JP5499980B2 - Method for producing graphene thin film - Google Patents
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本発明は、太陽電池の透明導電膜などへの適用が有望視される、グラフェン薄膜の製造方法に関するもので、特に静電吸着力を利用したグラフェン薄膜の製造方法に関する。 The present invention relates to a method for producing a graphene thin film, which is expected to be applied to a transparent conductive film of a solar cell, and particularly relates to a method for producing a graphene thin film using electrostatic adsorption force.
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、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薄膜を基板上に形成する方法である。この方法によれば、簡便で高品質のグラフェン薄膜が得られるが、大面積のグラフェン薄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, 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 to the adhesive tape is transferred. In this method, a graphene thin film composed of a graphene monolayer and a graphene stack is randomly formed on the substrate by rubbing on the substrate. According to this method, a simple and high-quality graphene thin film can be obtained, but it is not suitable for producing a large area graphene thin film.
近年においては、高品質で、かつ、大面積のグラフェン薄膜を製造する試みがなされている。その方法の１つとして、非特許文献３には、グラファイトを酸性中で酸化剤を用いて酸化した酸化グラファイトを、溶液中で単層に剥離し、酸化グラフェンを含む懸濁液形成するとともに、基板を懸濁液浸漬し、引き上げることで基板に酸化グラフェン薄膜を形成する。形成した酸化グラフェン薄膜を１１００℃以上で加熱還元してグラフェン薄膜を製造することが記載されている。 また、非特許文献４には、酸化グラフェンを含む懸濁液を吸引濾過によって酸化グラフェンと溶媒を分離し、濾紙上に形成された酸化グラフェン薄膜を任意の基板に転写し、ヒドラジンの存在下で酸化グラフェンを加熱還元することで、グラフェン薄膜が形成できることが記載されている。この方法では、任意の基板に酸化グラフェン薄膜を形成することは可能であるが、膜厚の制御が難しく、基板一面に均一な層数のグラフェン薄膜を形成することは難しいものであった。 In recent years, attempts have been made to produce high-quality, large-area graphene thin films. As one of the methods, Non-Patent Document 3 discloses that graphite oxide obtained by oxidizing graphite using an oxidizing agent in an acid is peeled into a single layer in a solution to form a suspension containing graphene oxide, A graphene oxide thin film is formed on the substrate by dipping the substrate in suspension and pulling it up. It describes that a graphene oxide thin film is heated and reduced at 1100 ° C. or higher to produce a graphene thin film. In Non-Patent Document 4, a suspension containing graphene oxide is separated from the graphene oxide and the solvent by suction filtration, the graphene oxide thin film formed on the filter paper is transferred to an arbitrary substrate, and in the presence of hydrazine. It is described that a graphene thin film can be formed by heating and reducing graphene oxide. In this method, it is possible to form a graphene oxide thin film on an arbitrary substrate, but it is difficult to control the film thickness, and it is difficult to form a graphene thin film having a uniform number of layers on one surface of the substrate.
本発明の目的は、基板選択の自由度が高く、簡易な方法により大面積のグラフェン薄膜を、原子層レベルで膜厚（薄膜層数）を自在に製造可能な、グラフェン薄膜の製造方法を提供することにある。 An object of the present invention is to provide a method for producing a graphene thin film, which has a high degree of freedom in substrate selection and can produce a large-area graphene thin film at a atomic layer level with a simple method. There is to do.
上記目的を達成するため、本発明のグラフェン薄膜の製造方法によれば、グラファイトを酸化して酸化グラファイトを得る工程と、酸化グラファイトを溶媒に分散し、該酸化グラファイトを層状に剥離して酸化グラフェンを含む懸濁液を得る工程と、前記懸濁液に基板を浸漬して酸化グラフェン薄膜を形成し、該酸化グラフェンを還元してグラフェン薄膜を形成する工程とを含むグラフェン薄膜の製造方法であって、
前記グラフェン薄膜を成膜する工程において、基板にカチオン材料の薄膜をあらかじめ形成し、前記基板表面を正に帯電させ、前記基板を酸化グラフェンを含む懸濁液に浸漬し、カチオン材料の正電荷と酸化グラフェンの負電荷による静電気力により酸化グラフェンを吸着させることで酸化グラフェン薄膜を形成し、ついで酸化グラフェン薄膜を還元してグラフェン薄膜を形成することとする。
In order to achieve the above object, according to the method for producing a graphene thin film of the present invention, a step of obtaining graphite oxide by oxidizing graphite, and dispersing graphite oxide in a solvent, peeling the graphite oxide into a layer, and graphene oxide And a step of forming a graphene oxide thin film by immersing a substrate in the suspension and reducing the graphene oxide to form a graphene thin film. And
In the step of forming the graphene thin film, a cationic material thin film is formed in advance on the substrate, the substrate surface is positively charged, the substrate is immersed in a suspension containing graphene oxide, and the positive charge of the cationic material is increased. A graphene oxide thin film is formed by adsorbing graphene oxide by an electrostatic force due to the negative charge of the graphene oxide, and then the graphene oxide thin film is reduced to form a graphene thin film.
