JP2014148423A - Method for producing single crystal graphene, and touch panel using single crystal graphene - Google Patents
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 133
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 105
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- 239000013078 crystal Substances 0.000 title claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 59
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 28
- 239000012159 carrier gas Substances 0.000 claims abstract description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 18
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 claims abstract description 17
- 241000723346 Cinnamomum camphora Species 0.000 claims abstract description 17
- 229960000846 camphor Drugs 0.000 claims abstract description 17
- 229930008380 camphor Natural products 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 229910052786 argon Inorganic materials 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000000197 pyrolysis Methods 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 150000001722 carbon compounds Chemical class 0.000 claims abstract description 3
- 238000009751 slip forming Methods 0.000 claims abstract description 3
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- 238000000034 method Methods 0.000 claims description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910000510 noble metal Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- 230000003287 optical effect Effects 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
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- 238000002834 transmittance Methods 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
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Abstract
【課題】樟脳等の炭素源を用いたＣＶＤにより、６角形状のグラフェンあるいは連続膜からなるグラフェンの製造方法を提供する。
【解決手段】炭素源の熱分解によりグラフェンを製造する方法であって、第１の領域に炭素源である化合物を配置させ、第２の領域に基板を配置させ、前記第１の領域を加熱して前記化合物を蒸気化し、加熱した前記第２の領域に少なくともアルゴンと水素とを含むキャリアガスにより前記樟脳の蒸気を導き、当該加熱された第２の領域において、前記炭素化合物を基板上で熱分解することで、前記基板の表面上にドメイン形状のグラフェンを複数個形成する、あるいは基板面全体に連続してグラフェンを形成する、単結晶グラフェンの製造方法。
【選択図】 図１A method for producing hexagonal graphene or graphene comprising a continuous film is provided by CVD using a carbon source such as camphor.
A method for producing graphene by pyrolysis of a carbon source, wherein a compound as a carbon source is disposed in a first region, a substrate is disposed in a second region, and the first region is heated. Then, the compound is vaporized, and the camphor vapor is guided to the heated second region by a carrier gas containing at least argon and hydrogen. In the heated second region, the carbon compound is deposited on the substrate. A method for producing single crystal graphene, in which a plurality of domain-shaped graphenes are formed on the surface of the substrate by pyrolysis, or the graphene is continuously formed on the entire substrate surface.
[Selection] Figure 1
Description
本発明は、透明電極あるいは電子デバイス等に用いられる単結晶グラフェンの製造方法に関する。 The present invention relates to a method for producing single crystal graphene used for a transparent electrode or an electronic device.
グラフェンは、炭素原子が六角形に繋がった平面構造であって化学的に安定しており、透明で、かつバリスティック伝導特性、大電流密度耐性などの優れた電気特性を持つことから、透明電極あるいは高移動度のＦＥＴ（電界効果トランジスタ）などの電子デバイスに利用できる材料として注目されている。グラフェン膜としては単層、二層、あるいは数〜数十層のものが知られている。 Graphene has a planar structure with carbon atoms connected to a hexagon, is chemically stable, transparent, and has excellent electrical properties such as ballistic conductivity and resistance to large current density. Alternatively, it has attracted attention as a material that can be used for electronic devices such as high mobility FETs (field effect transistors). As the graphene film, a single layer, a double layer, or several to several tens of layers are known.
グラフェン膜の製造方法としては、テープを用い、グラファイトから基板にグラフェンを転写する方法が知られている。しかしながら、この方法では大面積のグラフェン膜の作製が困難であり、大面積化に向けて、炭化ケイ素（ＳｉＣ）から選択的にＳｉを除く方法、あるいはＣＶＤ（化学蒸気相合成）法などが検討されている。 As a method for producing a graphene film, a method of transferring graphene from graphite to a substrate using a tape is known. However, it is difficult to produce a large-area graphene film by this method, and methods for selectively removing Si from silicon carbide (SiC) or CVD (Chemical Vapor Phase Synthesis) methods are being investigated for the purpose of increasing the area. Has been.
