CN110699749A - Method for preparing large-area continuous single-layer single-crystal graphene film - Google Patents
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- CN110699749A CN110699749A CN201810744460.3A CN201810744460A CN110699749A CN 110699749 A CN110699749 A CN 110699749A CN 201810744460 A CN201810744460 A CN 201810744460A CN 110699749 A CN110699749 A CN 110699749A
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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
- C30B25/02—Epitaxial-layer growth
- C30B25/18—Epitaxial-layer growth characterised by the substrate
- C30B25/186—Epitaxial-layer growth characterised by the substrate being specially pre-treated by, e.g. chemical or physical means
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/16—Polishing
- C25F3/22—Polishing of heavy metals
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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
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
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Abstract
The invention discloses a method for preparing a large-area continuous single-layer single-crystal graphene film. The method comprises the following steps: and carrying out electrochemical polishing on the single crystal copper to obtain a single crystal copper substrate, and then carrying out growth of graphene on the single crystal copper substrate to obtain the continuous single-layer single crystal graphene film. At high temperature, a lot of silicon-oxygen compounds are attached to the surface of metal copper, which seriously affects the growth of graphene, and electrochemical polishing can remove the silicon-oxygen compounds, so that the surface of the copper becomes flat and clean. And then growing graphene by using the single-crystal copper to obtain single-layer graphene islands with the same orientation, and connecting the single-layer graphene islands to obtain the continuous single-layer single-crystal graphene film.
Description
Technical Field
The invention relates to a method for preparing a large-area continuous single-layer single-crystal graphene film.
Background
Graphene is a two-dimensional atomic crystal with a hexagonal honeycomb structure, which is a single atomic layer thick. It was prepared in 2004 by andrelium and corestin norworth schoft, physicists of manchester university, uk, jointly by mechanical stripping, and was thereafter of widespread interest to global scientists. The graphene has unique and excellent properties including good electrical conductivity and thermal conductivity, excellent mechanical properties and light transmittance and the like, and the properties enable the graphene to have wide application prospects in the fields of field effect transistors, flexible transparent electrodes, supercapacitors, graphene paper and the like.
At present, the main methods for preparing graphene are: mechanical lift-off, SiC epitaxial growth, liquid phase lift-off, and Chemical Vapor Deposition (CVD). The chemical vapor deposition method is suitable for mass production and has relatively low price, so that the chemical vapor deposition method is the preparation method with the greatest industrial prospect. Among them, the preparation method using metal catalyst such as copper and nickel as substrate is the main one. Since a single layer of high quality graphene can be controllably obtained on copper, a chemical vapor deposition method using metallic copper as a substrate has been a hot spot of research in recent years. However, there are a number of problems with graphene grown using copper substrates. Most of the currently marketed copper foils are polycrystalline copper foils, and graphene growing on the polycrystalline graphene foils serving as substrates is a polycrystalline graphene film, and a plurality of crystal boundaries exist on the polycrystalline graphene film, so that the electrical properties of the polycrystalline graphene film are seriously influenced. Recently, it has been reported that a single crystal copper foil is successfully prepared and a large-sized single crystal graphene thin film is grown. However, it is found from experiments that a large amount of silicon oxide is attached to the surface of the copper foil, and the graphene film is damaged. In addition, small double-layer nucleation points are also introduced in the growth process, so that a plurality of double-layer islands exist after film formation, and the transmission of electrons is influenced. Whether these problems can be solved or not becomes a basis and a precondition for realizing the application of graphene or not.
Disclosure of Invention
The invention aims to provide a method for preparing a large-area continuous single-layer graphene film.
The invention provides a method for preparing a continuous single-layer single-crystal graphene film, which comprises the following steps:
and carrying out electrochemical polishing on the single crystal copper to obtain a single crystal copper substrate, and then carrying out growth of graphene on the single crystal copper substrate to obtain the continuous single-layer single crystal graphene film.
In the electrochemical polishing of the method, the polishing solution consists of water, phosphoric acid, ethanol, isopropanol and urea; the dosage ratio of the water, the phosphoric acid, the ethanol, the isopropanol and the urea is 250 mL: 125 mL: 125 mL: 25mL of: 4g of the total weight of the mixture;
the voltage of the electrochemical polishing is 3-5V; the current is 2-4A; polishing for 2-5 min; specifically 3 min.
In the graphene growing step, a carbon source is selected from at least one of methane, carbon monoxide, methanol, acetylene, ethanol, benzene, toluene, cyclohexane and phthalocyanine;
the reducing gas is hydrogen;
the inert gas is argon and/or nitrogen;
the growth temperature is 1070-1080 ℃; specifically 1075 ℃;
the reaction time is 0.5-1.5 h; specifically 40-60 min;
the flow rate of the inert gas is 100-400 sccm; specifically 250 sccm;
the flow rate of the reducing gas is 25-200 sccm;
the flow rate of the carbon source is 1-10 sccm; specifically 3-5 sccm; more specifically 3.5 sccm.
