JP2011168448A - Method for manufacturing graphene film - Google Patents
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本発明は、グラフェン膜の製造方法に関する。 The present invention relates to a method for manufacturing a graphene film.
グラフェンは、炭素原子がｓｐ２結合で結合して同一平面内に並んだ炭素原子のシートである。このグラフェンを丸めればフラーレンとなり、筒状にすればカーボンナノチューブとなる。このように、グラフェンは、様々なカーボン材料の母材となるものである。 Graphene is a sheet of carbon atoms in which carbon atoms are bonded by sp 2 bonds and arranged in the same plane. If this graphene is rounded, it becomes a fullerene, and if it is made cylindrical, it becomes a carbon nanotube. Thus, graphene is a base material for various carbon materials.
従来より、グラフェンは、機械的剥離法と呼ばれる方法で製造されていた。この方法は、下記非特許文献１，２に示されるように、グラファイト単結晶を粘着テープによって剥離して数十層のグラフェン積層体を粘着テープに転写し、粘着テープに転写されたグラフェン積層体を基板上に擦り付けて、ランダムにグラフェン単層体及びグラフェン積層体からなるグラフェン膜を基板上に形成する方法である。この方法は、簡便な方法で高品質のグラフェン膜が得られるが、大面積のグラフェン膜の製造には適さないものであった。 Conventionally, graphene has been produced by a method called a mechanical exfoliation method. In this method, as shown in Non-Patent Documents 1 and 2 below, a graphite single crystal is peeled off with an adhesive tape, a tens of layers of graphene laminate is transferred to the adhesive tape, and the graphene laminate transferred onto the adhesive tape Is rubbed onto the substrate, and a graphene film composed of a graphene monolayer and a graphene stack is randomly formed on the substrate. Although this method can provide a high-quality graphene film by a simple method, it is not suitable for producing a large-area graphene film.
また、デバイス応用を目指した、大面積のグラフェン膜の製造方法として、下記特許文献１には、有機化合物であるショウノウを炭素源として用い、ＣＶＤ法により、鉄、コバルト、ニッケル、炭化ケイ素、白金等で構成された基板上にグラフェン膜を成膜することが開示されている。 In addition, as a method for producing a large-area graphene film aimed at device application, Patent Document 1 listed below uses an organic compound, camphor, as a carbon source, and by CVD, iron, cobalt, nickel, silicon carbide, platinum It is disclosed that a graphene film is formed on a substrate constituted by the above.
しかしながら、特許文献１の方法では、その段落番号００２１に記されるように、石英管の内面にはグラフェン膜が形成されず、アモルファスカーボンとなると記載されている。このため、特許文献１の方法では、基板の種類によってはグラフェン膜を成膜できない問題があった。特に、工業的に頻繁に使用されるＳｉ基板、ＳｉＯ２／Ｓｉ基板、石英ガラス基板などにグラフェン膜を形成することは困難であった。 However, in the method of Patent Document 1, as described in paragraph number 0021, it is described that a graphene film is not formed on the inner surface of the quartz tube, and amorphous carbon is formed. For this reason, the method of Patent Document 1 has a problem that a graphene film cannot be formed depending on the type of substrate. In particular, it has been difficult to form a graphene film on a Si substrate, a SiO 2 / Si substrate, a quartz glass substrate, or the like that is frequently used industrially.
よって、本発明の目的は、基板選択の自由度が高く、大面積のグラフェン膜を基板上に形成することが可能なグラフェン膜の製造方法を提供することにある。 Therefore, an object of the present invention is to provide a method of manufacturing a graphene film that has a high degree of freedom in substrate selection and can form a large-area graphene film on the substrate.
上記目的を達成するため、本発明のグラフェン膜の製造方法は、種グラフェン結晶を設置した基板に炭素含有ガスを供給し、ＣＶＤ法により前記基板上にグラフェン膜を形成することを特徴とする。 In order to achieve the above object, a method for producing a graphene film of the present invention is characterized in that a carbon-containing gas is supplied to a substrate on which seed graphene crystals are placed, and the graphene film is formed on the substrate by a CVD method.
