JP2020100514A - Chemical doping method of graphene film - Google Patents

Chemical doping method of graphene film Download PDF

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JP2020100514A
JP2020100514A JP2018237639A JP2018237639A JP2020100514A JP 2020100514 A JP2020100514 A JP 2020100514A JP 2018237639 A JP2018237639 A JP 2018237639A JP 2018237639 A JP2018237639 A JP 2018237639A JP 2020100514 A JP2020100514 A JP 2020100514A
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graphene film
graphene
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正義 梅野
Masayoshi Umeno
正義 梅野
アブエルウェファ アムール
Abwelwafer Amur
アブエルウェファ アムール
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Cs Techno Inc
C's Techno Inc
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Abstract

To produce a metal-doped graphene film of high crystallinity.SOLUTION: There is provided a chemical doping method of a graphene film, comprising a process of irradiating a graphene film with laser light while immersing the graphene film in melt of a metal compound molten in a solvent. Thereby, the mobility of graphene is remarkably increased and the conductivity can be increased.SELECTED DRAWING: Figure 1

Description

本発明は、グラフェン膜に金属をドープする方法に関する。 The present invention relates to a method of doping a graphene film with a metal.

グラフェンは、ベンゼン環が同一平面内で多数縮合した巨大π共役系である。多層のグラフェンは、単層の単結晶グラフェンが、法線方向に積層されたものである。各層のグラフェンは、弱いファンデルワールス力のみにより引き合っている。多層グラフェンでは伝導帯と価電子帯の先端部分がオーバーラップしており、伝導特性は半金属性を示す。２層グラフェンでは伝導帯と価電子帯の先端が接する。単層グラフェンでは分散特性が線形であり、伝導帯と価電子帯はその先端が１点で接触し、円錐形のディラックコーンとなる。これらのことから移動度が高く、電子質量が小さく、移動速度が速いことから、グラフェンは多くの将来の用途が期待されている。 Graphene is a giant π-conjugated system in which many benzene rings are condensed in the same plane. Multi-layer graphene is obtained by stacking single-layer single-crystal graphene in the normal direction. The graphenes in each layer are attracted by only weak van der Waals forces. In the multi-layer graphene, the conduction band and the valence band have overlapping ends, and the conduction characteristic is semi-metallic. In double-layer graphene, the tips of the conduction band and the valence band are in contact with each other. In single-layer graphene, the dispersion characteristic is linear, and the conduction band and the valence band are in contact with each other at one point to form a conical Dirac cone. Due to these facts, graphene is expected to have many future applications because of its high mobility, small electronic mass, and high migration speed.

グラフェンの伝導特性の制御には、ドーピング技術が欠かせない。その一つに化学ドープング技術が知られている（特許文献１）。その方法は一電子酸化剤を含む溶液にグラフェンを浸漬することで抵抗率を低減させる方法である。また、次の方法も知られている（特許文献２）。まず、グラファイト粒子と金属又は金属酸化物とスルフォン化用固体酸触媒を、硫酸を含む反応媒体中に混合して、レーザアブレーションを行うことでスルフォン化グラファイト粒子の混濁液を生成する。レーザアブレーションはグラファイト粒子の層間を拡張し粒子を微細化するために行われる。次に、その混濁液に濃硝酸又は強酸化剤を添加して、グラファイト粒子のスルフォン化反応をさらに促進させる。次に、水及び塩酸を加えてスルフォン化グラファイト粒子を加水分解する。これにより金属がドープされ又は金属がインターカーレントされた（層間に保持された）還元型参加グラフェン粒子の懸濁液が製造される。最後に、この懸濁液を遠心分離し、沈殿物を乾燥させることにより、金属がドープされ又は金属がインターカーレントされた還元型酸化グラフェン粒子を得ている。なお、本願の特許請求の範囲及び明細書において、「ドープ」の用語は、金属がグラフェンの構成原子に置換又は原子間に介在される他、グラフェンの層間に金属がインターカーレントされたことを含む意味で使用している。 Doping techniques are essential for controlling the conductive properties of graphene. A chemical doping technique is known as one of them (Patent Document 1). The method is a method of reducing the resistivity by immersing graphene in a solution containing a one-electron oxidant. The following method is also known (Patent Document 2). First, graphite particles, a metal or a metal oxide, and a solid acid catalyst for sulfonation are mixed in a reaction medium containing sulfuric acid, and laser ablation is performed to generate a suspension of sulfonated graphite particles. Laser ablation is performed in order to expand the layers of graphite particles and miniaturize the particles. Next, concentrated nitric acid or a strong oxidant is added to the cloudy solution to further accelerate the sulfonation reaction of the graphite particles. Next, water and hydrochloric acid are added to hydrolyze the sulfonated graphite particles. This produces a suspension of reduced participating graphene particles that are metal-doped or metal-intercalated (retained between layers). Finally, this suspension is centrifuged and the precipitate is dried to obtain reduced graphene oxide particles doped with metal or intercalated with metal. In the claims and the specification of the present application, the term “doped” means that a metal is substituted for a constituent atom of graphene or is interposed between atoms, and that the metal is intercalated between graphene layers. It is used to include.

