JP5871213B2 - グラフェン基板の製造方法およびグラフェン基板 - Google Patents
グラフェン基板の製造方法およびグラフェン基板 Download PDFInfo
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- JP5871213B2 JP5871213B2 JP2012549708A JP2012549708A JP5871213B2 JP 5871213 B2 JP5871213 B2 JP 5871213B2 JP 2012549708 A JP2012549708 A JP 2012549708A JP 2012549708 A JP2012549708 A JP 2012549708A JP 5871213 B2 JP5871213 B2 JP 5871213B2
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Description
即ち、(1)剥離による製造方法(非特許文献2、参照)、(2)CVDによる製造方法(熱分解気相成長)(非特許文献3、参照)、(3)SiC(炭化ケイ素)の熱分解による製造方法(非特許文献4、参照)、(4)ガリウム・アモルファス炭素界面成長による製造方法(特許文献1および非特許文献5、参照)の4つの製造方法である。
即ち、金属層2は液体状態で炭素5を溶解するためのフラックスとして働く。
炭素含有層3は必ずしも均一な膜である必要はない。すなわち、原料用基板4の表面に局所的に配置されているだけで十分である。なぜなら、前述の通り、炭素含有層3は金属層2へ溶解する炭素5を供給するだけで、グラフェン9の成長には直接関係しないからである。
また、高品質なグラフェンを得るためには、成長用基板1はグラフェンを成長させる所望の平面内において平坦であることが望ましい。平坦性の観点からすると、成長用基板1として、単結晶基板もしくは単結晶を表面に製膜した基板が特に適している。
具体的には、ラマン分光で得られるDバンドとGバンドの比であるD/G比が小さいグラフェンが高品質である。D/G比は出来るだけ小さいほうが良く、D/G比≦0.2が望ましい。
なお、成長用基板1の表面は適当な方法で予め清浄しておく。
加熱する温度は、600℃以上が必要で、800℃以上が望ましく、1000℃以上がより好ましい。なお、600℃という温度範囲の下限は、グラフェン化に最低限必要な温度に対応する。また、加熱温度を800℃以上にすると、D/G比≦0.2である、高品質なグラフェンを形成することが可能である。さらに、加熱温度を1000℃以上にすると、D/G比≦0.1である、特に高品質なグラフェン9を得ることが出来る。
単位時間当たりの降下温度、すなわち、冷却速度は、加熱した温度から400℃までの範囲で、0〜100℃/分の範囲であることが望ましい。ここで、冷却速度0℃/分とは、ある温度を維持することを意味する。なお、400℃以下では自然冷却で構わない。また、急冷(例えば、冷却速度:50℃/分)の後に、徐冷(例えば、冷却速度:2℃/分)を行うことにより、炭素5の結晶化、すなわち、グラフェン9の成長に対し、その駆動力を増大させることが可能である。これによりグラフェンの品質を向上することが出来る。
第1段階では、金属層2を液体状態まま、吸引などの適当な方法で物理的に除去する。この段階で、金属層2の大部分はグラフェン基板10a、10bから取り除かれる。なお、第1段階で除去された金属層2の材料は再度、フラックスとして使用可能である。特に、レアメタルであるガリウム(Ga)を利用する場合、フラックスの再生は製造コストを顕著に低下させる効果がある。
第1の方法は、図2(b)に示される炭素含有層3を配置する際、予め、炭素含有層3にドーパント元素を添加しておく方法である。ドーパント元素単体をそのまま添加するか、ドーパント元素を含む材料を添加すればよい。また、もともとドーパント元素を含む材料を炭素含有層の材料として選択してもよい。
加熱した温度において、炭素含有層3中の炭素濃度が金属層2の炭素固溶度より低ければ、炭素含有層3は金属層2へ全量溶解する。従って、金属層2の炭素固溶度より低い範囲内で、炭素含有層3の炭素濃度を調整すれば、グラフェン9の層数を制御することが出来る。
金属層2の炭素固溶度は温度に依存するので、加熱温度を調整することによっても、グラフェン9の層数を制御することが出来る。一般に、金属中の炭素固溶度は温度上昇と伴に増加するので、炭素含有層3中の炭素量が十分あるとすると、加熱温度を上げるほど、層数の多いグラフェン9を形成することが出来る。
本発明の第2の実施形態は、基本的な製造の手順は第1の実施形態と同様であるが、異なる点が3つある。
ホルダ11は図4(a)に示すように、中央に凹部が形成された箱型の形状を有しており、凹部の寸法・形状は原料用基板4、成長用基板1の寸法・形状に対応している。
ここで示す実施例は、グラフェンの品質と加熱時間の関係に関するものである。
ここで示す実施例は、炭素量調整によるグラフェン層数制御に関するものである。