ＣＶＤを利用してグラフェン膜を形成する方法として、キャリアガスとしてアルゴンガスを流しながら、炭素源、特に樟脳を熱分解させ、加熱したＮｉ等の基板上に、２０〜３５層のグラフェン積層体を形成することが開示されている（特許文献１）。樟脳の供給量が少なく、基板温度が高いとグラフェン積層体を合成できるとしている。 As a method of forming a graphene film using CVD, a carbon source, particularly camphor, is pyrolyzed while flowing argon gas as a carrier gas, and 20 to 35 layers of graphene laminates are formed on a heated substrate such as Ni. It is disclosed to form (Patent Document 1). The graphene stack can be synthesized when the supply amount of camphor is small and the substrate temperature is high.
金属基板上へのＣＶＤによる単層あるいは数層のグラフェン形成の大面積化の研究もなされ、メタンガスの流量を多くした大気圧中で、Ｃｕ箔上に６角形状ドメイン群状の層数の少ないグラフェン膜が形成されること（非特許文献１）、一方、同じく金属箔上に、低メタン分圧で、大きなサイズの６角形状ドメイン群の単層グラフェン膜が形成されることも知られている。このグラフェンドメイン群をｍｍ幅の大きさに成長させることにより１１０００ｃｍ２Ｖ−１ｓ−１という大きなキャリア移動度が得られることが確認されている。（非特許文献２）。ドメイン状とは、基板表面に島状（アイランド状）の単結晶グラフェン膜（ドメイン）が複数個独立して存在している状態を示す。 Research has also been conducted to increase the area of single-layer or several-layer graphene formation on a metal substrate, and the number of hexagonal domain groups on the Cu foil is small at atmospheric pressure with an increased methane gas flow rate. It is also known that a graphene film is formed (Non-Patent Document 1), and that a single-layer graphene film of a large hexagonal domain group is also formed on a metal foil at a low methane partial pressure. Yes. It has been confirmed that a large carrier mobility of 11000 cm 2 V −1 s −1 can be obtained by growing this graphene domain group to a size of mm width. (Non-patent document 2). The domain shape indicates a state where a plurality of island-like (island-like) single-crystal graphene films (domains) exist independently on the substrate surface.
しかし、上記従来の方法では、６角形等の規則正しい形状の多数層からなるグラフェンが安定的に得られていなかった。このため、金属基板からプラスチック等の他の基板へ転写する場合には、何度も転写作業を繰り返さなければならず、その手間がかかること、また転写による品質の劣化は避けられなかった。特にタッチパネル等への応用には、可視光の透過率が多少低下しても導電性の向上がより重要であり、多数積層された所定形状のグラフェンへのニーズが高い。 However, in the conventional method, graphene composed of a large number of regular layers such as hexagons has not been stably obtained. For this reason, when transferring from a metal substrate to another substrate such as plastic, the transfer operation has to be repeated many times, which is troublesome and deterioration of quality due to transfer is inevitable. In particular, for application to a touch panel or the like, improvement in conductivity is more important even if the visible light transmittance is somewhat reduced, and there is a high need for graphene having a predetermined shape in which a large number of layers are laminated.
本発明の課題は、上記問題点に鑑みて、樟脳等の炭素源を用いたＣＶＤにより、ドメイン形状あるいは連続膜からなるグラフェンの製造方法を提供することである。 The subject of this invention is providing the manufacturing method of the graphene which consists of a domain shape or a continuous film by CVD using carbon sources, such as camphor, in view of the said problem.
本発明者らは、ＣＶＤの条件を工夫することにより、上記課題を解決しうることを見出した。すなわち、本発明によれば、以下の単結晶グラフェンの製造方法等が提供される。 The present inventors have found that the above-mentioned problems can be solved by devising the CVD conditions. That is, according to the present invention, the following method for producing single crystal graphene and the like are provided.