種グラフェン結晶を設置した基板に炭素含有ガスを供給すると、炭素原子が種グラフェン結晶の端部に選択的に付着して成長するので、グラフェンとの格子定数のマッチングが悪い材料からなる基板上であっても、大面積のグラフェン膜を成膜することができる。このため、本発明によれば、基板選択の自由度が高く、基板の材質によらず大面積のグラフェン膜を基板上に成膜できる。 When a carbon-containing gas is supplied to the substrate on which the seed graphene crystal is placed, carbon atoms selectively adhere to the edge of the seed graphene crystal and grow, so that on the substrate made of a material having a poor lattice constant matching with the graphene Even in such a case, a large-area graphene film can be formed. Therefore, according to the present invention, the degree of freedom of substrate selection is high, and a large-area graphene film can be formed on the substrate regardless of the substrate material.
本発明のグラフェン膜の製造方法は、前記炭素含有ガスが、炭化水素系化合物及び／又は炭化フッ素系化合物であることが好ましい。 In the method for producing a graphene film of the present invention, the carbon-containing gas is preferably a hydrocarbon compound and / or a fluorine-containing compound.
本発明のグラフェン膜の製造方法は、前記基板が、Ｓｉ基板、ＳｉＯ２／Ｓｉ基板及び石英ガラス基板から選ばれる一種以上であることが好ましい。 In the method for producing a graphene film of the present invention, the substrate is preferably at least one selected from a Si substrate, a SiO 2 / Si substrate, and a quartz glass substrate.
本発明のグラフェン膜の製造方法は、前記種グラフェン結晶が、グラフェン単層体及び／又はグラフェン積層体であることが好ましい。 In the method for producing a graphene film of the present invention, the seed graphene crystal is preferably a graphene monolayer and / or a graphene laminate.
本発明によれば、基板選択の自由度が高く、基板の材質によらず大面積のグラフェン膜を基板上に成膜できる。 According to the present invention, the degree of freedom of substrate selection is high, and a large-area graphene film can be formed on a substrate regardless of the material of the substrate.
本発明のグラフェン膜の製造方法は、種グラフェン結晶を設置した基板に炭素含有ガスを供給し、ＣＶＤ法により基板上にグラフェン膜を形成する。なお、本発明において、「グラフェン膜」とは、グラフェン単層体からなる膜に加えて、グラフェン単層体が複数積層したグラフェン積層体を含む膜を含むものとする。 In the method for producing a graphene film of the present invention, a carbon-containing gas is supplied to a substrate provided with seed graphene crystals, and the graphene film is formed on the substrate by a CVD method. In the present invention, the “graphene film” includes a film including a graphene stacked body in which a plurality of graphene single layer bodies are stacked in addition to a film formed of a graphene single layer body.
まず、種グラフェン結晶について説明する。 First, the seed graphene crystal will be described.
本発明において、種グラフェン結晶として、グラフェン単層体及び／又はグラフェン積層体を使用する。種グラフェン結晶としてグラフェン単層体を使用した場合、グラフェン単層体からなるグラフェン膜が得られ易くなる。また、種グラフェン結晶としてグラフェン積層体を使用した場合、グラフェン積層体からなるグラフェン膜が得られ易くなる。 In the present invention, a graphene monolayer and / or a graphene laminate is used as the seed graphene crystal. When a graphene monolayer is used as the seed graphene crystal, a graphene film composed of the graphene monolayer is easily obtained. In addition, when a graphene stack is used as the seed graphene crystal, a graphene film including the graphene stack is easily obtained.
グラフェン積層体の層数、すなわち、グラフェン積層体の厚みは、グラフェン膜の用途により異なるので特に限定しない。例えば、太陽電池の透明電極等の用途で使用する場合は、１〜１０ｎｍが好ましく、２〜３ｎｍがより好ましい。 The number of layers of the graphene stack, that is, the thickness of the graphene stack is not particularly limited because it varies depending on the use of the graphene film. For example, when used for applications such as a transparent electrode of a solar cell, 1 to 10 nm is preferable, and 2 to 3 nm is more preferable.