ここで示す実施例は、炭素含有層3として様々な炭素含有材料を用いて作製されるグラフェン基板10に関するものである。
ここで示す実施例は、様々な絶縁体基板上に作製されるグラフェン基板10に関するものである。
ここで示す実施例は、金属層2として様々な金属材料を用いて作製されるグラフェン基板10に関するものである。
ここで示す実施例は、グラフェン基板10を用いたデバイス作製に関するものである。
ここで示す実施例は、ドーピングされたグラフェン基板10と、それを用いたデバイス作製に関するものである。
2 金属層
3 炭素含有層
4 原料用基板
5 炭素
6 その他の元素
9、9a グラフェン
9b、9c、9d 3次元状グラフェン
9e 短冊状グラフェン
9f 2次元周期グラフェン
10a、10b、10c、10d、10e、10f グラフェン基板
11 ホルダ
12 スペーサ
13 フタ
31 マスク
32 ソース・ドレイン電極コンタクト部分
33 グラフェン・チャネル
34 ソース・ドレイン電極
35 ゲート絶縁体
36 ゲート電極
37 電界効果トランジスタ
Claims (17)
- (a)金属層を炭素含有層に接触させ、前記金属層を加熱することで、前記金属層中に前記炭素含有層中の炭素を溶解させる工程と、
(b)前記金属層を冷却することで、前記金属層に接触させた耐熱材料の表面に前記金属層中の前記炭素をグラフェンとして析出させる工程とを有することを特徴とするグラフェン基板の製造方法。 - 前記(b)工程の後に、更に、(c)前記金属層を除去する工程を有することを特徴とする請求項1に記載のグラフェン基板の製造方法。
- 前記(a)工程は、前記金属層中に前記炭素と伴に、アクセプター元素あるいはドナー元素を溶解させることを含み、
前記(b)工程は、前記炭素と伴に、アクセプター元素をp型グラフェンとして、あるいはドナー元素をn型グラフェンとして析出させることを含むことを特徴とする請求項2に記載のグラフェン基板の製造方法。 - 前記アクセプター元素は、2族元素及び13族元素からなる群から選ばれる少なくとも1種を有し、前記ドナー元素は、15族元素及び16族元素からなる群から選ばれる少なくとも1種を有することを特徴とする請求項3に記載のグラフェン基板の製造方法。
- 前記2族元素は、ベリリウム(Be)及びマグネシウム(Mg)を含み、
前記13族元素は、ホウ素(B)及びアルミニウム(Al)を含み、
前記15族元素は、窒素(N),リン(P)、ヒ素(As)及びSb(アンチモン)を含み、
前記16族元素は、イオウ(S)、セレン(Se)、及びテルル(Te)を含むことを特徴とする請求項4に記載のグラフェン基板の製造方法。 - 前記金属層は、ガリウム(Ga)、インジウム(In)、タリウム(Tl)、スズ(Sn)、アルミニウム(Al)、鉛(Pb)、ビスマス(Bi)、亜鉛(Zn)、Cd(カドミウム)及びHg(水銀)からなる群から選ばれる少なくとも1つを有することを特徴とする請求項1〜5のいずれか一項に記載のグラフェン基板の製造方法。
- 前記耐熱材料は、酸化物、窒化物、炭化物、フッ化物、雲母、及びダイヤモンドの内から選択される少なくとも一種であることを特徴とする請求項1〜6のいずれか一項に記載のグラフェン基板の製造方法。
- 前記酸化物は、石英(SiO2)、アルミナ及びサファイア(Al2O3)の少なくとも一種、酸化チタン(TiO2)、酸化亜鉛(ZnO)、酸化マグネシウム(MgO)、酸化ニッケル(NiO)、ジルコニア(ZrO2)、ニオブ酸リチウム(LiNbO3)、タンタル酸リチウム(LiTaO3)から選択され、前記窒化物は、窒化ホウ素(BN)、窒化アルミニウム(AlN)、窒化ガリウム(GaN)、窒化炭素(C3N4)、及び窒化炭素ホウ素(BCN)のうちから選択された少なくとも一種を含み、
前記炭化物は、炭化ケイ素(SiC)、炭化ホウ素(B4C)、炭化アルミニウム(Al4C3)、炭化チタン(TiC)、炭化ジルコニウム(ZrC)。炭化ハフニウム(HfC)、炭化バナジウム(VC)、炭化ニオブ(NbC)、炭化タンタル(TaC)、炭化クロム(CrC)、炭化モリブデン(MoC)、及び炭化タングステン(WC)から選択された少なくとも一種を含み、及び
前記フッ化は、フッ化バリウム(BaF2)、フッ化カルシウム(CaF2)、及びフッ化マグネシウム(MgF2)から選択された少なくとも一種を含むことを特徴とする請求項7に記載のグラフェン基板の製造方法。 - 前記耐熱材料は、凹凸形状を有することを特徴とする請求項1〜8のいずれか一項に記載のグラフェン基板の製造方法。
- 前記耐熱材料は、前記凹凸形状の凹部と凸部の両方にグラフェンを析出させることを特徴とする請求項9に記載のグラフェン基板の製造方法。
- 前記炭素含有層は、炭素同素体、低分子有機化合物、人工高分子有機化合物、天然高分子有機化合物及び炭素を含む無機化合物からなる群から選ばれる少なくとも1種を有することを特徴とする請求項1〜10のいずれか一項に記載のグラフェン基板の製造方法。
- 前記炭素同素体は、無定形炭素、ガラス状炭素、結晶性グラファイト、単層カーボンナノチューブ、多層カーボンナノチューブ、フラーレン、ダイヤモンド、ナノダイヤモンドの内の少なくとも一種を含み、