[１]炭素源の熱分解によりグラフェンを製造する方法であって、第１の領域に炭素
源である化合物を配置させ、第２の領域に基板を配置させ、前記第１の領域を加熱して前記化合物を蒸気化し、加熱した前記第２の領域に少なくともアルゴンと水素とを含むキャリアガスにより前記樟脳の蒸気を導き、当該加熱された第２の領域において、前記化合物を基板上で熱分解することで、前記基板の表面上に所定のドメイン形状のグラフェンを複数個形成する、あるいは基板面全体に連続してグラフェンを形成する、単結晶グラフェンの製造方法。
[1] A method for producing graphene by pyrolysis of a carbon source, wherein a compound that is a carbon source is disposed in a first region, a substrate is disposed in a second region, and the first region is heated. The compound is vaporized and the camphor vapor is guided to the heated second region by a carrier gas containing at least argon and hydrogen, and the compound is pyrolyzed on the substrate in the heated second region. Thus, a method for producing single crystal graphene, in which a plurality of graphenes having a predetermined domain shape are formed on the surface of the substrate, or the graphene is continuously formed on the entire substrate surface.
［２］前記基板が、前記キャリアガスの流れる方向に対して、１０°〜８０°傾斜している、前記［１］に記載の単結晶グラフェンの製造方法。 [2] The method for producing single crystal graphene according to [1], wherein the substrate is inclined by 10 ° to 80 ° with respect to a direction in which the carrier gas flows.
［３］前記キャリアガスの導入側とは反対側の基板面にグラフェンを形成する前記［１］または［２］に記載の単結晶グラフェンの製造方法。 [3] The method for producing single-crystal graphene according to [1] or [2], wherein graphene is formed on a substrate surface opposite to the carrier gas introduction side.
［４］前記炭素源が、炭素の６員環、炭化水素、および酸素を含む化合物である、前記［１］〜［３］のいずれかに記載のグラフェンの製造方法。 [4] The method for producing graphene according to any one of [1] to [3], wherein the carbon source is a compound containing a carbon six-membered ring, a hydrocarbon, and oxygen.
［５］前記炭素源が樟脳を含む炭素源である、前記［１］〜［４］のいずれかに記載のグラフェンの製造方法。 [5] The method for producing graphene according to any one of [1] to [4], wherein the carbon source is a carbon source including camphor.
［６］前記アルゴンガスに対する水素ガスの流量比が０．０２０〜０．２０である、前記［１］〜［５］のいずれかに記載のグラフェンの製造方法。 [6] The method for producing graphene according to any one of [1] to [5], wherein a flow rate ratio of hydrogen gas to argon gas is 0.020 to 0.20.
［７］前記基板が少なくともその表面に、Ｃｕ、Ａｌ、Ｆｅ、Ｃｏ、Ｎｉ、Ａｕ、Ａｇ のいずれかまたはそれらの合金、またはそれらの化合物、炭化ケイ素、あるいは白金その他の貴金属が形成されている、前記［１］〜［６］のいずれかに記載のグラフェンの製造方法。 [7] At least on the surface of the substrate, any of Cu, Al, Fe, Co, Ni, Au, Ag, or an alloy thereof, a compound thereof, silicon carbide, platinum, or other noble metal is formed. The method for producing graphene according to any one of [1] to [6].
［８］前記グラフェンが、６角形、円形、またはリボン形状のグラフェン構造である、前記［１］〜［７］のいずれかに記載のグラフェンの製造方法。 [8] The method for producing graphene according to any one of [1] to [7], wherein the graphene has a hexagonal, circular, or ribbon-shaped graphene structure.
［９］前記グラフェンが１００層以下の積層体である、前記［１］〜［８］のいずれかに記載のグラフェンの製造方法。 [9] The method for producing graphene according to any one of [1] to [8], wherein the graphene is a laminate of 100 layers or less.
［１０］前記［９］によって得られたグラフェンの積層体が転写されたタッチパネル。 [10] A touch panel onto which the graphene laminate obtained in [9] is transferred.
以下、図面を参照しつつ本発明の実施の形態について説明する。本発明は、以下の実施形態に限定されるものではなく、発明の範囲を逸脱しない限りにおいて、変更、修正、改良を加え得るものである。 Hereinafter, embodiments of the present invention will be described with reference to the drawings. The present invention is not limited to the following embodiments, and changes, modifications, and improvements can be added without departing from the scope of the invention.
