CN112265984A - Method for preparing high-quality graphene in batches in situ and product thereof - Google Patents
Method for preparing high-quality graphene in batches in situ and product thereof Download PDFInfo
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- CN112265984A CN112265984A CN202011194328.3A CN202011194328A CN112265984A CN 112265984 A CN112265984 A CN 112265984A CN 202011194328 A CN202011194328 A CN 202011194328A CN 112265984 A CN112265984 A CN 112265984A
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Abstract
The invention relates to a method for preparing high-quality graphene in batches in situ and a product thereof, belonging to the technical field of graphene preparation. According to the invention, after a plurality of copper foils are vertically placed, a self-made quartz rod is placed between the substrates, so that a plurality of limited domain channel structures are formed (because metal on the inner surface of the substrate can be deposited on the surface after being evaporated at high temperature, the roughness of the surface of the substrate can be obviously reduced in the limited domain channel structures), and the high-temperature annealing treatment is carried out in a CVD (chemical vapor deposition) tube furnace, and then carbon source gas is introduced to grow to form high-quality graphene. Because the smooth surface is not beneficial to the nucleation of the graphene, the method greatly reduces the nucleation density of the graphene on the surface of the substrate by pretreating the growth substrate, creates conditions for the growth of high-quality graphene, and can carry out batch treatment.
Description
Technical Field
The invention belongs to the technical field of graphene preparation, and particularly relates to a method for preparing high-quality graphene in batches in situ and a product thereof.
Background
Graphene is a two-dimensional material consisting of sp-based carbon atoms of one atomic layer thickness2A hexagonal honeycomb structure formed by hybridization. Graphene has many excellent properties, such as ultra-high mechanical strength (young's modulus of graphene is 1TPa, intrinsic strength of graphene is 130GPa), good thermal conductivity (thermal conductivity of graphene at room temperature is 5000 WmK)-1) High optical transmittance (graphene has a full-band light transmittance of up to 97.7%), and ultra-high conductivity (the electron mobility of graphene exceeds 2.5 × 105 cm)2V-1s-1) Thus, graphene has a wide range of applications.
In recent years, how to improve the quality of graphene has become a focus of research. Although graphene can grow over various microscopic features (such as steps and the like) and most defects (such as dislocations, atomic protrusions and the like) of the copper surface, the rough surface structure of copper still directly affects the quality of graphene grown thereon: firstly, the step structure on the copper surface may deflect the crystal orientation of graphene, so as to form defects such as crystal boundary and the like; second, studies have found that graphene tends to nucleate preferentially at defects and microstructural asperities, and thus the copper asperity surface structure increases nucleation density, which may reduce the quality of graphene. Therefore, the surface morphology and quality of copper can largely determine the quality of graphene prepared thereon. Although researchers treat the surface of the copper foil by using methods such as mechanical polishing and electrochemical polishing, the methods improve the quality of graphene to a certain extent, but the methods are only limited to single-sheet treatment.
Therefore, research on a method for preparing high-quality graphene, which enables mass production, is required.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a method for preparing high-quality graphene in situ in batch; the second purpose of the invention is to provide the high-quality graphene prepared by the method for preparing the high-quality graphene in batches in situ.
In order to achieve the purpose, the invention provides the following technical scheme:
1. a method for in-situ batch preparation of high quality graphene, the method comprising the steps of:
(1) preparing a growth substrate: vertically placing N substrates, and placing quartz rods among the substrates to form a plurality of limited area channel structures at intervals and avoid the adhesion among the substrates at high temperature;
(2) substrate pretreatment: putting the growth substrate in the step (1) into a CVD tubular furnace, and introducing auxiliary gas for high-temperature annealing pretreatment;
(3) growing graphene: introducing a carbon source gas after the pretreatment in the step (2), and growing in situ on the substrate to form graphene;
(4) and (3) post-treatment: and stopping introducing the carbon source gas after the growth is finished, and continuously introducing the auxiliary gas until the temperature is reduced to the normal temperature state and then taking out the carbon source gas.
Preferably, the substrate in step (1) is made of metal.
Further preferably, the metal is an alloy formed by any one or more of copper, nickel, iron or cobalt.
