructure. As can be seen from FIG. 4 (e), a thin layer MoTe is obtained after the PMMA is completely removed by the acetone vapor 2 Heterostructures stacked with single layer graphene.
Example 7
(1) At 3X 5cm 2 The silicon/silicon oxide of (2) was used as a substrate, and the surface of the substrate was treated with oxygen plasma at a power of 50mW for 200 seconds.
(2) Quartz boat is placed at the upstream of the tube furnace, the boat is filled with weighed high-purity sulfur powder, and the ceramic boat is used in a high-temperature area to form WO 2.9 The powder was used as a precursor, and the substrate in (1) was placed upside down on top of the boat with a flow rate of 80sccm, a growth temperature of 850℃and maintained at high temperature for 40 minutes. WSe finally obtaining CVD growth on a substrate 2 Triangular crystals.
(3) Thin layer WSe with CVD growth 2 Spin-coating PMMA solvent on the surface of the substrate, drying, attaching PDMS as a supporting layer, placing into a container with water vapor at 90 ℃ for 15 minutes, taking out and uncovering the PDMS supporting layer to obtain a thin layer WSe 2 -PMMA-PDMS sample.
(4) The thin layer WSe obtained in (3) is subjected to 2 Attachment of PMMA-PDMS sample to Pre-transfer with Bi 2 O 2 Heating the substrate of Se at 80 ℃ to facilitate thin layer WSe 2 With substrate-Bi 2 O 2 Se is tightly attached. After that, the PDMS support layer was lifted off after being left in acetone vapor for a period of time. FIG. 4 (f) shows a sheet WSe obtained in example 7 2 -Bi 2 O 2 Se heterostructures. As can be seen from FIG. 4 (f), a thin layer WSe is obtained after the PMMA is completely removed by the acetone vapor 2 -Bi 2 O 2 Heterostructure of Se stacks.
Example 8
The preparation was performed according to the preparation method of example 1, except that the spin-coating of PMMA solvent in step (3) was adjusted to sequentially spin-coat rosin and PMMA solvent, and drying was performed for 1min after spin-coating of rosin, to obtain a silver pattern structure covered with graphene film. The surface roughness of the transferred sample was lower than in example 1.
While the invention has been described in detail in the foregoing general description and specific examples, it will be apparent to those skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (15)
1. A method of two-dimensional material transfer or stacking based on water vapor, comprising:
s100, treating the substrate by oxygen plasma to obtain a pretreated substrate;
s200, generating a layered two-dimensional material on the surface of the pretreated substrate to obtain a prefabricated composite substrate;
s300, spin-coating a transfer medium on the surface of the prefabricated composite substrate, drying, and covering support gel on the surface of the dried transfer medium to obtain the prefabricated transfer substrate;
s400, fumigating the prefabricated transfer substrate in a steam environment to obtain a transfer substrate;
s500, stripping the pretreated substrate on the transfer substrate to obtain a transfer substrate;
s600, transferring the transfer substrate to a target substrate, baking, and eluting the transfer medium to finish transfer or stacking of the two-dimensional material.
2. A method of two-dimensional material transfer or stacking based on water vapour according to claim 1 wherein the substrate material is selected from one or more of silicon, sapphire and mica.
3. A method of two-dimensional material transfer or stacking based on water vapour according to claim 1 or 2, wherein the layered two-dimensional material is provided by graphite or metal chalcogenides.
4. A two-dimensional material transfer or stacking method based on water vapor according to claim 3, wherein said metal chalcogenides have the formula MX 2 Wherein M is selected from Mo, W, sn, ta, nb, pt or Ga, and X is selected from S, se or Te.
5. A two-dimensional material transferring or stacking method based on water vapor according to claim 3, wherein said graphite is pyrolytic graphite crystal or natural graphite crystal with high orientation.
6. A method of transferring or stacking two-dimensional material based on water vapor as claimed in claim 1 or 2, wherein the layered two-dimensional material is formed in step S200 by mechanical cleavage or chemical vapor deposition.
7. A method of two-dimensional material transfer or stacking based on water vapour according to claim 1 or 2, wherein said transfer medium in step S300 is selected from one or more of polymethyl methacrylate, polystyrene and rosin.
8. A two-dimensional material transfer or stacking method based on water vapour according to claim 7 wherein the spin-coated transfer medium has a thickness of 200nm-10 μm after drying.
9. The method of two-dimensional material transfer or stacking based on water vapor according to claim 7, wherein the temperature of the drying process in step S300 is 100-140 ℃ for 2-10min.
10. A method of transferring or stacking two-dimensional materials based on water vapor according to claim 9, wherein the transfer medium is selected from polymethyl methacrylate and rosin, and the spin-coating process comprises:
s301, spin-coating rosin on the surface of a prefabricated composite substrate, lightly touching the surface of the rosin by adopting a rough surface, and then placing the substrate in a first temperature condition for drying for 1-2min to obtain a substrate young body;
s302, spin-coating polymethyl methacrylate on the surface of the rosin layer on the obtained substrate young body, and then drying for 1-9min at a second temperature; wherein,,
the temperature value of the first temperature is smaller than the temperature value of the second temperature.
11. The two-dimensional material transferring or stacking method based on water vapor according to claim 10, wherein the surface area of the spin-coated rosin in step S301 is smaller than the area of the spin-coated polymethyl methacrylate in step S302, and the spin-coated polymethyl methacrylate has a rim formed on the outer edge of the spin-coated rosin.
12. A method of two-dimensional material transfer or stacking based on water vapour according to claim 1 or 2, wherein the support gel is polydimethylsiloxane and/or silica gel.
13. A method of two-dimensional material transfer or stacking based on water vapour according to claim 12, wherein the support gel has a thickness of 200 μm-2mm.
14. A two-dimensional material transferring or stacking method based on water vapor according to claim 1 or 2, wherein the fumigation time in step S400 is 10-30min.
15. A two-dimensional material transferring or stacking method based on water vapor according to claim 14, wherein the baking process in step S600 is performed at 120-150 ℃ for 1-3min.
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| CN105152162A (en) * | 2014-11-28 | 2015-12-16 | 游学秋 | Batch large-scale production method of two dimensional material film |
| CN106283052A (en) * | 2016-08-23 | 2017-01-04 | 北京航空航天大学 | A kind of two-dimensional material regulation and control silicon-carbon composite construction hydrogen resistance coating and preparation method thereof |
| CN110983287A (en) * | 2019-10-21 | 2020-04-10 | 武汉大学 | Method for transferring large-area two-dimensional materials |
| CN111704128A (en) * | 2020-05-27 | 2020-09-25 | 东南大学 | Two-dimensional material transfer method based on substrate with steps |
| CN111763923A (en) * | 2020-06-30 | 2020-10-13 | 中国科学院上海微系统与信息技术研究所 | Two-dimensional material layer transfer method after preparation |
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