図１-ａに示すように、通常ＣＶＤは円筒状容器内でキャリアガスを流す方向の上流側に昇華あるいは蒸発させる原料を配置し、下流側に基板を配置する。そして、基板はキャリアガスの流れる方向に平行に膜形成を行う面を向ける。すなわち、本発明の製造方法においては、ＣＶＤ装置の第１の領域に炭素源の化合物、第２の領域に基板を配置させる。前記第１の領域を加熱して前記炭素源の化合物を蒸気化し、加熱した前記第２の領域に少なくともアルゴンと水素とを含むキャリアガスにより前記蒸気を導き、当該加熱された第２の領域において、前記化合物を基板上で熱分解することで、前記基板の表面上にドメイン形状のグラフェンあるいは基板全体に連続したグラフェンを形成する。ただし、本発明においては、図１-ｂに示すように、基板が前記キャリアガスの流れる方向に対して、１０°〜８０°傾斜していることが好ましく、キャリアガスの導入側（基板表面側）とは反対側の基板面、すなわち、基板表面側より炭素化合物の蒸気の少ない裏面にグラフェンを形成することがより好ましい。一方、炭素原子の量を減らすことにより、基板表面側にドメイン形状のグラフェンを成長させることもできる。すなわち、基板面近傍のガス圧がグラフェン形状にクリティカルな影響を与える。 基板表面側では基板裏面側に比してガス圧が高く、非定型形状のグラフェンが形成されやすい。一方、基板裏面側ではガス圧が相対的に低く、特有の核形成と核成長が生じて６角形状グラフェン等の定型のグラフェンが形成される。さらに、前記炭素源が、炭素の６員環、炭化水素、および酸素を含む化合物であることが好ましく、樟脳であることがより好ましい。キャリアガスとして、アルゴンガスに対する水素ガスの流量比が０．０２０〜０．２０であり、ＣＶＤ装置内は減圧でも構わないが、大気圧であることがより好ましい。基板としては、少なくともその表面に、Ｃｕ、Ｆｅ、Ｃｏ、Ｎｉのいずれかまたはそれらの合金、またはそれらの化合物、炭化ケイ素、あるいは白金その他の貴金属が形成されていることが好ましい。なお、基板は６００℃〜１１００℃に加熱することが好ましく、８００℃〜１０００℃がより好ましい。 As shown in FIG. 1A, in general CVD, a raw material to be sublimated or evaporated is arranged on the upstream side in the flow direction of the carrier gas in a cylindrical container, and a substrate is arranged on the downstream side. The substrate faces the surface on which the film is formed in parallel with the direction in which the carrier gas flows. That is, in the manufacturing method of the present invention, the compound of the carbon source is disposed in the first region of the CVD apparatus, and the substrate is disposed in the second region. The first region is heated to vaporize the compound of the carbon source, the vapor is guided to the heated second region by a carrier gas containing at least argon and hydrogen, and in the heated second region By thermally decomposing the compound on the substrate, domain-shaped graphene or continuous graphene is formed on the entire surface of the substrate. However, in the present invention, as shown in FIG. 1B, it is preferable that the substrate is inclined by 10 ° to 80 ° with respect to the flow direction of the carrier gas. It is more preferable to form graphene on the substrate surface opposite to (), that is, on the back surface with less vapor of the carbon compound than on the substrate surface side. On the other hand, domain-shaped graphene can be grown on the substrate surface side by reducing the amount of carbon atoms. That is, the gas pressure near the substrate surface has a critical effect on the graphene shape. The gas pressure on the substrate front side is higher than that on the back side of the substrate, and atypical graphene is easily formed. On the other hand, the gas pressure is relatively low on the back side of the substrate, and specific nucleation and growth occur to form regular graphene such as hexagonal graphene. Furthermore, the carbon source is preferably a compound containing a carbon 6-membered ring, a hydrocarbon, and oxygen, and more preferably camphor. As a carrier gas, the flow rate ratio of hydrogen gas to argon gas is 0.020 to 0.20, and the inside of the CVD apparatus may be depressurized, but is preferably atmospheric pressure. As the substrate, it is preferable that at least the surface thereof is formed of any one of Cu, Fe, Co, Ni or an alloy thereof, a compound thereof, silicon carbide, platinum, or other noble metal. In addition, it is preferable to heat a board | substrate at 600 to 1100 degreeC, and 800 to 1000 degreeC is more preferable.