特許第５７５３５８４号Patent No. 5735584 特許第５３５７３４６号Patent No. 5357346

しかし、特許文献１の酸化方法ではグラフェンの抵抗率を十分に低くすることはできない。また、特許文献２の方法は、グラファイト粉末を溶液中に分散させて、その粉末を酸化させてレーザアブレーションにより、溶液中に酸化グラフェンを生成している。その後に酸化グラファイトを還元して還元型酸化グラフェンを得るものである。したがって、特許文献２の方法で得られるグラフェンは、酸素や官能基が結合しており、純粋なグラフェン膜自体ではない。また、特許文献２の方法は、グラフェン膜を原材料として、このグラフェン膜に金属を直接作用させる方法ではない。したがって、製造が複雑であると同時に導電特性も不十分である。 However, the oxidation method of Patent Document 1 cannot sufficiently reduce the resistivity of graphene. In the method of Patent Document 2, graphite powder is dispersed in a solution, the powder is oxidized, and laser ablation is performed to generate graphene oxide in the solution. After that, the graphite oxide is reduced to obtain reduced graphene oxide. Therefore, the graphene obtained by the method of Patent Document 2 is not a pure graphene film itself because oxygen and functional groups are bonded. Further, the method of Patent Document 2 is not a method in which a graphene film is used as a raw material and a metal is allowed to directly act on the graphene film. Therefore, the manufacturing is complicated and, at the same time, the conductive property is insufficient.

本発明は上記の課題を解決するために成されたものであり、その目的は抵抗率の低いグラフェン膜を得ることである。 The present invention has been made to solve the above problems, and an object thereof is to obtain a graphene film having a low resistivity.

本発明の構成は、グラフェン膜の化学ドープ方法において、金属化合物を溶媒に溶融させた融液に、グラフェン膜を浸漬しつつ、このグラフェン膜にレーザを照射することを特徴とするグラフェン膜の化学ドープ方法である。この方法において、金属化合物には金属塩化物を用いることができる。また、金属塩化物は、例えば、ＡｕＣｌ3 、ＣｕＣｌ3 、ＡｌＣｌ3 、ＫＣｌ3 のうちの少なくとも１種とすることができる。溶媒にはニトロ化合物を用いることができる。さらに、溶媒にはニトロメタン（ＣＨ3 ＮＯ2 ）を用いることができる。ドープされる物質であるグラフェン膜には、少なくとも炭素と水素とを有する化合物の原料気体を基板上に流し、この基板上に、マイクロ波励起により原料気体のプラズマを生成して、基板上に生成されたグラフェン膜を用いることができる。 The structure of the present invention is a chemical doping method for a graphene film, characterized by irradiating the graphene film with a laser while immersing the graphene film in a melt obtained by melting a metal compound in a solvent. It is a dope method. In this method, the metal compound may be a metal chloride. Further, the metal chloride can be at least one kind of AuCl 3 , CuCl 3 , AlCl 3 and KCl 3 , for example. A nitro compound can be used as the solvent. Further, nitromethane (CH 3 NO 2 ) can be used as the solvent. In the graphene film, which is a substance to be doped, a raw material gas of a compound having at least carbon and hydrogen is caused to flow on a substrate, and a plasma of the raw material gas is generated by microwave excitation on the substrate to generate it on the substrate. The graphene film can be used.