The single crystal copper may be specifically single crystal Cu (111).
A method of preparing the single crystal Cu (111) may include the steps of: processing the polycrystalline copper foil for a plurality of times to obtain the single crystal Cu (111);
each treatment comprises polishing and annealing;
after each annealing, the copper foil was naturally cooled to room temperature.
In the above method for producing single crystal Cu (111), each of the treatments is polishing and annealing;
the number of times is at least 3 times; specifically 3 times or 4 times.
In the polishing step, the polishing method is electrochemical polishing.
In the electrochemical polishing step, the polishing solution consists of water, phosphoric acid, ethanol, isopropanol and urea; in the polishing solution, the dosage ratio of water, phosphoric acid, ethanol, isopropanol and urea is 250 mL: 125 mL: 125 mL: 25mL of: 4g of the total weight of the mixture;
the voltage is 3V-5V;
the current is 2A-4A;
the polishing time is 2min-5 min.
The annealing is carried out in the presence of an inert gas and a reducing gas; the inert gas is argon or nitrogen;
the reducing gas is hydrogen.
The flow rate of the inert gas is 100sccm-400 sccm;
the flow rate of the reducing gas is 50sccm-200 sccm;
the annealing temperature is 1070-1083 ℃;
the annealing time is 30min-180 min.
In addition, the continuous single-layer single-crystal graphene film prepared by the method also belongs to the protection scope of the invention.
The method for preparing the continuous single-layer single-crystal graphene film selects single-crystal copper as a growth substrate. The single crystal copper eliminates a large amount of crystal boundaries and crystal faces existing on the surface of the commercially available copper, and highly oriented graphene islands can be obtained when graphene grows. And continuously growing the graphene islands until the graphene islands are connected together, so that the single crystal graphene film can be obtained. However, a very large amount of silicon oxide compounds adhere to the (111) surface of the single crystal copper after annealing, and these silicon oxide compounds form projections, which make the surface of the single crystal copper uneven; the silicon-oxygen compound can not catalyze the carbon source to decompose and grow the graphene, so that the obtained graphene film is broken and discontinuous. Furthermore, graphene grown with other copper foils can have a non-conductive white particle observed in the center, which is presumed to be a silicon-oxygen compound. Therefore, the elimination of silicon oxide compounds attached to the single crystal copper is important for preparing a high-quality graphene continuous film.
The single crystal copper (111) surface obtained by annealing is subjected to electrochemical polishing in advance and then graphene growth is carried out, so that pollutants and attached silicon oxide compounds on the surface of the single crystal copper can be removed, and the surface of the single crystal copper is very clean and flat. The graphene grown by using the single crystal copper has a very clean surface, and the obtained film is very complete and has no any cavity or damage; all the graphene islands are single-layer single-crystal graphene with the same orientation. When single-crystal copper is used for growth without electrochemical polishing, the obtained graphene is mostly multilayer graphene under the same conditions.
The Scanning Electron Microscope (SEM) characterization shows that a plurality of small white particles exist on the surface of the single crystal copper obtained after annealing, and the shapes of the small white particles are different. White in color because it is not electrically conductive. Energy scattering X-ray spectroscopy (EDX) and Auger Electron Spectroscopy (AES) showed that this material contained Si and O, and was identified as a silica compound. After electrochemical polishing, it can be seen on SEM that all white particles have disappeared and the surface of the copper sheet is very flat and clean.
Under SEM, it can be seen that after the graphene is grown, many particles are still present on the single crystal copper that is not electrochemically polished, and are present on the surface of the graphene. When treated with hydrofluoric acid (HF), holes were clearly visible under SEM in the original silicon oxide, which proved to hinder the growth of graphene and to damage and discontinue it, thus affecting the quality of graphene. After the electrochemical polishing treatment, the graphene has no protrusion under an Optical Microscope (OM), and the surface is very flat and clean. In addition, under the same condition, a plurality of multilayer regions can be generated before electrochemical polishing is carried out, and almost all the graphene is single-layer graphene after the electrochemical polishing, so that the regulation and control of the number of graphene layers not only depend on the condition, but also the quality of a substrate can play a decisive role.
Drawings
FIG. 1 is a scanning electron micrograph of a single-crystal copper (111) plane obtained after annealing at 1075 ℃.
FIG. 2 is a graph of energy scattering X-ray spectroscopy analysis of white particles on a single crystal copper (111) plane in example 1.