種グラフェン結晶の最大径は、１μｍ〜２００μｍが好ましく、２０μｍ〜２００μｍが好ましく、１００μｍ〜２００μｍが特に好ましい。種グラフェン結晶の最大径が１μｍ未満であると、アモルファスカーボンになり易い。また、２００μｍを超えると、種グラフェン結晶にしわが入りやすくなる。なお、本発明において種グラフェン結晶の最大径とは、光学顕微鏡や、電子顕微鏡で測定した種グラフェン結晶の最長部の径を意味する。 The maximum diameter of the seed graphene crystal is preferably 1 μm to 200 μm, more preferably 20 μm to 200 μm, and particularly preferably 100 μm to 200 μm. If the maximum diameter of the seed graphene crystal is less than 1 μm, amorphous carbon tends to be formed. On the other hand, if it exceeds 200 μm, the seed graphene crystal will be wrinkled easily. In the present invention, the maximum diameter of the seed graphene crystal means the longest diameter of the seed graphene crystal measured with an optical microscope or an electron microscope.
種グラフェン結晶は、従来公知の方法により、基板上に設置できる。例えば、一例として次の方法が挙げられる。 The seed graphene crystal can be placed on the substrate by a conventionally known method. For example, the following method is mentioned as an example.
Ｈｕｍｍｅｒｓ法により酸化グラフェンを合成し、これを溶媒に展開することで、酸化グラフェンが自然に層方向に剥離され、酸化グラフェンを含む懸濁液が得られる。この懸濁液を基板に塗布し、還元処理を行うことで、基板上に種グラフェン結晶を設置できる。 By synthesizing graphene oxide by the Hummers method and developing it in a solvent, the graphene oxide is naturally peeled in the layer direction, and a suspension containing graphene oxide is obtained. By applying this suspension to a substrate and performing a reduction treatment, seed graphene crystals can be placed on the substrate.
具体的には、まず、グラファイトを濃硫酸中に浸し、過マンガン酸カリウムを加えて反応させた後、反応物を硫酸中に浸し、過酸化水素を加えて反応させて、酸化グラファイトを得る。グラファイトを濃硫酸中で過マンガン酸カリウムを加えて反応させることで、六員環に酸素の官能基が結合された状態となる。そして、その後硫酸中で過酸化水素を加えて未反応の過マンガン酸カリウムを反応させて精製することで酸化グラファイトが得られる。 Specifically, first, graphite is immersed in concentrated sulfuric acid, potassium permanganate is added and reacted, and then the reaction product is immersed in sulfuric acid and hydrogen peroxide is added and reacted to obtain graphite oxide. By reacting graphite with concentrated potassium permanganate in concentrated sulfuric acid, the oxygen functional group is bonded to the six-membered ring. Then, graphite oxide is obtained by adding hydrogen peroxide in sulfuric acid and reacting with unreacted potassium permanganate for purification.
このようにして得られる酸化グラファイトを、溶媒に分散することで、層間に溶媒分子が挿入され、層方向にのみ剥離させることができ、面方向のサイズが大きい酸化グラフェンを高い収率で回収できる。 By dispersing the graphite oxide thus obtained in a solvent, solvent molecules are inserted between the layers and can be peeled only in the layer direction, and the graphene oxide having a large size in the surface direction can be recovered with a high yield. .
溶媒としては、特に限定はないが極性溶媒が好ましい。例えば、水、アセトン、メタノール、エタノール、イソプロパノールから選ばれる１種又は２種以上の混合液等が挙げられる。 Although there is no limitation in particular as a solvent, A polar solvent is preferable. For example, 1 type, or 2 or more types of liquid mixture chosen from water, acetone, methanol, ethanol, isopropanol, etc. are mentioned.
このようにして得られる酸化グラフェンを含む溶液を基板に流延塗付し、その後還元することで、最大径が１００〜２００μｍの酸化グラフェンを基板上に設置できる。 The solution containing graphene oxide thus obtained is cast-applied on a substrate and then reduced, whereby graphene oxide having a maximum diameter of 100 to 200 μm can be placed on the substrate.
酸化グラフェンの還元方法としては、特に限定はない、従来公知の方法を採用できる。例えば、還元剤を用いる従来公知の還元反応等を利用できる。 The method for reducing graphene oxide is not particularly limited, and a conventionally known method can be employed. For example, a conventionally known reduction reaction using a reducing agent can be used.