本発明によると、抵抗率を低下させた純粋なグラフェン膜を得ることができる。 According to the present invention, a pure graphene film with reduced resistivity can be obtained.

本発明に実施例の製造方法に用いられるグラフェン膜の製造装置を示す構成図。The block diagram which shows the manufacturing apparatus of the graphene film used for the manufacturing method of the Example in this invention. 実施例の製造方法によるレーザ照射方法を示す説明図。Explanatory drawing which shows the laser irradiation method by the manufacturing method of an Example. 実施例の製造方法で製造されたグラフェン膜の測定されたラマン分光特性。The measured Raman spectroscopic characteristic of the graphene film manufactured by the manufacturing method of an Example.

以下、本発明を実施例に基づいて説明するが、本発明は以下の実施例に限定されるものではない。 Hereinafter, the present invention will be described based on examples, but the present invention is not limited to the following examples.

本実施例では、原料気体として、メタン（ＣＨ4 ) とアセチレン（Ｃ2 Ｈ2 ）を用いた。キャリアガスとしてアルゴン（Ａｒ）を用いた。もちろん、メタン（ＣＨ4 ) とアルゴン（Ａｒ）や他の不活性ガスとの混合ガスでも良く、これに水素（Ｈ2 ）を混合しても良い。
図１は本発明に係るグラフェン膜の製造装置１００の構成を示す構成図である。図１に示されるように、製造装置１００は、ＣＶＤ反応容器１と、その上部に配設された導波管２とを有する。ＣＶＤ反応容器１と導波管２との間には、石英から成るプラズマ励振板３が設けられている。プラズマ励振板３のＣＶＤ反応容器１側に面した面には多数の微小な凹部３０が形成されている。この凹部３０に電界が集中することにより、凹部３０がプラズマの発生起点となり、低電力でのプラズマの発生が容易になる。また、ＣＶＤ反応容器１の内部及びプラズマ励振板３をマイクロ波で励振するために導波管２の下部にスロットアンテナ４が設けられている。導波管２には２．４５ＧＨｚのマイクロ波が供給され、スロットアンテナ４を介して、ＣＶＤ反応容器１の内部及びプラズマ励振板３に電磁波が供給される。 In this example, methane (CH 4 ) and acetylene (C 2 H 2 ) were used as raw material gases. Argon (Ar) was used as a carrier gas. Of course, a mixed gas of methane (CH 4 ) and argon (Ar) or another inert gas may be used, and hydrogen (H 2 ) may be mixed therein.
FIG. 1 is a configuration diagram showing a configuration of a graphene film manufacturing apparatus 100 according to the present invention. As shown in FIG. 1, the manufacturing apparatus 100 has a CVD reaction container 1 and a waveguide 2 arranged above it. A plasma excitation plate 3 made of quartz is provided between the CVD reaction container 1 and the waveguide 2. A large number of minute recesses 30 are formed on the surface of the plasma excitation plate 3 facing the CVD reaction container 1 side. By concentrating the electric field in the recess 30, the recess 30 serves as a starting point of plasma generation, which facilitates generation of plasma with low power. Further, a slot antenna 4 is provided below the waveguide 2 in order to excite the inside of the CVD reaction vessel 1 and the plasma excitation plate 3 with microwaves. A microwave of 2.45 GHz is supplied to the waveguide 2, and an electromagnetic wave is supplied to the inside of the CVD reaction container 1 and the plasma excitation plate 3 via the slot antenna 4.