カチオン材料は正に帯電しており、負に帯電している酸化グラフェンを引き寄せ吸着させることが出来る。このため、本発明では酸化グラフェン溶液中に基板を浸漬させるだけでグラフェン薄膜を形成させることが出来る。 The cationic material is positively charged and can attract and adsorb negatively charged graphene oxide. For this reason, in this invention, a graphene thin film can be formed only by immersing a board | substrate in a graphene oxide solution.
また、本発明によれば、前記カチオン材料に吸着した前記酸化グラフェン薄膜が部分的に２層以上重なっている箇所を、超音波処理により、重なっている酸化グラフェン薄膜の上層を剥がし、酸化グラフェン薄膜を単層薄膜にすることが好ましい。これにより、所望とするグラフェン薄膜を、原子層単位で、自由に形成することが可能になる。漆に金箔を貼った場合に金箔が重なった部分が剥がれるのと同じように、酸化グラフェン薄膜に超音波処理を施すと、部分的に重なった箇所が破れるようにして剥がれる。 Further, according to the present invention, the superficial graphene oxide thin film is peeled off by ultrasonic treatment at a location where two or more layers of the graphene oxide thin film adsorbed on the cationic material partially overlap, and the graphene oxide thin film Is preferably a single layer thin film. Thereby, a desired graphene thin film can be freely formed in units of atomic layers. In the same way as when the gold foil is overlapped with lacquer, the portion where the gold foil overlaps is peeled off, and when the graphene oxide thin film is subjected to ultrasonic treatment, the partially overlapped portion is peeled off.
このカチオン材料はアミノ基を有する化合物であることが望ましく、特にポリジアリルジメチルアンモニウムクロライドが望ましい。アミノ基は、正に帯電する一般的な基である。 The cationic material is preferably a compound having an amino group, and particularly polydiallyldimethylammonium chloride. Amino groups are common groups that are positively charged.
また、カチオン材料の膜厚が1nm以下であることが望ましい。カチオン材料とカチオン材料同士では、共に正に帯電しているので、１ｎｍ以上にまでカチオン材料を重ねて膜厚を厚くすることは困難である。 Further, it is desirable that the thickness of the cationic material is 1 nm or less. Since both the cation material and the cation material are positively charged, it is difficult to increase the film thickness by overlapping the cation material to 1 nm or more.
酸化グラフェンを分散させる溶媒として、水、エタノール、メタノール、アセトン、Ｎ−ジメチルホルムアミド及びＮ−メチルピロリドンから選ばれる１種又は２種以上の混合液を用いることが望ましい。これらの溶媒は、経験的に酸化グラフェンの溶解度パラメータと合っていることを知見した。また、分散させる酸化グラフェンは平均サイズが１００nm〜２００μｍであることが望ましい。平均サイズは１０μm以上がより好ましい。１０μm以上であれば、酸化グラフェンが重なっている箇所を低減することが出来、単一の酸化グラフェンでカバーできる面積を大きく出来る。 As a solvent for dispersing graphene oxide, it is desirable to use one or a mixture of two or more selected from water, ethanol, methanol, acetone, N-dimethylformamide, and N-methylpyrrolidone. These solvents were empirically found to match the solubility parameters of graphene oxide. The graphene oxide to be dispersed preferably has an average size of 100 nm to 200 μm. The average size is more preferably 10 μm or more. If it is 10 micrometers or more, the location which the graphene oxide overlaps can be reduced and the area which can be covered with a single graphene oxide can be enlarged.
本発明によれば、基板選択の自由度が高く、基板上に原子層レベルで膜厚を制御できるグラフェン薄膜を形成することが可能となる。 According to the present invention, it is possible to form a graphene thin film having a high degree of freedom in substrate selection and capable of controlling the film thickness at the atomic layer level on the substrate.