酸化グラフェンを含む溶液の塗布量は、溶液中の酸化グラフェン濃度、種グラフェン結晶の設置密度により異なるので特に限定しない。例えば、一辺が１０ｍｍ四方の基板の場合、酸化グラフェン濃度が０．０１質量％で、溶液の塗布量は、１０〜５０μlが好ましく、１０〜２０μlがより好しい。塗布量が１０μlであると、塗布直後に乾燥してしまい均一に成膜することが困難である。また、２０μlを超えると、乾燥の際に酸化グラフェンの濃度が上昇し、均一に成膜することが困難である。 The application amount of the solution containing graphene oxide is not particularly limited because it varies depending on the graphene oxide concentration in the solution and the installation density of the seed graphene crystals. For example, in the case of a 10 mm square substrate, the graphene oxide concentration is 0.01% by mass, and the coating amount of the solution is preferably 10 to 50 μl, more preferably 10 to 20 μl. When the coating amount is 10 μl, it is difficult to form a uniform film because it dries immediately after coating. On the other hand, if it exceeds 20 μl, the concentration of graphene oxide increases during drying, and it is difficult to form a uniform film.
また、他の方法としては、次の方法が挙げられる。すなわち、グラフェンをジメチルホルムアミド、Ｎ−メチルピロリドン等の溶媒に懸濁させ、超音波を照射してグラファイトを層方向に剥離させた後、グラファイトの層間剥離物を含む溶液を基板に流延塗付し、乾燥する。このようにすることで、最大径が１００〜１０００ｎｍの種グラフェン結晶を、基板上に設置できる。 Moreover, the following method is mentioned as another method. That is, after suspending graphene in a solvent such as dimethylformamide or N-methylpyrrolidone and irradiating ultrasonic waves to exfoliate the graphite in the layer direction, a solution containing the exfoliation product of graphite is cast on the substrate. And dry. By doing so, seed graphene crystals having a maximum diameter of 100 to 1000 nm can be placed on the substrate.
種グラフェンを設置させる基板は、特に限定はない。ＣＶＤ法での成膜温度に耐えうる材料からなるものであれば、いずれの材質からなる基板も使用できる。好ましくは、Ｓｉ基板、ＳｉＯ２／Ｓｉ基板及び石英ガラス基板から選ばれる一種以上である。これらの材質からなる基板は工業的に頻繁に使用され、汎用的である。 There is no particular limitation on the substrate on which the seed graphene is placed. A substrate made of any material can be used as long as it is made of a material that can withstand the film formation temperature by the CVD method. Preferably, it is at least one selected from a Si substrate, a SiO 2 / Si substrate, and a quartz glass substrate. Substrates made of these materials are frequently used industrially and are general purpose.
次に、種グラフェン結晶を設置した基板をＣＶＤ炉に導入し、炭素含有ガスを供給してＣＶＤ法により基板上にグラフェン膜を形成する。 Next, the substrate on which the seed graphene crystal is installed is introduced into a CVD furnace, a carbon-containing gas is supplied, and a graphene film is formed on the substrate by a CVD method.
炭素含有ガスとしては、特に限定はない。例えば、メタン、プロパン、アセチレン、エタノール、ベンゼン等の炭化水素系化合物、六フッ化エタン、四フッ化メタン等の炭化フッ素系化合物が挙げられる。 The carbon-containing gas is not particularly limited. Examples thereof include hydrocarbon compounds such as methane, propane, acetylene, ethanol and benzene, and fluorine compounds such as ethane hexafluoride and methane tetrafluoride.
ＣＶＤ法としては、特に限定はない。熱ＣＶＤ法、プラズマＣＶＤ法等従来公知の方法を採用できる。 There is no particular limitation on the CVD method. Conventionally known methods such as a thermal CVD method and a plasma CVD method can be employed.
例えば、熱ＣＶＤ法によりグラフェン膜を形成する場合、ＣＶＤ炉の圧力を１０−２〜１０−３Ｔｏｒｒに真空引きし、基板温度を９００〜１０００℃に加温した後、炭素含有ガスを１００〜５００ｍＴｏｒｒ供給して行う。 For example, when a graphene film is formed by a thermal CVD method, the pressure in the CVD furnace is evacuated to 10 −2 to 10 −3 Torr, the substrate temperature is heated to 900 to 1000 ° C., and then the carbon-containing gas is changed to 100 to 100 ° C. Supply 500 mTorr.