ＣＶＤ反応容器１の内部には、グラフェン膜を成長させる基板５が設置されるサセプタ６及び基板５を加熱するための加熱装置７が設けられている。メタンガスとアセチレンガスは、キャリアガスのアルゴン（Ａｒ）との混合ガスにより、マスフローコントローラにより供給量が調整されて、ＣＶＤ反応容器１の右側に設けられた導入口１１からＣＶＤ反応容器１内に導入される。ＣＶＤ反応容器１の左側には、ガスを外部へ排出する排出口１２が設けられている。ＣＶＤ反応容器１の内部は、図示しない真空ポンプにより１０-3torr程度に減圧できるようになっている。基板５にはガラスを用いたが、Ｃｕなどの金属、Ｓｉなどの半導体、ＳｉＯ2 などの誘電体を用いることができる。 Inside the CVD reaction container 1, a susceptor 6 on which a substrate 5 for growing a graphene film is placed and a heating device 7 for heating the substrate 5 are provided. The supply amount of methane gas and acetylene gas is adjusted by a mass flow controller with a mixed gas of argon (Ar) as a carrier gas, and introduced into the CVD reaction container 1 through an inlet 11 provided on the right side of the CVD reaction container 1. To be done. On the left side of the CVD reaction container 1, a discharge port 12 for discharging gas to the outside is provided. The inside of the CVD reaction container 1 can be depressurized to about 10 −3 torr by a vacuum pump (not shown). Although glass is used for the substrate 5, a metal such as Cu, a semiconductor such as Si, or a dielectric such as SiO 2 can be used.

また、供給するマイクロ波は周波数２．５ｋＨｚ、デューティ比０．５のパルスとした。マイクロ波電力は１．５ｋＷである。ＣＶＤ反応容器１の内部の圧力は２．６Ｐａとした。この装置は、パルス化マイクロ波表面波プラズマＣＶＤ装置である。ＣＶＤ反応容器１の内部の圧力は、１〜５００Ｐａの範囲でグラフェン膜の成膜が可能である。また、温度は、１５０℃以上、６００℃以下の範囲で、望ましくは、１５０℃以上、３００℃以下の範囲でグラフェン膜の成膜が可能である。 The microwave to be supplied was a pulse having a frequency of 2.5 kHz and a duty ratio of 0.5. The microwave power is 1.5 kW. The pressure inside the CVD reaction container 1 was set to 2.6 Pa. This device is a pulsed microwave surface wave plasma CVD device. The graphene film can be formed within the pressure of the CVD reaction container 1 in the range of 1 to 500 Pa. In addition, the graphene film can be formed at a temperature in the range of 150 °C to 600 °C, preferably in the range of 150 °C to 300 °C.

次に、グラフェン膜を基板５上に製造する方法について説明する。基板５には、ガラス基板が用いられた。基板５の表面は、アセトン及びメタノール中で超音波洗浄され、その後乾燥され、その基板５はサセプタ６上に設置された。 Next, a method of manufacturing the graphene film on the substrate 5 will be described. A glass substrate was used as the substrate 5. The surface of the substrate 5 was ultrasonically cleaned in acetone and methanol and then dried, and the substrate 5 was placed on the susceptor 6.

グラフェン膜の製造において、ＣＶＤ反応容器１の内部にメタンとアセチレンとアルゴンが一定量流され、ＣＶＤ反応容器１の内部の圧力は２．６ｐＰａに設定された。そして、加熱装置７により基板５は加熱されて、基板５の温度は目的温度３００℃に設定された。この状態で、メタンとアセチレンは、キャリアガス流により基板５の上に、流量がマスフローコントローラにより制御されて、輸送される。なお、キャリアガスには、アルゴン（Ａｒ）の他、水素（Ｈ2 ）や、ヘリウム（Ｈｅ）、窒素（Ｎ2 ）等の不活性ガス、これらの混合ガスを用いることができる。次に、電力１．５ｋＷ、２．４５ＧＨｚのマイクロ波を、周波数２．５ｋＨｚ、デューティ比０．５のパルスで変調したパルス化マイクロ波が導波管２に供給され、ＣＶＤ反応容器１の内部においてメタン気体とアセチレン気体とアルゴン気体のプラズマが生成された。マイクロ波の電力は５００Ｗ〜２０００Ｗの範囲とすることができる。特に、基板５の表面上に、これらの気体の表面波プラズマが生成された。基板５上にグラフェン膜が、所定時間、成長された後、加熱装置７の通電が停止され、基板５の温度は室温まで低下された。
なお、基板５の温度は、１５０〜６００℃の範囲の任意の温度にすることができる。また、基板５の温度を１５０〜３００℃の低温にしても、良質で広い面積のグラフェン膜を得ることができる。 In the production of the graphene film, a certain amount of methane, acetylene, and argon were flown inside the CVD reaction container 1, and the pressure inside the CVD reaction container 1 was set to 2.6 pPa. Then, the substrate 5 was heated by the heating device 7, and the temperature of the substrate 5 was set to the target temperature of 300°C. In this state, methane and acetylene are transported onto the substrate 5 by the carrier gas flow, the flow rate of which is controlled by the mass flow controller. In addition to argon (Ar), hydrogen (H 2 ), an inert gas such as helium (He) and nitrogen (N 2 ), or a mixed gas thereof can be used as the carrier gas. Next, a pulsed microwave obtained by modulating a microwave having a power of 1.5 kW and a power of 2.45 GHz with a pulse having a frequency of 2.5 kHz and a duty ratio of 0.5 is supplied to the waveguide 2, and the inside of the CVD reaction container 1 is Plasma of methane gas, acetylene gas and argon gas was generated at. Microwave power may range from 500W to 2000W. In particular, surface wave plasmas of these gases were generated on the surface of the substrate 5. After the graphene film was grown on the substrate 5 for a predetermined time, the heating device 7 was turned off, and the temperature of the substrate 5 was lowered to room temperature.
The temperature of the substrate 5 can be any temperature in the range of 150 to 600°C. Moreover, even if the temperature of the substrate 5 is set to a low temperature of 150 to 300° C., it is possible to obtain a high-quality graphene film having a large area.