本発明のグラフェン薄膜の製造方法は、酸化グラフェンを含む懸濁液をカチオン材料の薄膜を形成した基板に浸漬することで、静電吸着により酸化グラフェン薄膜を形成し、該酸化グラフェン薄膜を還元することでグラフェン薄膜を得る。なお、本発明において、「グラフェン薄膜」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 thin film of the present invention, a graphene oxide thin film is formed by electrostatic adsorption by immersing a suspension containing graphene oxide in a substrate on which a thin film of a cationic material is formed, and the graphene oxide thin film is reduced. Thus, a graphene thin film is obtained. In the present invention, the “graphene thin film” includes a film including a graphene stack in which a plurality of graphene single layers are stacked in addition to a film formed of a graphene single layer.
酸化グラフェンを含む懸濁液は、従来公知の方法により製造できる。例えば、Ｈｕｍｍｅｒｓ法により酸化グラファイトを合成し、これを溶媒に展開して超音波を照射することで、酸化グラファイトが層方向に剥離され、酸化グラフェンを含む懸濁液が得られる。 A suspension containing graphene oxide can be produced by a conventionally known method. For example, by synthesizing graphite oxide by the Hummers method, developing this in a solvent and irradiating ultrasonic waves, the graphite oxide is peeled off in the layer direction, and a suspension containing graphene oxide is obtained.
具体的には、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、炭素原子に酸素原子が結合し、層間に酸素原子が導入されて酸化グラファイトが得られる。次いで、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。また、溶媒に分散後の溶液を遠心分離し、上澄み液を回収することで、酸化グラフェンを高濃度含む懸濁液が得られる。溶媒としては、特に限定はないが極性溶媒が好ましい。極性溶媒は、溶解度パラメータが高い。例えば、水、アセトン、メタノール、エタノール、Ｎ−ジメチルホルムアミド及びＮ−メチルピロリドンから選ばれる１種又は２種以上の混合液等が挙げられる。 Specifically, after immersing graphite in concentrated sulfuric acid and adding potassium permanganate to react, the reaction product is immersed in sulfuric acid and reacted by adding hydrogen peroxide to obtain graphite oxide. By reacting graphite by adding potassium permanganate in concentrated sulfuric acid, oxygen atoms are bonded to carbon atoms, and oxygen atoms are introduced between layers to obtain graphite oxide. Next, by dispersing the graphite oxide obtained in this way 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 is recovered with a high yield. it can. In addition, a suspension containing a high concentration of graphene oxide is obtained by centrifuging the solution after dispersion in a solvent and collecting the supernatant. Although there is no limitation in particular as a solvent, A polar solvent is preferable. Polar solvents have a high solubility parameter. For example, 1 type, or 2 or more types of liquid mixture chosen from water, acetone, methanol, ethanol, N-dimethylformamide, and N-methylpyrrolidone etc. are mentioned.
懸濁液中の酸化グラフェンの濃度は、０．００１〜０．１ｍｇ／ｍｌが好ましく、０．００３〜０．０１ｍｇ／ｍｌがより好ましい。０．００１ｍｇ／ｍｌ未満であると、最終的に得られるグラフェン薄膜の厚みを大きくすることが困難になる傾向にある。０．１ｍｇ／ｍｌを超えると、成膜の際に酸化グラフェン同士が凝集し、均一に成膜することが難しくなる傾向にある。 The concentration of graphene oxide in the suspension is preferably 0.001 to 0.1 mg / ml, and more preferably 0.003 to 0.01 mg / ml. If it is less than 0.001 mg / ml, it tends to be difficult to increase the thickness of the finally obtained graphene thin film. When it exceeds 0.1 mg / ml, graphene oxides aggregate during film formation, and it tends to be difficult to form a film uniformly.
カチオン材料の薄膜の形成方法は、ポリジアリルジメチルアンモニウムクロライド水溶液中に基板を浸漬し、その後、純水にて洗浄を行う。カチオン材料の水溶液の濃度は１−５wt＆が望ましく、より好ましくは２−３wt％とすることで均一にカチオン材料を基板に形成することが出来る。 In the method of forming a thin film of a cationic material, the substrate is immersed in an aqueous solution of polydiallyldimethylammonium chloride, and then washed with pure water. The concentration of the aqueous solution of the cationic material is desirably 1-5 wt &, more preferably 2-3 wt%, so that the cationic material can be uniformly formed on the substrate.