基板に形成されるグラフェンは、６角形、円形、リボン形状のドメイン構造であることが好ましく、あるいは基板面全体に連続した膜であってもよい。また、ドメイン状でも連続した膜であっても、１００層以下の積層体であることが好ましい。さらには、この積層体をプラスチック等の他の基板に転写してタッチパネルを形成することが好ましい。 The graphene formed on the substrate preferably has a hexagonal, circular, or ribbon-shaped domain structure, or may be a film continuous over the entire substrate surface. Moreover, it is preferable that it is a laminated body of 100 layers or less, whether it is a domain shape or a continuous film. Furthermore, it is preferable to transfer the laminate to another substrate such as plastic to form a touch panel.
以下、本発明を実施例に基づいてさらに詳細に説明するが、本発明はこれら実施例に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these Examples.
炭素源として、図２-ａのように、植物由来の樟脳の固体粉末を用いた。樟脳の分子構造はグラフェンの成長に影響し、図２-ｂに示すように、炭素の６員環、炭化水素、および酸素を含む化合物であり、２００℃での加熱により容易に昇華する。図２-ｃのように、固体の樟脳のラマンスペクトラムは、炭素の員環に対応して、６５２ｃｍ−１に最も大きなピークが得られ、Ｃ＝Ｏ拡張振動結合に対応して１７４１ｃｍ−１にも次に大きなピーク、さらにはＣ-Ｈに対応して８５７、１０９３、および１４４７ｃｍ−１に小さなピークが存在する。 As a carbon source, as shown in FIG. 2-a, plant-derived camphor solid powder was used. The molecular structure of camphor affects the growth of graphene, and as shown in FIG. 2B, it is a compound containing a 6-membered ring of carbon, a hydrocarbon, and oxygen, and is easily sublimated by heating at 200 ° C. As in FIG. 2-c, the Raman spectrum of the solid camphor, corresponding to membered ring of carbon, the largest peak is obtained 652cm -1, the 1741Cm -1 corresponds to C = O extension vibration bond There are also the next largest peaks and even smaller peaks at 857, 1093 and 1447 cm −1 corresponding to C—H.
キャリアガス中の、アルゴンガスに対する水素ガスの流量を変え、さらに、キャリアガスとして他に、Ｎ２とＮＨ３を流した。基板としてのＣｕ箔はキャリアガスが流れる方向に対して４５°傾けて設置した。基板は１０００℃に加熱した。 The flow rate of hydrogen gas relative to argon gas in the carrier gas was changed, and N 2 and NH 3 were also flowed as the carrier gas. The Cu foil as the substrate was installed at an angle of 45 ° with respect to the direction in which the carrier gas flows. The substrate was heated to 1000 ° C.
なお、合成されたグラフェン膜の評価はラマン分光、光学顕微鏡、および走査電子顕微鏡（ＳＥＭ）にて行った。ラマン分光は、ＮＲＳ３３００レーザーラマン分光計（波長５３２．０８ｎｍのレーザー励起）、光学顕微鏡はデジタルマイクロスコープＶＨＸ-５００、走査電子顕微鏡はＨｉｔａｃｈｉ Ｓ-４３００を使用した。なお、プラスチック上のグラフェン膜の透光度評価はＪＡＳ-Ｖ５７０分光計にてＵＶ-Ｖｉｓ-ＮＩＲを用いて行った。 Note that the synthesized graphene film was evaluated by Raman spectroscopy, an optical microscope, and a scanning electron microscope (SEM). For Raman spectroscopy, an NRS3300 laser Raman spectrometer (laser excitation with a wavelength of 532.08 nm) was used, a digital microscope VHX-500 was used as the optical microscope, and a Hitachi S-4300 was used as the scanning electron microscope. Note that the transmittance of the graphene film on the plastic was evaluated using UV-Vis-NIR with a JAS-V570 spectrometer.
