KR101093657B1 - Fabrication method of graphene film by using joule heating - Google Patents
Fabrication method of graphene film by using joule heating Download PDFInfo
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- KR101093657B1 KR101093657B1 KR20090078057A KR20090078057A KR101093657B1 KR 101093657 B1 KR101093657 B1 KR 101093657B1 KR 20090078057 A KR20090078057 A KR 20090078057A KR 20090078057 A KR20090078057 A KR 20090078057A KR 101093657 B1 KR101093657 B1 KR 101093657B1
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Abstract
It provides a graphene film manufacturing method using a heat resistance heating (joule heating). In the present invention, a substrate on which a graphitized metal film is formed is charged into a chamber, and a current is passed through at least one of the graphitized metal film and the substrate in the chamber to heat the graphitized metal film by the heat transfer effect at that time. By supplying a gaseous carbon source into the chamber to solidify a carbon component in the graphitized metal film while the graphitized metal film is heated, the amount of current is controlled to cool the graphitized metal film at a controlled rate. Graphene is deposited on the surface of the graphitized metal film from the solid solution of carbon.
Description
The present invention relates to a method for producing a graphene film, and more particularly, to a method for producing graphene by supplying a gaseous carbon source to a substrate on which a graphitized metal catalyst is formed.
Graphene is a material composed of carbon atoms bonded in two dimensions like graphite, and unlike graphite, it is formed as a single layer or a very thin layer of 2-3 layers. Since graphene is flexible, very high in electrical conductivity, and transparent, studies are being conducted to use it as a transparent and curved electrode or to use it as an electron transport material such as an electron transport layer in an electronic device.
Graphene has attracted much attention as an electron transport layer and a transparent electrode of an electronic device, in particular, using a photovoltaic principle of receiving light and converting it into electricity, such as a solar cell or a photodetector. Indium Tin Oxide (ITO) is the most widely used transparent electrode of electronic devices, but the manufacturing cost is increasing due to the price rise and depletion of indium (In), which is a main material. have.
Conventional methods for obtaining a graphene film include a micromechanical method and a SiC crystal pyrolysis method. The micromechanical method is to attach a scotch tape to a graphite sample and then remove it to obtain graphene in the form of a sheet separated from graphite on the scotch tape surface. In this case, the peeled off graphene sheet has a constant number of layers, and its shape is not constant due to the tearing of paper. Moreover, there is a disadvantage in that it is extremely difficult to obtain a graphene sheet in a large area. In the SiC crystal pyrolysis method, when SiC single crystal is heated, SiC on the surface is decomposed to remove Si and graphene is generated by the remaining carbon (C). In this method, SiC single crystals used as starting materials are very expensive, and graphene is very difficult to obtain in large areas.
Conventionally, a method of manufacturing a graphene film for transparent electrodes includes a method of obtaining a graphene film by coating a catalyst on graphite attached on a substrate, covering the polymer thereon, and heat treating the graphene to obtain graphene from the graphite, and then removing the substrate. This method produces a high quality graphene film, but the process is rather complicated.
Another method is to oxidize graphene, mix and disperse it in a solution, and then form it directly as an electrode or an electron transport layer through spin coating. The method of using oxidized graphene has advantages of simple and easy formation of large-area graphene film because it can use general polymer process such as spin coating, and it is simpler than the method of refining graphite. . However, since the graphene is oxidized, the electrical characteristics are lower than those of pure graphene, and the transparent electrode is divided into small pieces rather than a single thin film, and thus the characteristics of the transparent electrode are inferior to those of the conventional ITO.
The problem to be solved by the present invention is to provide a method for obtaining a high quality graphene film simply and easily in large area.
In the graphene film production method according to the present invention for solving the above problems it is proposed to produce a graphene by supplying a gaseous carbon source while heating the substrate on which the graphitized metal catalyst is formed by a joule heating. In the present invention, a substrate on which a graphitized metal film is formed is charged into a chamber, and a current is passed through at least one of the graphitized metal film and the substrate in the chamber to heat the graphitized metal film by the heat transfer effect at that time. By supplying a gaseous carbon source into the chamber to solidify a carbon component in the graphitized metal film while the graphitized metal film is heated, the amount of current is controlled to cool the graphitized metal film at a controlled rate. Graphene is deposited on the surface of the graphitized metal film from the solid solution of carbon.
The gaseous carbon source may comprise a CH 4 gas and may further supply hydrogen with the gaseous carbon source. The heating temperature of the graphitized metal film may be 600 to 1000 ° C. when supplying the gaseous carbon source, and the cooling rate of the graphitized metal film may be 1 to 50 ° C. per second when the graphene is deposited. The thickness of the precipitated graphene may be 1 to 1000nm, the graphitized metal film is Ni, Co, Fe, Pt, Au, Al, Cr, Cu, Mg, Mn, Mo, Rh, Si, Ta, Ti, It may be at least one selected from the group consisting of W, U, V and Zr.