Preferably, the diameter of the quartz rod in the step (1) is 3-20 mm.
Preferably, the auxiliary gas in the step (2) and the step (4) is a mixed gas formed by hydrogen and argon, the flow rate of the introduced hydrogen is 5-200 sccm, and the flow rate of the introduced argon is 50-1000 sccm in the process of introducing the auxiliary gas.
Preferably, the high-temperature annealing pretreatment in the step (2) is specifically: the temperature in the CVD tube furnace is raised to 1000-1060 ℃ at a speed of 10-15 ℃/min and then kept for 30-240 min.
Preferably, the carbon source gas in the step (3) is any one of methane, ethylene or acetylene.
Preferably, the flow rate of the carbon source gas introduced in the step (3) is 3-100 sccm.
2. And preparing the obtained graphene film according to the method for preparing the high-quality graphene in batches in situ.
The invention has the beneficial effects that:
the invention discloses a method for preparing high-quality graphene in batches in situ, which comprises the steps of vertically placing a plurality of substrates (made of alloy or single metal), placing quartz rods between the substrates to form a plurality of limited-area channel structures, avoiding adhesion among the substrates at high temperature, placing the limited-area channel structures into a CVD (chemical vapor deposition) tube furnace for high-temperature annealing treatment, and introducing carbon source gas and auxiliary gas into the limited-area channel structures, wherein the carbon source gas and the auxiliary gas can be deposited on the surfaces of the substrates after metal on the inner surfaces of the substrates is evaporated under the high-temperature condition, so that the substrates are all in the same environmental condition in the limited-area channel structures, and a growth substrate with a flat and uniform surface is obtained, thereby preparing the high-quality graphene. Because the flat surface is not beneficial to the nucleation of the graphene, the method greatly reduces the nucleation density of the graphene on the surface of the substrate by pretreating the growth substrate, so that the graphene crystal domain with uniform crystal domain size and shape is obtained, conditions are created for the growth of high-quality graphene, and batch treatment and in-situ growth can be carried out. The method for preparing the graphene solves the problems of high cost, long treatment period, low efficiency and the like of a method for processing the copper foil by a single piece in the process of preparing the graphene in a large scale in the prior art, is beneficial to in-situ batch preparation of the graphene, and is also beneficial to promotion of application and popularization of graphene materials.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objectives and other advantages of the invention may be realized and attained by the means of the instrumentalities and combinations particularly pointed out hereinafter.
Drawings
For the purposes of promoting a better understanding of the objects, aspects and advantages of the invention, reference will now be made to the following detailed description taken in conjunction with the accompanying drawings in which:
FIG. 1 is an AFM image of a copper foil substrate in example 1 before (a) and after (b) pretreatment;
fig. 2 is a domain microscopic view of graphene prepared on each copper foil substrate by the preparation method in example 1, wherein a, b, c, d, e and f are the graphene prepared on different copper foil substrates, respectively;
fig. 3 is a graph of the sheet resistance of graphene obtained by testing after transferring graphene on each copper foil substrate prepared in example 1 onto a PET substrate, wherein a, b, c, d, e and f are respectively derived from the obtained graphene on different copper foil substrates (a, b, c, d, e and f) in fig. 2;
FIG. 4 is a schematic cross-sectional view of a substrate holder during a manufacturing process of the present invention.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It should be noted that, in the following embodiments, features in the embodiments may be combined with each other without conflict.
Example 1
Preparing high-quality graphene in situ in batch, specifically comprising the following steps:
(1) preparing a growth substrate: taking six copper foils as substrates (wherein the AFM image of the copper foils is shown as a in figure 1), vertically placing the six copper foils, wherein quartz rods with the diameter of 3mm are placed between the copper foil substrates, and separating the six copper foils to form a growth substrate with 6 confinement channel structures;
(2) substrate pretreatment: putting the growth substrate in the step (1) into a CVD (chemical vapor deposition) tube furnace, introducing a mixed gas formed by hydrogen and argon as an auxiliary gas (the flow of the introduced hydrogen is 50sccm and the flow of the introduced argon is 500sccm in the process of introducing the auxiliary gas), carrying out high-temperature annealing pretreatment (the temperature in the CVD tube furnace is raised to 1000 ℃ at a speed of 10 ℃/min and then is maintained) for 60min, and forming an AFM (atomic force microscopy) diagram of the pretreated copper foil substrate as shown in b in FIG. 1;
(3) growing graphene: introducing a carbon source gas (methane) for 30min at the flow rate of 5sccm after the pretreatment in the step (2), and growing in situ on the substrate to form graphene;
(4) and (3) post-treatment: and after the growth is finished, stopping introducing the carbon source gas, continuing introducing the auxiliary gas (the flow of introducing the hydrogen is 50sccm and the flow of introducing the argon is 500sccm in the process of introducing the auxiliary gas) until the temperature is reduced to the normal temperature state, and taking out the gas to obtain the high-quality graphene grown on the copper foil substrate, wherein a domain microscopic image of the graphene grown on each copper foil is shown in fig. 2.