また、プラズマＣＶＤ法によりグラフェン膜を形成する場合、ＣＶＤ炉の圧力を１０−２〜１０−３Ｔｏｒｒに真空引きし、基板温度を６５０〜８００℃に加温した後、プラズマ化した炭素含有ガスを１００ｍＴｏｒｒ〜５０Ｔｏｒｒ、好ましくは４００〜５００ｍＴｏｒｒ供給して行う。 When a graphene film is formed by plasma CVD, the pressure of the CVD furnace is evacuated to 10 −2 to 10 −3 Torr and the substrate temperature is heated to 650 to 800 ° C. For 100 mTorr to 50 Torr, preferably 400 to 500 mTorr.
図１は、プラズマＣＶＤ装置の概略図である。このプラズマＣＶＤ装置は、真空チャンバー１の上部にプラズマ発生装置２が設置されている。真空チャンバー１内の基板ホルダ３に基板１０を設置し、排気口５から真空チャンバー１内を真空引きする。そして、基板ホルダに内蔵されたヒータを作動して基板温度を所定温度まで昇温した後、原料ガス導入路４からプラズマ発生装置２に炭素含有ガスを導入する。プラズマ発生装置２に導入された炭素含有ガスは、ここでラジカル化してダウンフローにて基板１０に供給される。 FIG. 1 is a schematic view of a plasma CVD apparatus. In this plasma CVD apparatus, a plasma generator 2 is installed on an upper portion of a vacuum chamber 1. The substrate 10 is placed on the substrate holder 3 in the vacuum chamber 1, and the vacuum chamber 1 is evacuated from the exhaust port 5. Then, after operating the heater built in the substrate holder to raise the substrate temperature to a predetermined temperature, the carbon-containing gas is introduced from the source gas introduction path 4 into the plasma generator 2. The carbon-containing gas introduced into the plasma generator 2 is radicalized here and supplied to the substrate 10 by downflow.
前述したように、種グラフェン結晶を設置した基板に炭素含有ガスを供給すると、炭素原子が種グラフェン結晶の端部に選択的に付着して成長する。このため、グラフェンとの格子定数のマッチングが悪い材料からなる基板上であってもアモルファスになり難く、大面積のグラフェン膜を効率よく製造できる。 As described above, when a carbon-containing gas is supplied to the substrate on which the seed graphene crystal is installed, carbon atoms selectively grow on the end portion of the seed graphene crystal. For this reason, even on a substrate made of a material having a poor lattice constant matching with graphene, it is difficult to become amorphous, and a large-area graphene film can be efficiently manufactured.
このようにして得られるグラフェン膜は、最大径が１００μｍ以上であることが好ましく、１０００μｍ以上であることがより好ましい。 The graphene film thus obtained preferably has a maximum diameter of 100 μm or more, and more preferably 1000 μm or more.
また、グラフェン膜の膜厚は、用途により異なるので特に限定しない。例えば、太陽電池の用途で使用する場合、１〜１０ｎｍが好ましく、２〜３ｎｍがより好ましい。なお、得られるグラフェン膜の膜厚を調整するには、成膜時間を調整すれば良い。 Further, the thickness of the graphene film is not particularly limited because it varies depending on the application. For example, when using it for the use of a solar cell, 1-10 nm is preferable and 2-3 nm is more preferable. Note that the film formation time may be adjusted in order to adjust the thickness of the obtained graphene film.