基板は、還元時の加熱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。本発明では、３００℃以上、６００℃以下の温度でも酸化グラフェンをグラフェンまで還元することができるので、３００℃以上の加熱に耐えうる材料で構成されたものでも適用可能である。具体的には、Ｓｉ基板、ＳｉＯ2／Ｓｉ基板、石英ガラス基板、ガラス基板、等が挙げられる。特に、ガラス基板は安価であるが、耐熱温度が６００℃以下であるため、本発明において特に効果的である。 The substrate made of any material can be used as long as it is made of a material that can withstand the heating during the reduction. In the present invention, graphene oxide can be reduced to graphene even at a temperature of 300 ° C. or higher and 600 ° C. or lower. Specific examples include Si substrates, SiO 2 / Si substrates, quartz glass substrates, glass substrates, and the like. In particular, the glass substrate is inexpensive, but the heat-resistant temperature is 600 ° C. or lower, so that it is particularly effective in the present invention.
次に、カチオン材料を形成した基板を酸化グラフェンの懸濁液に浸漬し、カチオン材料の正の電荷と酸化グラフェンの負の電荷による静電気力により、カチオン材料上に酸化グラフェンを均一に吸着させる。酸化グラフェンが吸着した基板を純水中で超音波処理を行うことで、余分な酸化グラフェンを取り除き、カチオン材料と静電気力で結合した酸化グラフェンのみが基板上に形成される。このように、前述したように、酸化グラフェン薄膜同士が重なった部分は、超音波処理により、除去するので、単層の酸化グラフェン薄膜、ひいては、単層のグラフェン薄膜、更には所望の層数のグラフェン薄膜を得ることができる。 Next, the substrate on which the cation material is formed is immersed in a suspension of graphene oxide, and the graphene oxide is uniformly adsorbed on the cation material by electrostatic force due to the positive charge of the cation material and the negative charge of the graphene oxide. By ultrasonically treating the substrate on which graphene oxide is adsorbed in pure water, excess graphene oxide is removed, and only graphene oxide bonded to the cationic material by electrostatic force is formed on the substrate. Thus, as described above, the overlapped portions of the graphene oxide thin films are removed by ultrasonic treatment, so that the single-layer graphene oxide thin film, the single-layer graphene thin film, and the desired number of layers are further reduced. A graphene thin film can be obtained.
所望の層数のグラフェン薄膜を製造する場合には、上述する工程を繰り返えすことで、原子層レベルで層数を制御することが可能である。
すなわち、所望の層数のグラフェン薄膜を製膜する場合には、カチオン塗付⇒酸化グラフェン浸漬⇒超音波処理、を繰り返す。したがって作製された膜は、基板／カチオン材料／酸化グラフェン／カチオン材料／酸化グラフェンと、ミルフィーユのように重なる。
When a graphene thin film having a desired number of layers is manufactured, the number of layers can be controlled at the atomic layer level by repeating the above-described steps.
That is, when a graphene thin film having a desired number of layers is formed, cation coating ⇒ graphene oxide immersion ⇒ ultrasonic treatment is repeated. Therefore, the produced film overlaps with substrate / cationic material / graphene oxide / cationic material / graphene oxide like mille-feuille.
さて、還元にはヒドラジン一水和物の水蒸気に加熱しながら暴露することで行っている。加熱温度は、基板がポリイミド基板のように、耐熱温度が３００℃程度の基板の場合は、上記とは異なり、好ましくは５０〜３００℃、より好ましくは９０〜３００℃の温度である。還元する時間は、好ましくは５分以上、より好ましくは１０分以上行う。このようにして酸化グラフェン薄膜を還元することで、酸化グラフェン薄膜が還元されグラフェン薄膜となる。 The reduction is carried out by exposure to water vapor of hydrazine monohydrate while heating. When the substrate is a substrate having a heat resistant temperature of about 300 ° C., such as a polyimide substrate, the heating temperature is preferably 50 to 300 ° C., more preferably 90 to 300 ° C., unlike the above. The reduction time is preferably 5 minutes or more, more preferably 10 minutes or more. By reducing the graphene oxide thin film in this manner, the graphene oxide thin film is reduced to become a graphene thin film.
なお、加熱温度は６００℃以上であってもよいが、ガラス基板やポリイミド基板などの使用がいずれも適さず、基板選択の自由度が損なわれる傾向にある。更には、得られるグラフェン薄膜が熱的損傷を受けて、特性が低下する恐れがある。 In addition, although heating temperature may be 600 degreeC or more, neither use of a glass substrate, a polyimide substrate, etc. is suitable, and it exists in the tendency for the freedom degree of board | substrate selection to be impaired. Furthermore, the graphene thin film obtained may be thermally damaged and the characteristics may deteriorate.