キャリアガスが、Ｈ２：１ｓｃｃｍおよびＡｒ：９８ｓｃｃｍの条件では、デンドライト（樹枝状）の核が発生したが、Ｈ２：２ｓｃｃｍおよびＡｒ：９８ｓｃｃｍの条件では、６角形のグラフェンが形成された。さらに、Ｈ２の流量と基板表面への樟脳の量により、形成されるグラフェンの形態が異なり、ガス供給側の基板表面ではグラフェンの連続膜が形成されるが、基板裏面ではド６角形状のグラフェンドメイン群が形成される（図３-ａ、図３-ｂ参照）。グラフェンドメインを光学顕微鏡で観察した結果を図４に示す。基板面のＣｕ箔表面より明るく見えているのはグラフェンドメインである（図４-ａ）。グラフェンドメインは、多結晶Ｃｕ箔の結晶粒界にまたがって形成され、このドメインを拡大してみると６角形となっており、ドメインの大きさは８〜１１μｍである（図４-ｂ）。さらに、高分解能で観察すると多結晶Ｃｕ箔の結晶粒界をまたいでドメインが成長している（図４-ｃ）。本発明の樟脳を炭素源とするグラフェンのドメインは、既報告のメタンガスを炭素源とするグラフェンと同じようにその形状が制御できる。 Dendritic (dendritic) nuclei were generated when the carrier gas was H 2 : 1 sccm and Ar: 98 sccm, but hexagonal graphene was formed under the conditions of H 2 : 2 sccm and Ar: 98 sccm. Furthermore, the amount of camphor to the flow rate and substrate surface H 2, different forms of graphene formed, in the substrate surface of the gas supply side continuous film of graphene is formed, in the substrate back surface de hexagonal shape A graphene domain group is formed (see FIGS. 3-a and 3-b). The result of observing the graphene domain with an optical microscope is shown in FIG. The graphene domains appear brighter than the Cu foil surface on the substrate surface (FIG. 4-a). The graphene domain is formed across the crystal grain boundary of the polycrystalline Cu foil. When this domain is enlarged, it is hexagonal, and the size of the domain is 8 to 11 μm (FIG. 4B). Furthermore, when observed with high resolution, domains grow across the grain boundaries of the polycrystalline Cu foil (FIG. 4-c). The shape of the graphene domain using camphor as a carbon source in the present invention can be controlled in the same manner as the graphene using methane gas as a carbon source.
ドメイン状グラフェンの結晶性およびその均一性を評価するため、ラマン分光を行った。６角形のドメイン内のラマン分光マッピングからは、Ｄ〜Ｇのピーク、さらにはＧ〜２Ｄのピークともに、ドメイン内分布は見られず、欠陥がきわめて少なく、均一な膜であることが判明した。 In order to evaluate the crystallinity and uniformity of domain graphene, Raman spectroscopy was performed. From the Raman spectroscopic mapping in the hexagonal domain, it was found that neither the D to G peak nor the G to 2D peak was observed in the domain, and the film was uniform with very few defects.
６角形グラフェンドメインのエッジ形状をより明確に確認するため、走査電子顕微鏡観察を行った。６角形であることが明確に確認され、また近接するドメイン同士が同じ方向に整列して成長していることが分かった（図５-ａ）。また、６角形グラフェンドメインがＣｕ箔の結晶粒界にまたがって成長していることが分かる（図５-ｂ）。このことより、ドメインの成長は基板の結晶粒界に影響されないことが分かる。 In order to more clearly confirm the edge shape of the hexagonal graphene domain, observation with a scanning electron microscope was performed. It was clearly confirmed to be hexagonal, and it was found that adjacent domains grew in alignment in the same direction (FIG. 5-a). It can also be seen that hexagonal graphene domains grow across the crystal grain boundaries of the Cu foil (FIG. 5-b). This shows that the domain growth is not affected by the crystal grain boundaries of the substrate.