FIG. 3 is an Auger electron spectroscopy analysis chart of white particles on the (111) plane of single crystal copper in example 1.
FIG. 4 is a SEM photograph of a single crystal copper (111) surface after electrochemical polishing in example 1.
Fig. 5 is an optical microscopic photograph of graphene grown on a single-crystal copper (111) plane after electrochemical polishing used in example 1.
Fig. 6 is a scanning electron micrograph of graphene grown using a single crystal copper (111) plane without electrochemical polishing in example 1.
Fig. 7 is a scanning electron micrograph of graphene grown on a single-crystal copper (111) plane after hydrofluoric acid treatment in example 1 without electrochemical polishing.
Fig. 8 is an optical micrograph of graphene grown on a single-crystal copper (111) plane without electrochemical polishing in example 1.
Fig. 9 is an optical micrograph of graphene islands alone prior to film formation in example 2.
Fig. 10 is an optical micrograph of a graphene thin film formed and then etched in example 2.
Detailed Description
The method of the present invention is illustrated by the following specific examples, but the present invention is not limited thereto, and any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included within the scope of the present invention.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Examples 1,
First, a single crystal copper (111) plane is prepared
Firstly, cutting a commercial copper foil (with the purity of 99.9%) with the thickness of 100 microns into a size of about 4cm multiplied by 6cm, and carrying out electrochemical polishing in an ethanol/phosphoric acid system (wherein the specific composition of the polishing solution comprises deionized water (mL), phosphoric acid (mL), ethanol (mL), isopropanol (mL) and urea (g) according to the proportion of 250: 125: 125: 25: 4, and the conditions of the electrochemical polishing comprise that the voltage is kept at 5V, the current is 2A, and the polishing time is 3 min.) to remove the residual polishing solution on the surface by washing with the deionized water, and drying with nitrogen.
And secondly, placing the copper foil obtained in the first step into a high-temperature tube furnace, introducing 200sccm argon and 100sccm hydrogen, and starting heating. Heating the tube furnace to 1075 deg.C for 45 min. And keeping for 1h for annealing. And naturally cooling to room temperature, and taking out the sample.
And thirdly, carrying out electrochemical polishing treatment and high-temperature annealing on the copper foil obtained in the second step again until the surface of the sample is completely converted into a single crystal copper (111) surface. Fig. 1 is an SEM photograph of the single crystal copper (111) surface obtained after annealing, from which it can be seen that there are very many white particles on the surface, covering the copper foil surface. Fig. 2 and 3 show EDX characterization and AES characterization, respectively, and both confirm that the white particles are silicon oxide compounds and that the surface flat regions have no silicon oxide signal, indicating that they are present only in the protrusions.
Secondly, preparing a single-layer continuous graphene film
And (3) performing electrochemical polishing on the single crystal copper (111) obtained in the third step, placing the single crystal copper in the center of a tube furnace, introducing 250sccm argon and 25sccm hydrogen, and starting to heat. The temperature rise time is 45min, and when the temperature reaches 1075 ℃, 3.5sccm of methane is introduced and the growth lasts for 1 h. And naturally cooling to room temperature after the reaction is finished. Fig. 4 is an SEM photograph of a single crystal copper (111) surface after electrochemical polishing, on which no trace of white particles has been seen, and the surface is a flat and clean copper (111) surface. Fig. 5 is an OM diagram of the grown graphene, where there is no protrusion on the graphene, and the surface is very flat and clean.
As a control, graphene was grown under the same conditions using single crystal copper (111) that was not electrochemically polished.
Fig. 6 is an SEM photograph of the obtained graphene, in which a silicon oxide compound is embedded, having an influence on the intrinsic texture orientation of the graphene. Then, HF treatment was performed thereon, and the results are shown in FIG. 7. The original place where the silicon oxide compound exists is changed into a hole, so that the graphene is damaged, and the fact that the silicon oxide compound on the surface of the single crystal copper can seriously influence the quality of the graphene and cause the graphene to be damaged and incomplete is proved. Fig. 8 is a photograph of OM thereof, and it can be seen from comparison with fig. 5 that under the same conditions, graphene grown on single crystal copper without electrochemical polishing has many multilayer structures, while fig. 5 is a uniform single layer, which illustrates that for the regulation of the number of graphene layers, not only the conditions are depended, but also the quality of the substrate plays a decisive role.