After the graphene precipitation may be further included by removing the graphitized metal film by an acid treatment, separating the precipitated graphene from the substrate. Graphene separated from the substrate has a film or sheet shape, which can be used as a transparent electrode of devices such as solar cells and photodetectors.
According to the present invention, a current is passed through at least one of the graphitized metal film and the substrate and the graphitized metal film is heated by the heat transfer effect at that time. That is, the heat resistance heating method is used. The electric field formed by the flowing current causes the particle size of the graphitized metal film to be large, thereby making the surface very flat. This makes it possible to obtain a higher quality graphene film.
Cooling, the last step in the graphene process, is the most important factor in controlling the quality of the graphene formed. In the present invention, cooling by adjusting the amount of current flowing in the heat resistance heating method without flowing an inert gas or using natural cooling. Since the thermal resistance can be precisely controlled by the amount of current, it is possible to accurately control the amount of heat generated accordingly, so that it is easy to adjust the cooling rate exactly to the desired cooling rate.
In addition, since the present invention can proceed at atmospheric pressure, the process is simple and mass production is possible, and the heater design is not a method of heating the substrate indirectly by the radiant heat of the resistance heater or the lamp, but directly by the heat resistance heating method. No change is necessary, which is advantageous for large area at low cost.
Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but will be implemented in various forms, and only the present embodiments are intended to complete the disclosure of the present invention and to those skilled in the art to fully understand the scope of the invention. It is provided to inform you.
1 is a flowchart of the present invention, and FIGS. 2 to 4 are schematic implementation views accordingly.
First, a
The
The
The graphitized
The
In particular, in the
Next, an electric current flows in at least one of the
As mentioned above, the
In this step peculiar to the present invention, the
Next, a gaseous carbon source is supplied into the
The gaseous carbon source may use a hydrocarbon gas family such as ethane, ethylene, ethanol, acetylene, propane, propylene, butane, butadiene, pentane, hexanes, and in particular may include CH 4 gas, You can supply more. In other words, CH 4 gas, which is a gaseous carbon source, can be supplied at this stage while continuously supplying a mixed gas of hydrogen-argon gas for maintaining the atmospheric pressure in the
In the processing of the substrate which normally requires heating, a method of heating the substrate indirectly by radiant heat of a resistance heater or a lamp is mainly used. In recent years, due to the increase in the size of a thin film display, the increase in the demand for inexpensive solar panels, and the like, it is required to increase the size of the graphene film for transparent electrodes. In order to obtain such a large graphene film, the
However, in the present invention, since the
Next, the supply of the gaseous carbon source is stopped and the amount of current flowing in the heat resistance heating method is reduced to cool the
This cooling process is an important step to obtain high quality by uniformly depositing graphene, and rapid cooling can lead to obtaining graphene that is less than the desired thickness or to causing cracks in the resulting graphene film. Since the thickness is too thick or the productivity is impaired, it is desirable to cool it at a controlled constant rate if possible. The ideal cooling rate is 1 to 50 ° C per second, and most ideally 10 ° C per second.
Cooling after normal film formation is mainly performed by flowing inert gas or natural cooling. However, if the cooling using an inert gas after the production of the graphene as in the present invention, since the temperature is indirectly controlled by the inert gas, accurate temperature control is difficult. Natural cooling is a method that does not control the temperature at all, so if natural cooling is performed after the production of graphene as in the present invention, the process becomes simple, but the quality of graphene may be greatly degraded.
In the present invention, since the calorific value can be controlled by adjusting the amount of current, it is very easy to accurately control the cooling rate of the
Next, the
As described above, according to the present invention, it is possible to raise the temperature of the graphitized metal film easily by using a heat resistance heating method, to flatten the surface of the graphitized metal film, and to form a high-quality graphene film by controlling the temperature during cooling. . In addition, since the present invention can proceed at atmospheric pressure, the process is simple and mass production is possible, and the heater design of the chamber is not required, and thus, it is advantageous for large area.
Experimental Example
The p-type silicon substrate on which SiO 2 was formed was sonicated with acetone and ethanol and then washed with deionized water (DI-water). The washed substrate was dried with N 2 gas and a Ni film was thermally evaporated at least 200 nm as a graphitized metal film on the substrate.
In order to carry out the method according to the present invention, a Ni film-deposited substrate was placed in a chamber for CVD rules, and the air was evacuated to create a vacuum state, and then filled with atmospheric pressure with a gas of 1: 4 mixed with hydrogen and argon. An electric current was made to flow through the board | substrate and Ni film | membrane in the state which maintained the normal pressure, and the temperature of the Ni film | membrane was raised to 800 degreeC, and Ni surface was made flat.
When heating using the heat resistance heating method, there are differences in current and voltage conditions depending on the size of the specimen and the doping concentration of the silicon substrate. Usually, a p-type silicon substrate, which is readily available, can be heated to 800-900 ° C by applying a voltage of 5-10V and a current of 10-20A when the specimen size is 1cm x 6cm. When the size of the specimen is 2.5cm x 6cm, it can be heated to 800 ~ 900 ℃ by flowing a voltage of 10 ~ 15V, current 20 ~ 30A.