次に、このようにして製造されたグラフェン膜のシート抵抗は２ｋΩ／□であり、透過率は８０％であった。
次に、このグラフェン膜に次のように化学ドープを施した。図２に示すように、ニトロメタン（ＣＨ3 ＮＯ2 ）の溶媒に、ＡｕＣｌ3 の金属塩化物を２０ｍＭ、溶解させて融液５０を製造した。この融液５０に、上記の方法により製造したグラフェンを表面に有する基板５を１〜４分間浸漬した。そして、この浸漬の期間において、グラフェン膜上の全面に一様にレーザを照射した。レーザの出力は１０Ｗで、波長は４０６ｎｍである。その後に、基板５を融液５０から取り出して、洗浄乾燥させた後に、電気特性を測定した。融液に浸漬する前のグラフェンの移動度は２７．１８ｃｍ2 ／Ｖ・ｓ、シート抵抗率は６３９１Ω／□、キャリア面密度は３．５９×１０13／ｃｍ2 、光透過率は７４％であった。グラフェン膜を４分間だけ融液に浸漬し、その間レーザを照射した後のグラフェン膜の移動度は２９２１ｃｍ2 ／Ｖ・ｓ、シート抵抗率は３８９Ω／□、キャリア面密度は５．４８×１０12／ｃｍ2 、光透過率は３４％であった。伝導型はｐ型であった。 Next, the sheet resistance of the graphene film manufactured in this manner was 2 kΩ/□ and the transmittance was 80%.
Next, this graphene film was chemically doped as follows. As shown in FIG. 2, 20 mM of a metal chloride of AuCl 3 was dissolved in a solvent of nitromethane (CH 3 NO 2 ) to prepare a melt 50. The substrate 5 having the graphene produced by the above method on its surface was immersed in the melt 50 for 1 to 4 minutes. Then, during this immersion period, the entire surface of the graphene film was uniformly irradiated with laser. The laser output is 10 W and the wavelength is 406 nm. After that, the substrate 5 was taken out from the melt 50, washed and dried, and then the electrical characteristics were measured. The mobility of graphene before immersion in the melt is 27.18 cm 2 /V·s, the sheet resistivity is 6391 Ω/□, the carrier areal density is 3.59×10 13 /cm 2 , and the light transmittance is 74%. there were. The graphene film was immersed in the melt for 4 minutes only, and the graphene film after being irradiated with laser during that time had a mobility of 2921 cm 2 /V·s, a sheet resistivity of 389 Ω/□, and a carrier surface density of 5.48×10 12 /Cm 2 , and the light transmittance was 34%. The conductivity type was p-type.