Example 2 verification of Single Crystal Properties of graphene thin films
In order to verify the single crystallinity of the obtained graphene film, the judgment of the same orientation ratio of the graphene islands before film formation and the experiment of performing local etching on the film after film formation were performed, and the results are shown in fig. 9 and 10, respectively. In the first step of this example, the growth time after methane was fed was shortened from 1 hour to 40min, and the results in FIG. 9 were obtained. In the operation step, after the growth is finished, the flow rates of argon and hydrogen are kept unchanged, methane is closed, the temperature is kept constant for 5min, and then the temperature is naturally reduced to obtain the data in the graph 10. In fig. 9, most of the graphene islands have the same orientation, which is shown in that they have a same boundary pointing to the same direction, and all the graphene islands are hexagonal single crystals, so that the graphene film is also a single crystal film. In the etching action, the obtained holes have the same orientation as the grown graphene single crystal, so that the orientation of the grown single crystal graphene can be judged according to the orientation of the etched holes, and the monocrystallinity of the generated graphene film can be judged. As can be seen in fig. 10, the obtained holes all have the same orientation and are standard regular hexagons, which proves that the graphene islands are single-crystal graphene with the same orientation, and the graphene film is laterally confirmed to be single-crystal graphene.
Claims (10)
1. A method for preparing a continuous single-layer single-crystal graphene film comprises the following steps:
and carrying out electrochemical polishing on the single crystal copper to obtain a single crystal copper substrate, and then carrying out growth of graphene on the single crystal copper substrate to obtain the continuous single-layer single crystal graphene film.
2. The method of claim 1, wherein: in the electrochemical polishing, polishing solution consists of water, phosphoric acid, ethanol, isopropanol and urea; the dosage ratio of the water, the phosphoric acid, the ethanol, the isopropanol and the urea is 250 mL: 125 mL: 125 mL: 25mL of: 4g of the total weight of the mixture;
the voltage of the electrochemical polishing is 3-5V; the current is 2-4A; polishing for 2-5 min; specifically 3 min.
3. The method according to claim 1 or 2, characterized in that: in the graphene growing step, a carbon source is selected from at least one of methane, carbon monoxide, methanol, acetylene, ethanol, benzene, toluene, cyclohexane and phthalocyanine;
the reducing gas is hydrogen;
the inert gas is argon and/or nitrogen;
the growth temperature is 1070-1080 ℃; specifically 1075 ℃;
the reaction time is 0.5-1.5 h; specifically 40-60 min;
the flow rate of the inert gas is 100-400 sccm; specifically 250 sccm;
the flow rate of the reducing gas is 25-200 sccm;
the flow rate of the carbon source is 1-10 sccm; specifically 3-5 sccm; more specifically 3.5 sccm.
4. A method according to any one of claims 1-3, characterized in that: the single crystal copper is single crystal Cu (111).
5. The method of claim 4, wherein: a method for preparing the single crystal Cu (111), comprising the steps of: processing the polycrystalline copper foil for a plurality of times to obtain the single crystal Cu (111);
each treatment comprises polishing and annealing;
after each annealing, the copper foil was naturally cooled to room temperature.
6. The method of claim 5, wherein: each treatment is polishing and annealing;
the number of times is at least 3 times; specifically 3 times or 4 times.
7. The method of claim 6, wherein: in the polishing step, the polishing method is electrochemical polishing.
8. The method of claim 7, wherein: in the electrochemical polishing step, the polishing solution consists of water, phosphoric acid, ethanol, isopropanol and urea; in the polishing solution, the dosage ratio of water, phosphoric acid, ethanol, isopropanol and urea is 250 mL: 125 mL: 125 mL: 25mL of: 4g of the total weight of the mixture;
the voltage is 3V-5V;
the current is 2A-4A;
the polishing time is 2min-5 min.
9. The method according to any one of claims 5-8, wherein: the annealing is carried out in the presence of an inert gas and a reducing gas; the inert gas is argon or nitrogen;
the reducing gas is hydrogen.
The flow rate of the inert gas is 100sccm-400 sccm;
the flow rate of the reducing gas is 50sccm-200 sccm;
the annealing temperature is 1070-1083 ℃;
the annealing time is 30min-180 min.
10. A continuous single-layered single-crystal graphene thin film prepared by the method of any one of claims 1 to 9.
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| CN111188021A (en) * | 2020-01-19 | 2020-05-22 | 南京大学 | Pretreatment method of graphene growth substrate |
| CN111979525A (en) * | 2020-07-06 | 2020-11-24 | 上海交通大学 | Preparation method of high-conductivity graphene/copper composite wire |
| CN114657635A (en) * | 2022-03-22 | 2022-06-24 | 西南交通大学 | Method for rapidly preparing single crystal graphene |
| CN114684813A (en) * | 2020-12-28 | 2022-07-01 | 中国科学院化学研究所 | Preparation method of large-area uniform single-layer graphene film |
| CN115287757A (en) * | 2022-07-08 | 2022-11-04 | 中国科学院电工研究所 | Preparation method of copper single crystal wafer and single crystal graphene |
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