Example 2
Preparing high-quality graphene in situ in batch, specifically comprising the following steps:
(1) preparing a growth substrate: vertically placing six cobalt substrates, wherein quartz rods with the diameter of 3mm are placed between the cobalt substrates, and 6 growth substrates with limited area channel structures are formed at intervals;
(2) substrate pretreatment: putting the growth substrate in the step (1) into a CVD (chemical vapor deposition) tubular furnace, introducing a mixed gas formed by hydrogen and argon as an auxiliary gas (the flow of introduced hydrogen is 5sccm and the flow of introduced argon is 50sccm in the process of introducing the auxiliary gas), and performing high-temperature annealing pretreatment (heating the temperature in the CVD tubular furnace to 1060 ℃ at a speed of 15 ℃/min and then keeping the temperature for 30 min) to form a pretreated cobalt-based sheet;
(3) growing graphene: introducing carbon source gas (ethylene) for 300min at the flow rate of 3sccm after the pretreatment in the step (2), and growing in situ on the substrate to form graphene;
(4) and (3) post-treatment: and stopping introducing the carbon source gas after the growth is finished, and continuing introducing the auxiliary gas (the flow of introducing hydrogen is 5sccm and the flow of introducing argon is 50sccm in the process of introducing the auxiliary gas) until the temperature is reduced to the normal temperature state, and taking out the gas to obtain the high-quality graphene grown on the cobalt-based substrate.
Example 3
Preparing high-quality graphene in situ in batch, specifically comprising the following steps:
(1) preparing a growth substrate: taking six copper-iron alloys as substrates to be vertically placed, wherein quartz rods with the diameter of 20mm are placed between the copper-iron alloy substrates, and 6 growth substrates with limited area channel structures are formed in a spaced mode;
(2) substrate pretreatment: putting the growth substrate in the step (1) into a CVD (chemical vapor deposition) tube furnace, introducing mixed gas formed by hydrogen and argon as auxiliary gas (the flow of the introduced hydrogen is 200sccm and the flow of the introduced argon is 1000sccm in the process of introducing the auxiliary gas), and performing high-temperature annealing pretreatment (the temperature in the CVD tube furnace is heated to 1040 ℃ at the speed of 12 ℃/min and then is maintained) for 200min to form a pretreated copper-iron alloy substrate;
(3) growing graphene: introducing carbon source gas (acetylene) for 10min at the flow of 100sccm after the pretreatment in the step (2), and growing in situ on the substrate to form graphene;
(4) and (3) post-treatment: and stopping introducing the carbon source gas after the growth is finished, and continuing introducing the auxiliary gas (the flow of introducing hydrogen is 200sccm and the flow of introducing argon is 1000sccm in the process of introducing the auxiliary gas) until the temperature is reduced to the normal temperature state, and taking out the graphene to obtain the high-quality graphene grown on the copper-iron alloy substrate.
In fig. 1, a and b are AFM images before and after pretreatment of the copper foil substrate, respectively, and it can be seen from comparison of the images and corresponding roughness measurement (Rq before pretreatment is 109nm, Rq after pretreatment is 2.6nm), that the roughness of the copper foil is significantly reduced by the pretreatment of the present invention.
Fig. 2 is a domain microscopic view of graphene prepared on each copper foil substrate by the preparation method in example 1, wherein a, b, c, d, e, and f are the graphene prepared on different copper foil substrates, respectively.