また、グラフェン膜を２分間だけ融液に浸漬し、この浸漬の期間において、グラフェン膜上の全面に一様に上記出力のレーザを照射した。レーザを照射した場合には、次の結果得られた。融液に浸漬する前のグラフェンの移動度は１９．６ｃｍ2 ／Ｖ・ｓ、シート抵抗率は２１２６Ω／□、キャリア面密度は１．５２×１０14／ｃｍ2 、光透過率は７４％であった。グラフェン膜を２分間だけ融液に浸漬し、その間レーザを照射した後のグラフェン膜の移動度は５６．４ｃｍ2 ／Ｖ・ｓ、シート抵抗率は１９８Ω／□、キャリア面密度は３．４５×１０14／ｃｍ2 、光透過率は７８％であった。伝導型はｐ型であった。 The graphene film was immersed in the melt for 2 minutes, and the entire surface of the graphene film was uniformly irradiated with the laser having the above output during the immersion. When laser irradiation was performed, the following results were obtained. The mobility of graphene before immersion in the melt was 19.6 cm 2 /V·s, the sheet resistivity was 2126 Ω/□, the carrier surface density was 1.52×10 14 /cm 2 , and the light transmittance was 74%. there were. The graphene film was immersed in the melt for 2 minutes only, and the graphene film after being irradiated with laser during that time had a mobility of 56.4 cm 2 /V·s, a sheet resistivity of 198 Ω/□, and a carrier areal density of 3.45×. The light transmittance was 10 14 /cm 2 , and the light transmittance was 78%. The conductivity type was p-type.

本発明のグラフェンへの化学ドープ方法により、最も効果が高い場合には、抵抗率は化学ドープ前の値の０．０６倍に低下し、移動度は１０７倍に増加し、キャリア濃度は２．３倍に増加し、光透過率は低減がなかった。グラフェンへのレーザ照射により移動度が大きく向上したのは、レーザの照射によりグラフェンの原子の配列が整列されて理想的な単結晶構造に近くなったことによるものと思われる。 According to the method for chemically doping graphene of the present invention, when the effect is the highest, the resistivity is reduced to 0.06 times the value before the chemical doping, the mobility is increased to 107 times, and the carrier concentration is 2. It was increased three times, and the light transmittance was not reduced. The reason that the mobility of graphene was greatly improved by laser irradiation is considered to be that the alignment of graphene atoms was aligned by laser irradiation and became closer to an ideal single crystal structure.

また、化学ドープの前後でグラフェン膜のラマン分光分析を行った。図３にその結果を示す。スペクトルに変化はなかった。層数は、２〜５程度であると考えられる。 In addition, Raman spectroscopic analysis of the graphene film was performed before and after the chemical doping. The results are shown in FIG. There was no change in the spectrum. The number of layers is considered to be about 2-5.

上記実施例により金属原子がグラフェン膜にドープされるか、金属原子がグラフェンの層間にインターカーレントされる効果は、金属原子の種類には依存しないと考えられる。したがって、グラフェン膜を融液中に浸漬している期間に、レーザを照射することによって、照射しない場合に比べて電気的特性が向上する効果は、他の金属についても当てはまると思われる。したがって、実施例では、ニトロメタン（ＣＨ3 ＮＯ2 ）の溶媒に、ＡｕＣｌ3 の金属塩化物を溶解させた融液を用いたが、他の金属塩化物をニトロメタン（ＣＨ3 ＮＯ2 ）の溶媒に溶解させた融液、又は金属塩化物を溶解させる溶媒に溶解させた融液を用いることができると思われる。特に、Ａｕに特性の近い、Ｃｕ Ａｇ、Ａｌを用いた金属塩化物をニトロメタン（ＣＨ3 ＮＯ2 ）等の溶媒に溶解させた融液を化学ドープの融液に用いることができる。また、金属の塩化物に限らず、金属の硫化物も用いることができると思われる。 It is considered that the effect that metal atoms are doped into the graphene film or that the metal atoms are intercalated between the layers of graphene according to the above examples does not depend on the type of metal atoms. Therefore, it is considered that the effect of improving the electrical characteristics by irradiating the laser during the period in which the graphene film is immersed in the melt is applicable to other metals as compared with the case of not irradiating the laser. Therefore, in the examples, the melt in which the metal chloride of AuCl 3 was dissolved in the solvent of nitromethane (CH 3 NO 2 ) was used, but another metal chloride was used as the solvent of nitromethane (CH 3 NO 2 ). It is considered possible to use a melt that has been dissolved or a melt that has been dissolved in a solvent that dissolves the metal chloride. In particular, a melt obtained by dissolving a metal chloride using Cu Ag or Al, which has characteristics similar to Au, in a solvent such as nitromethane (CH 3 NO 2 ) can be used as the chemically doped melt. Further, it is considered that not only metal chloride but also metal sulfide can be used.