（実施例１）
Ｈｕｍｍｅｒｓ法によりグラファイトを濃硫酸中に浸し、過マンガン酸カリウムを加えて反応させた後、反応物を硫酸中に浸し、過酸化水素を加えて反応させて、酸化グラファイトを合成した。そして、その後硫酸中で過酸化水素を加えて未反応の過マンガン酸カリウムを反応させて精製し、酸化グラファイトを得た。得られた酸化グラファイトを、純水に分散して層方向に剥離し、酸化グラフェンを作製した。得られた酸化グラフェンを１０ｍｇ/ｍｌに調整し、この溶液を１０ｍｌ基板に滴下、乾燥させ、還元することでＳｉＯ２／Ｓｉ基板に基板上に、最大径２００μｍ、単層の種グラフェン結晶を設置した。
次に、種グラフェン結晶が設置された基板を、図１に示すプラズマＣＶＤ装置の基板ホルダ３に設置し、真空チャンバー１内の圧力を１０−３Ｔｏｒｒに真空引きを行い、基板を１０００℃に加熱した。そして、プラズマ発生装置２にメタンガスを５００ｍＴｏｒｒ流入してラジカル化し、ラジカル化したメタンガスをダウンフローで基板に３０分間供給して、プラズマＣＶＤ法によりグラフェン膜の成膜を行った。
基板上には、最大径が１０００μｍ、厚さ０．４ｎｍの膜が成膜されていた。この膜をラマン分光法で分析したところ、単層のグラフェン膜であることが確認できた。
Example 1
Graphite was synthesized by immersing graphite in concentrated sulfuric acid by the Hummers method and adding potassium permanganate to react, and then immersing the reaction product in sulfuric acid and adding hydrogen peroxide to react. Then, hydrogen peroxide was added in sulfuric acid to react with unreacted potassium permanganate and purified to obtain graphite oxide. The obtained graphite oxide was dispersed in pure water and peeled in the layer direction to produce graphene oxide. The obtained graphene oxide was adjusted to 10 mg / ml, and this solution was dropped onto a 10 ml substrate, dried, and reduced to place a single-layer seed graphene crystal with a maximum diameter of 200 μm on the substrate on a SiO 2 / Si substrate. did.
Next, the substrate on which the seed graphene crystal is placed is placed on the substrate holder 3 of the plasma CVD apparatus shown in FIG. 1, the pressure in the vacuum chamber 1 is evacuated to 10 −3 Torr, and the substrate is brought to 1000 ° C. Heated. Then, 500 mTorr of methane gas was flowed into the plasma generator 2 for radicalization, and the radicalized methane gas was supplied to the substrate for 30 minutes by downflow, and a graphene film was formed by plasma CVD.
A film having a maximum diameter of 1000 μm and a thickness of 0.4 nm was formed on the substrate. When this film was analyzed by Raman spectroscopy, it was confirmed to be a single-layer graphene film.
（実施例２）
実施例１において、メタンガスの代わりに六フッ化エタンを用いた以外は実施例１と同様にして、プラズマＣＶＤ法によりグラフェン膜の成膜を行った。
基板上には、最大径が５００μｍ、厚さ０．４ｎｍの膜が成膜されていた。
(Example 2)
In Example 1, a graphene film was formed by the plasma CVD method in the same manner as in Example 1 except that hexafluoroethane was used instead of methane gas.
A film having a maximum diameter of 500 μm and a thickness of 0.4 nm was formed on the substrate.
（実施例３）
実施例１において、ＳｉＯ２／Ｓｉ基板の代わりにＳｉ基板を使用した以外は実施例１と同様にして、プラズマＣＶＤ法によりグラフェン膜の成膜を行った。
基板上には、最大径が１０００μｍ、厚さ０．４ｎｍの膜が成膜されていた。
(Example 3)
In Example 1, a graphene film was formed by plasma CVD in the same manner as in Example 1 except that a Si substrate was used instead of the SiO 2 / Si substrate.
A film having a maximum diameter of 1000 μm and a thickness of 0.4 nm was formed on the substrate.
（比較例１）
実施例１において、ＳｉＯ２／Ｓｉ基板上に種グラフェン結晶を設置しなかった以外は実施例１と同様にして、プラズマＣＶＤ法によりグラフェン膜の成膜を行った。
基板上には、アモルファスカーボン膜が形成されていた。基板上に形成されていた膜がアモルファスカーボンであることは、ラマン分光法で確認した。
(Comparative Example 1)
In Example 1, a graphene film was formed by plasma CVD in the same manner as in Example 1 except that no seed graphene crystal was placed on the SiO 2 / Si substrate.
An amorphous carbon film was formed on the substrate. It was confirmed by Raman spectroscopy that the film formed on the substrate was amorphous carbon.
１：真空チャンバー
２：プラズマ発生装置
３：基板ホルダ
４：原料ガス導入路
５：排気口
１０：基板
1: Vacuum chamber 2: Plasma generator 3: Substrate holder 4: Source gas introduction path 5: Exhaust port 10: Substrate
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