グラファイト粉末（平均粒径４0０μｍ）を１ｇ、ＮａＮＯ3ヲ０．７６ｇ、Ｈ2ＳＯ4を３３．８ｍｌをフラスコに加え、均一になるまで攪拌した。次に、ＫＭｎＯ４４．５０ｇを攪拌しながらフラスコに少量ずつ添加した。その際、フラスコの温度を５〜７℃以下に冷却した。２時間攪拌した後、冷却をはずし、３０℃に保った状態で５日間攪拌してスラリーを得た。 1 g of graphite powder (average particle size: 400 μm), 0.76 g of NaNO 3 and 33.8 ml of H 2 SO 4 were added to the flask and stirred until uniform. Next, 44.50 g of KMnO was added to the flask little by little with stirring. At that time, the temperature of the flask was cooled to 5 to 7 ° C. or lower. After stirring for 2 hours, the cooling was removed, and the mixture was stirred for 5 days while being kept at 30 ° C. to obtain a slurry.
このスラリーを撹拌しながらＨ2ＳＯ4（５ｗｔ％）水溶液５００ｍｌ中に添加し溶解させ、２時間撹拌した。攪拌後、Ｈ2Ｏ2（３０ｗｔ％）溶液を茶色から明るい黄色になるまで添加し、2時間撹拌した。 This slurry was added to 500 ml of an aqueous solution of H 2 SO 4 (5 wt%) with stirring, dissolved, and stirred for 2 hours. After stirring, a H 2 O 2 (30 wt%) solution was added from brown to light yellow and stirred for 2 hours.
この溶液を1日以上放置し、溶液中の浮遊物を沈殿させた。沈殿させた上澄液を捨て、Ｈ2ＳＯ4（３ｗｔ％）水溶液５００ｍｌ、Ｈ2Ｏ2（０．５ｗｔ％）水溶液を５００ｍｌ添加した。この工程を１０回繰り返し、沈殿物を回収して酸化グラファイトを得た。 This solution was allowed to stand for 1 day or longer to precipitate the suspended matter in the solution. The precipitated supernatant was discarded, and 500 ml of H 2 SO 4 (3 wt%) aqueous solution and 500 ml of H 2 O 2 (0.5 wt%) aqueous solution were added. This process was repeated 10 times, and the precipitate was collected to obtain graphite oxide.
得られた酸化グラファイトにメタノールを０．０３ｍｇ／ｍｌになるように添加し、よく攪拌した。この時に酸化グラファイトの層間が剥離され、酸化グラフェンが得られた。得られた酸化グラフェン溶液500ｇを、５分間遠心分離を行い、未剥離の酸化グラファイトを取り除いて酸化グラフェン溶液を得た。 Methanol was added to the obtained graphite oxide so that it might become 0.03 mg / ml, and it stirred well. At this time, the graphite oxide layer was peeled off, and graphene oxide was obtained. 500 g of the obtained graphene oxide solution was centrifuged for 5 minutes to remove unexfoliated graphite oxide to obtain a graphene oxide solution.
カチオン材料としてポリジアリルジメチルアンモニウムクロライドを2ｗｔ％となるように純水に添加し攪拌することで、ポリジアリルジメチルアンモニウムクロライド溶液、１００ｍｌを得た。この溶液にＵＶ−オゾン処理したＳｉＯ2／Ｓｉ基板（熱酸化膜基板）を図２のように20分浸漬し、その後純水にて良く洗浄をおこない、純水を乾燥させることで図３のようにポリジアリルジメチルアンモニウムクロライドを基板上に形成した。 As a cationic material, polydiallyldimethylammonium chloride was added to pure water so as to be 2 wt% and stirred to obtain 100 ml of a polydiallyldimethylammonium chloride solution. The SiO 2 / Si substrate (thermal oxide film substrate) treated with UV-ozone is immersed in this solution for 20 minutes as shown in FIG. 2, and then thoroughly washed with pure water and dried with pure water as shown in FIG. Thus, polydiallyldimethylammonium chloride was formed on the substrate.
そして、この基板を酸化グラフェン溶液に図４のように１０分間浸漬を行うことで静電気力により酸化グラフェンを吸着させた。その後、超音波処理を１分行うことで余分な酸化グラフェンを取り除き、基板一面に、重なり合う部分が無い単層の酸化グラフェン薄膜を形成した。 Then, this substrate was immersed in a graphene oxide solution for 10 minutes as shown in FIG. 4 to adsorb graphene oxide by electrostatic force. Thereafter, ultrasonic treatment was performed for 1 minute to remove excess graphene oxide, and a single-layer graphene oxide thin film having no overlapping portion was formed over the entire surface of the substrate.