本発明は、結晶性の高い、電気特性に優れたグラフェン膜の製法に用いることができる。 INDUSTRIAL APPLICABILITY The present invention can be used in a method for producing a graphene film having high crystallinity and excellent electric characteristics.

１：ＣＶＤ反応容器
３：励振板
５：基板
７：加熱装置
２０…レーザ
３０：凹部 1: CVD reaction container 3: Excitation plate 5: Substrate 7: Heating device 20... Laser 30: Recess

Claims (6)

グラフェン膜の化学ドープ方法において、
金属化合物を溶媒に溶融させた融液に、前記グラフェン膜を浸漬しつつ、このグラフェン膜にレーザを照射する
ことを特徴とするグラフェン膜の化学ドープ方法。 In the chemical doping method of the graphene film,
A method for chemically doping a graphene film, which comprises irradiating the graphene film with a laser while immersing the graphene film in a melt obtained by melting a metal compound in a solvent. 前記金属化合物は金属塩化物であることを特徴とする請求項１に記載のグラフェン膜の化学ドープ方法。 The method for chemically doping a graphene film according to claim 1, wherein the metal compound is a metal chloride. 前記金属塩化物はＡｕＣｌ3 、ＣｕＣｌ3 、ＡｌＣｌ3 、ＫＣｌ3 のうちの少なくとも１種であることを特徴とする請求項２に記載のグラフェン膜の化学ドープ方法。 The method for chemically doping a graphene film according to claim 2, wherein the metal chloride is at least one of AuCl 3 , CuCl 3 , AlCl 3 and KCl 3 . 前記溶媒はニトロ化合物であることを特徴とする請求項１乃至請求項３の何れか１項に記載のグラフェン膜の化学ドープ方法。 The method of chemically doping a graphene film according to claim 1, wherein the solvent is a nitro compound. 前記溶媒はニトロメタン（ＣＨ3 ＮＯ2 ）であることを特徴とする請求項４に記載のグラフェン膜の化学ドープ方法。 The method of chemically doping a graphene film according to claim 4, wherein the solvent is nitromethane (CH 3 NO 2 ). 前記グラフェン膜は、少なくとも炭素と水素とを有する化合物の原料気体を基板上に流し、該基板上に、マイクロ波励起により原料気体のプラズマを生成して、基板上に生成されたグラフェン膜であることを特徴とする請求項１乃至請求項５の何れか１項に記載のグラフェン膜の化学ドープ方法。 The graphene film is a graphene film generated on a substrate by flowing a source gas of a compound containing at least carbon and hydrogen onto a substrate and generating plasma of the source gas on the substrate by microwave excitation. The method for chemically doping a graphene film according to any one of claims 1 to 5, wherein:
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006121155A1 (en) * 2005-05-12 2006-11-16 Japan Science And Technology Agency Carbon nanotube composition, process for producing the same, array and electronic device
JP2015048269A (en) * 2013-08-30 2015-03-16 独立行政法人産業技術総合研究所 Method of producing graphene laminate and method of producing transparent electrode using the same

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006121155A1 (en) * 2005-05-12 2006-11-16 Japan Science And Technology Agency Carbon nanotube composition, process for producing the same, array and electronic device
JP2015048269A (en) * 2013-08-30 2015-03-16 独立行政法人産業技術総合研究所 Method of producing graphene laminate and method of producing transparent electrode using the same

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114213706A (en) * 2021-12-02 2022-03-22 北京石墨烯技术研究院有限公司 Graphene composite material, preparation method thereof, heat dissipation member and electronic device

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