前記低分子有機化合物は、メタロセン、ナフタレン、アントラセン、及びペンタセンの内の少なくとも一種を含み、
前記人工高分子有機化合物は、テフロン、PMMA(ポリメタクリル酸メチル)、ポリエチレンの内の少なくとも一種を含み、
前記天然高分子有機化合物は、タンパク質、核酸、脂質、及び多糖類の内の少なくとも一種を含み、
前記炭素を含む無機化合物は、炭化ケイ素(SiC)、炭化ホウ素(B4C)、炭化アルミニウム(Al4C3)、炭化チタン(TiC)、炭化ジルコニウム(ZrC)、炭化ハフニウム(HfC)、炭化バナジウム(VC)、炭化ニオブ(NbC)、炭化タンタル(TaC)、炭化クロム(CrC)、炭化モリブデン(MoC)、炭化タングステン(WC)、窒化炭素(C3N4)、及び窒化炭素ホウ素(BCN)の内の少なくとも一種を含むことを特徴とする請求項11に記載のグラフェン基板の製造方法。 - 前記(a)工程は、加熱する温度が600℃以上であることを特徴とする請求項1〜12のいずれか一項に記載のグラフェン基板の製造方法。
- 前記(a)工程は、加熱する温度が600℃以上であり、
前記(b)工程は、400℃まで冷却させる単位時間当たりの降下温度が0〜100℃/分の範囲であることを特徴とする請求項1〜12のいずれか一項に記載のグラフェン基板の製造方法。 - 前記(a)工程は、ホルダの中に前記炭素含有層を配置し、前記基板の上にスペーサを配置し、前記スペーサ内に前記金属層を配置し、その上に前記耐熱材料層を配置してから、前記金属層を加熱することで前記金属層中に前記炭素含有層中の炭素を溶解させることを特徴とする請求項1〜14のいずれか一項に記載のグラフェン基板の製造方法。
- 前記(b)工程は、前記凹凸形状の凸部にのみグラフェンを析出させることを含むことを特徴とする請求項1〜15に記載のグラフェン基板の製造方法。
- 前記(b)工程は、前記凹凸形状の凸部を架橋するようにグラフェンを析出させることを含むことを特徴とする請求項1〜15に記載のグラフェン基板の製造方法。
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2017174802A (ja) * | 2016-03-17 | 2017-09-28 | 国立大学法人 名古屋工業大学 | 結晶性炭素ナノ材料を含む導電性材料の製造方法、導電性材料、透明電極、電極、配線、電子装置および半導体装置 |
Families Citing this family (46)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2937343B1 (fr) * | 2008-10-17 | 2011-09-02 | Ecole Polytech | Procede de croissance controlee de film de graphene |
US8652946B2 (en) | 2012-04-16 | 2014-02-18 | Uchicago Argonne, Llc. | Graphene layer formation on a carbon based substrate |
KR101878739B1 (ko) * | 2011-10-24 | 2018-07-17 | 삼성전자주식회사 | 그래핀 전사부재, 그래핀 전사방법 및 이를 이용한 그래핀 소자 제조방법 |
JP5927522B2 (ja) * | 2012-03-16 | 2016-06-01 | 日本電気株式会社 | 炭素材料構造材の製造方法および炭素材料構造材 |
US9360905B2 (en) * | 2012-04-09 | 2016-06-07 | Nanotek Instruments, Inc. | Thermal management system containing an integrated graphene film for electronic devices |
US9875894B2 (en) * | 2012-04-16 | 2018-01-23 | Uchicago Argonne, Llc | Graphene layer formation at low substrate temperature on a metal and carbon based substrate |
US9899120B2 (en) | 2012-11-02 | 2018-02-20 | Nanotek Instruments, Inc. | Graphene oxide-coated graphitic foil and processes for producing same |
KR102059129B1 (ko) * | 2012-11-21 | 2019-12-24 | 삼성전자주식회사 | 그래핀의 제조 방법 및 이를 포함하는 그래핀 적용 소자 |
US9533889B2 (en) | 2012-11-26 | 2017-01-03 | Nanotek Instruments, Inc. | Unitary graphene layer or graphene single crystal |