次に、得られた酸化グラフェン薄膜を90℃にしたシャーレに配置し、ヒドラジン一水和物の蒸気に１０分間暴露して還元する。
更に、基板表面に付着しているカチオン材料を、１０００℃でアニールすることにより熱分解させ、図５のようなグラフェン薄膜を得た。
Next, the obtained graphene oxide thin film is placed in a petri dish set at 90 ° C., and reduced by exposure to vapor of hydrazine monohydrate for 10 minutes.
Furthermore, the cationic material adhering to the substrate surface was thermally decomposed by annealing at 1000 ° C. to obtain a graphene thin film as shown in FIG.
なお、このカチオン材料の除去は、基板がポリイミドのような低耐熱性の材料の場合は、ＵＶオゾン処理することにより、カチオン材料を燃やす。
図６に、本方法により作製したグラフェン薄膜の光学顕微鏡像を示す。 図５に示すように、基板にグラフェンが敷き詰められた状態で成膜されており、基板に均一に成膜されている。図７に示す原子間力顕微鏡像から得られたグラフェン薄膜は単層である。
The removal of the cation material burns the cation material by UV ozone treatment when the substrate is a low heat resistant material such as polyimide.
In FIG. 6, the optical microscope image of the graphene thin film produced by this method is shown. As shown in FIG. 5, the film is formed in a state where graphene is spread over the substrate, and the film is uniformly formed on the substrate. The graphene thin film obtained from the atomic force microscope image shown in FIG. 7 is a single layer.
基板にカチオン材料で吸着される酸化グラフェンの重なり合う部分を除去して、再度、酸化グラフェンを、基板に、再度カチオン材料を付着させて吸着させることにより、原子層単位で層数を選択され。グラフェン薄膜の膜厚を制御できることが可能となった。 By removing the overlapping part of graphene oxide adsorbed by the cation material on the substrate and adsorbing the graphene oxide again by adhering the cation material to the substrate, the number of layers can be selected in units of atomic layers. The film thickness of the graphene thin film can be controlled.
複数層のグラフェン薄膜を作製する場合には、基板に付着しているカチオン材料の除去は、酸化グラフェンの還元処理の後で、１０００℃で加熱するか、ＵＶオゾン処理して、カチオン材料を除去する。 In the case of producing a multi-layer graphene thin film, the cationic material adhering to the substrate is removed by removing the cationic material by heating at 1000 ° C. or UV ozone treatment after the reduction treatment of graphene oxide. To do.
１０：カチオン材料
１１：基板
１２：酸化グラフェン
１３：グラフェン
２０：カチオン材料分散溶媒
２１：酸化グラフェン分散溶媒
10: Cationic material 11: Substrate 12: Graphene oxide 13: Graphene 20: Cationic material dispersion solvent 21: Graphene oxide dispersion solvent
Claims (6)
前記グラフェン薄膜を成膜する工程において、基板にカチオン材料の薄膜をあらかじめ形成し、前記基板表面を正に帯電させ、前記基板を酸化グラフェンを含む懸濁液に浸漬し、カチオン材料の正電荷と酸化グラフェンの負電荷による静電気力により、カチオン材料に酸化グラフェンを吸着させることで酸化グラフェン薄膜を形成し、ついで酸化グラフェン薄膜を還元してグラフェン薄膜を形成することを特徴とするグラフェン薄膜の製造方法。 A step of obtaining graphite oxide by oxidizing graphite, a step of dispersing graphite oxide in a solvent, peeling the graphite oxide into a layer to obtain a suspension containing graphene oxide, and immersing a substrate in the suspension Forming a graphene oxide thin film, and reducing the graphene oxide to form a graphene thin film.
In the step of forming the graphene thin film, a cationic material thin film is formed in advance on the substrate, the substrate surface is positively charged, the substrate is immersed in a suspension containing graphene oxide, and the positive charge of the cationic material is increased. A method for producing a graphene thin film, comprising forming graphene oxide thin film by adsorbing graphene oxide to a cationic material by electrostatic force due to negative charge of graphene oxide, and then reducing the graphene oxide thin film to form the graphene thin film .
The method for producing a graphene thin film according to claim 1, wherein the graphene oxide has an average size of 100 nm to 200 μm.
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