上記のように、６角形のドメインのグラフェン以外に、円形のドメインが形成された。
円形のドメインの光学顕微鏡写真と走査電子顕微鏡写真をそれぞれ示す（図６-ａ、図６-ｂ）。これらドメイン形状の差異はキャリアガスの組成に大きく影響される。Ｃｕ箔上にドメイン状のグラフェンが形成され、個々のドメインが面内方向に成長して連続的なグラフェン膜になった状態を光学顕微鏡で観察した（図7）。グラフェン膜が欠陥なく、Ｃｕ表面全体を覆っており、そのなかに６角形のドメイン状グラフェンが確認できる。このような連続膜は基板表面が多量の樟脳分子に晒され、グラフェン核形成密度が大きくなることに拠ると考える。
As described above, in addition to hexagonal domain graphene, circular domains were formed.
An optical micrograph and a scanning electron micrograph of the circular domain are shown (FIGS. 6a and 6b), respectively. These domain shape differences are greatly influenced by the composition of the carrier gas. Domain-shaped graphene was formed on the Cu foil, and the state in which individual domains grew in the in-plane direction to form a continuous graphene film was observed with an optical microscope (FIG. 7). The graphene film has no defects and covers the entire Cu surface, and hexagonal domain graphene can be confirmed therein. It is considered that such a continuous film is based on the fact that the substrate surface is exposed to a large amount of camphor molecules and the graphene nucleation density is increased.
Ｃｕ箔上に合成されたグラフェンは種々の電子デバイスに応用できる。ガス供給側の基板表面に形成されるグラフェン連続膜は、透明導電膜あるいは種々の電子デバイスの光学窓に好適である。一方、６角形グラフェンドメインは、高速トランジスタ、ダイオード、あるいはセンサーに好適である。 Graphene synthesized on Cu foil can be applied to various electronic devices. The graphene continuous film formed on the substrate surface on the gas supply side is suitable for an optical window of a transparent conductive film or various electronic devices. On the other hand, hexagonal graphene domains are suitable for high-speed transistors, diodes, or sensors.
Ｃｕ箔上のグラフェンを化学エッチングによりプラスチックその他の基板に転写するプロセスを図８に模式的に示す。グラフェンの層数はキャリアガスの組成および流量によって制御できる。この形成される層数の制御は、電子デバイスに必要な、透光性を有しつつ大きな導電性を得るために重要であり、本発明によりこの両立性を制御できるようになった。厚みの異なるグラフェン膜の透光性の光波長依存性を測定した結果を図９に示す。波長５５０ｎｍの光に対する透光度が８９％と７３％であった（グラフェン膜の厚みはそれぞれ０．００４５μｍ、０．０１１μｍ）。また、光波長５５０ｎｍに対する透光度とシート抵抗との関係を図１０に示す。透光度が大きいほどシート抵抗が大きくなることを示している。 FIG. 8 schematically shows a process of transferring graphene on a Cu foil to a plastic or other substrate by chemical etching. The number of graphene layers can be controlled by the composition and flow rate of the carrier gas. The control of the number of layers to be formed is important for obtaining large conductivity while having translucency necessary for an electronic device, and this compatibility can be controlled by the present invention. FIG. 9 shows the results of measuring the light wavelength dependency of the translucency of graphene films having different thicknesses. The transmissivity for light having a wavelength of 550 nm was 89% and 73% (the thicknesses of the graphene films were 0.0045 μm and 0.011 μm, respectively). Further, FIG. 10 shows the relationship between the light transmittance and the sheet resistance with respect to the light wavelength of 550 nm. It shows that the sheet resistance increases as the translucency increases.
本発明の製造方法によって得られたグラフェンは透明電極あるいは電子デバイス等に利用することができる。
The graphene obtained by the production method of the present invention can be used for a transparent electrode or an electronic device.
Claims (10)
A touch panel to which the graphene laminate of claim 9 is transferred.
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| CN104695012A (en) * | 2015-03-24 | 2015-06-10 | 山东大学 | Device and method for preparing large-size high-quality graphene single crystal |
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| CN104695012A (en) * | 2015-03-24 | 2015-06-10 | 山东大学 | Device and method for preparing large-size high-quality graphene single crystal |
| CN104695012B (en) * | 2015-03-24 | 2017-03-22 | 山东大学 | Device and method for preparing large-size high-quality graphene single crystal |
| CN106119806A (en) * | 2016-06-27 | 2016-11-16 | 重庆墨希科技有限公司 | A kind of continuous-flow type continuous Large-scale graphene film preparation device |
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