While maintaining the surface of the Ni film at 800 ° C., CH 4 gas and hydrogen-argon mixed gas were respectively flowed at a rate of 50 sccm and 200 to 300 sccm for 30 seconds, and then cooled down to room temperature by 10 ° C. per second by reducing the amount of current.
FIG. 5A is a SEM photograph of a Ni-film thermally-deposited state (as-depo) as a graphitized metal film. The Ni film in the thermally evaporated state is a polycrystalline film made of particles of very small size, as shown in FIG. 5 (a), and the surface roughness is poor because it occupies a large portion of the interface between the particles.
Figure 5 (b) is a SEM photograph when the Ni film is simply heat-treated at 900 ℃ for 15 minutes in the furnace for comparison with the present invention, Figure 5 (c) is a Ni film and a substrate according to the present invention It is a SEM photograph when a Ni film is heat-treated by passing an electric current. At this time, the size of the specimen was 1cm x 5cm and a voltage of 10V and a current of 15A were flowed.
5 (b) and 5 (c) show that the particle size of Ni is increased and surface roughness is also improved as compared with FIG. It can be seen that even when the heat treatment at the same time and the same temperature (c), which is the case of applying heat treatment by applying the heat transfer effect at that time, does not use a current, the particle size becomes larger and the surface becomes flat. According to the present invention, since graphene is produced by supplying a gaseous carbon source on the Ni film having a flat surface in the state (c), graphene is formed in high quality.
Figure 6 is a SEM photograph showing that the graphene is grown on the Ni film by the heat resistance heating method according to the experimental example of the present invention. Graphene was formed by supplying a source of CH 4 gas on a Ni film having a flat surface, and the cooling rate was controlled to be constant. Thus, the graphene film formed was formed along the flat surface state of the Ni film and has excellent surface quality. You can see that.
The graphene-grown substrate was placed in an HF solution to etch SiO 2 , and then the Ni film was etched in a TFG solution to finally extract only a sheet-like graphene film. The graphene film was evaluated to have excellent mechanical and electrical properties such that it can be used as a transparent electrode of a device such as a solar cell or a photodetector.
Although the preferred embodiments of the present invention have been shown and described above, the present invention is not limited to the specific preferred embodiments described above, and the present invention belongs to the present invention without departing from the gist of the present invention as claimed in the claims. Various modifications can be made by those skilled in the art, and such changes are within the scope of the claims.
1 is a flow chart of the present invention.
2 to 4 are schematic implementation figures in accordance with the present invention.
Figure 5 is a SEM image of the surface of the Ni film in the thermally evaporated state, the Ni film heat-treated for comparison with the present invention, and the Ni film heat-treated by the heat resistance heating method according to the present invention.
6 is a SEM photograph showing the growth of graphene on the Ni film according to the experimental example of the present invention.
<Explanation of symbols for the main parts of the drawings>
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Claims (8)
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KR20090078057A KR101093657B1 (en) | 2009-08-24 | 2009-08-24 | Fabrication method of graphene film by using joule heating |
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Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2012134161A2 (en) * | 2011-03-29 | 2012-10-04 | 국립대학법인 울산과학기술대학교 산학협력단 | Graphene sheet, transparent electrode including graphene sheet, active layer, and display device, electronic device, photovoltaic device, battery, solar cell, and dye-sensitized solar cell employing transparent electrode |
US20120234240A1 (en) | 2011-03-17 | 2012-09-20 | Nps Corporation | Graphene synthesis chamber and method of synthesizing graphene by using the same |
WO2012150761A1 (en) * | 2011-05-03 | 2012-11-08 | 한국과학기술원 | Method for manufacturing graphene and device for manufacturing graphene |
KR101188988B1 (en) * | 2011-05-23 | 2012-10-08 | 한양대학교 산학협력단 | Method for seperating of graphene thin film |
JP5862080B2 (en) * | 2011-07-06 | 2016-02-16 | ソニー株式会社 | Graphene production method and graphene production apparatus |
KR101878735B1 (en) * | 2011-07-29 | 2018-07-17 | 삼성전자주식회사 | Process for preparing graphene sheet |
KR101465419B1 (en) * | 2012-12-17 | 2014-12-01 | (주)우주일렉트로닉스 | Pruducing method for graphite sheet |
KR102650379B1 (en) | 2017-09-28 | 2024-03-25 | 아톰 드레드즈 코퍼레이션 | Graphene fiber manufactured by joule heating and fabricating method of the same |
CN112678808B (en) * | 2020-12-24 | 2021-08-03 | 广东工业大学 | Device and method for producing graphene by electric impact method |
KR102477237B1 (en) * | 2022-07-05 | 2022-12-14 | (주)스피너스 | Method for mamufacturing graphene |
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