Fig. 3 shows the sheet resistance of graphene obtained by transferring graphene on each copper foil substrate prepared in example 1 onto a PET substrate and testing the sheet resistance of the obtained graphene, wherein a, b, c, d, e and f are respectively obtained from the obtained graphene on different copper foil substrates (a, b, c, d, e and f) in fig. 2. Therefore, the high-quality graphene with uniform sheet resistance is prepared in batch by the method.
FIG. 4 is a schematic cross-sectional view of a substrate holder during a manufacturing process of the present invention.
The same test results show that the graphene prepared in example 1 and example 2 has the same quality as the graphene in example 1.
In summary, the invention discloses a method for preparing high-quality graphene in batches in situ, which comprises the steps of vertically placing a plurality of substrates, placing a self-made quartz rod between the substrates to form a plurality of limited-area channel structures, placing the limited-area channel structures into a CVD (chemical vapor deposition) tube furnace for high-temperature annealing treatment, and introducing carbon source gas and auxiliary gas to prepare high-quality graphene, wherein the carbon source gas and the auxiliary gas can be deposited on the surfaces of the substrates after metal on the inner surfaces of the substrates is evaporated under the high-temperature condition, so that the substrates are in the same environmental condition in the limited-area channel structures, and the smooth and uniform surfaces of the growth substrates are obtained. The method has the advantages that the smooth surface is not beneficial to the nucleation of the graphene, so that the nucleation density of the graphene on the surface of the substrate is greatly reduced by pretreating the growth substrate, the graphene crystal domain with uniform crystal domain size and shape is obtained, conditions are created for the growth of high-quality graphene, and batch treatment and in-situ growth can be carried out. The problems of high cost, long treatment period, low efficiency and the like of a method for processing the substrate by using a single chip in the process of preparing graphene on a large scale in the prior art are solved, and the method is favorable for application and popularization of graphene materials.
Finally, the above embodiments are only intended to illustrate the technical solutions of the present invention and not to limit the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all of them should be covered by the claims of the present invention.
Claims (9)
1. A method for preparing high-quality graphene in batches in situ is characterized by comprising the following steps:
(1) preparing a growth substrate: vertically placing N substrates, and placing quartz rods among the substrates to form a plurality of limited area channel structures at intervals and avoid the adhesion among the substrates at high temperature;
(2) substrate pretreatment: putting the growth substrate in the step (1) into a CVD tubular furnace, and introducing auxiliary gas for high-temperature annealing pretreatment;
(3) growing graphene: introducing a carbon source gas after the pretreatment in the step (2), and growing in situ on the substrate to form graphene;
(4) and (3) post-treatment: and stopping introducing the carbon source gas after the growth is finished, and continuously introducing the auxiliary gas until the temperature is reduced to the normal temperature state and then taking out the carbon source gas.
2. The method for preparing high-quality graphene in situ in batch according to claim 1, wherein the diameter of the quartz rod in the step (1) is 3-20 mm.
3. The method for preparing high-quality graphene in batches in situ according to claim 1, wherein the auxiliary gas in the step (2) and the step (4) is a mixed gas formed by hydrogen and argon, the flow of the introduced hydrogen is 5-200 sccm and the flow of the introduced argon is 50-1000 sccm in the process of introducing the auxiliary gas.
4. The method for preparing high-quality graphene in batches in situ according to claim 1, wherein the high-temperature annealing pretreatment in the step (2) is specifically: the temperature in the CVD tube furnace is raised to 1000-1060 ℃ at a speed of 10-15 ℃/min and then kept for 30-240 min.
5. The method for preparing high-quality graphene in situ in batch according to claim 1, wherein the carbon source gas in the step (3) is any one of methane, ethylene or acetylene.
6. The method according to claim 1, wherein the carbon source gas is introduced at a flow rate of 3 to 100sccm in the step (3).
7. The method according to claim 1, wherein the substrate in step (1) is made of metal.
8. The method for preparing high-quality graphene in situ in batch according to claim 7, wherein the metal is an alloy formed by any one or more of copper, nickel, iron or cobalt.
9. The graphene thin film prepared by the method for preparing high-quality graphene in batches in situ according to any one of claims 1 to 8.
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