US10566482B2 (en) | 2013-01-31 | 2020-02-18 | Global Graphene Group, Inc. | Inorganic coating-protected unitary graphene material for concentrated photovoltaic applications |
US10087073B2 (en) | 2013-02-14 | 2018-10-02 | Nanotek Instruments, Inc. | Nano graphene platelet-reinforced composite heat sinks and process for producing same |
KR20140114199A (ko) | 2013-03-18 | 2014-09-26 | 삼성전자주식회사 | 이종 적층 구조체 및 그 제조방법, 및 상기 이종 적층 구조체를 구비하는 전기소자 |
EP4293707A3 (en) * | 2013-05-09 | 2024-03-27 | GlobalWafers Co., Ltd. | Direct and sequential formation of monolayers of boron nitride and graphene on substrates |
US9344127B2 (en) * | 2013-11-22 | 2016-05-17 | The Trustees Of Columbia University In The City Of New York | Graphene resonator based mixer-first receiver on CMOS for digitally controlled and widely tunable RF interface |
CN104710445B (zh) * | 2013-12-15 | 2017-01-25 | 中国科学院大连化学物理研究所 | 一种硼、氮共掺杂石墨烯及其制备和应用 |
JP6201801B2 (ja) * | 2014-02-14 | 2017-09-27 | 株式会社デンソー | グラファイト薄膜の製造方法 |
JP6118288B2 (ja) * | 2014-03-31 | 2017-04-19 | クアーズテック株式会社 | 窒化物半導体中の炭素濃度測定方法および窒化物半導体の製造方法 |
JP6457766B2 (ja) * | 2014-09-17 | 2019-01-23 | 国立大学法人岩手大学 | 絶縁材料のラマン散乱スペクトルを用いた2次元薄膜原子構造の積層数決定装置及び積層数決定方法 |
CN104656996B (zh) * | 2015-03-03 | 2017-08-29 | 京东方科技集团股份有限公司 | 触控单元、触控基板及其制作方法和柔性触控显示装置 |
JP6544624B2 (ja) * | 2015-05-19 | 2019-07-17 | 国立大学法人九州工業大学 | グラフェン層積層ダイヤモンド基板の製造方法 |
JP6403638B2 (ja) * | 2015-06-15 | 2018-10-10 | 信越化学工業株式会社 | 非水電解質二次電池用負極活物質、非水電解質二次電池用負極、及び非水電解質二次電池、並びに非水電解質二次電池用負極材の製造方法 |
JP6478862B2 (ja) | 2015-07-29 | 2019-03-06 | 株式会社東芝 | 半導体装置 |
JP6481582B2 (ja) * | 2015-10-13 | 2019-03-13 | 住友電気工業株式会社 | 炭化珪素エピタキシャル基板および炭化珪素半導体装置の製造方法 |
JP6555069B2 (ja) * | 2015-10-15 | 2019-08-07 | 富士通株式会社 | 半導体デバイス及びその製造方法 |
US10083831B2 (en) | 2016-03-10 | 2018-09-25 | Sumitomo Electric Industries, Ltd. | Substrate and electronic device |
EP3436402A4 (en) * | 2016-03-30 | 2020-03-18 | Massachusetts Institute of Technology | GROWTH OF CARBON-BASED NANOSTRUCTURES USING ACTIVE GROWTH MATERIALS INCLUDING ALKALINE METALS AND / OR ALKALINE EARTH METALS |
US10529807B2 (en) * | 2016-04-19 | 2020-01-07 | Sumitomo Electric Industries, Ltd. | Stacked body and electronic device |
US10580869B2 (en) * | 2016-04-19 | 2020-03-03 | Sumitomo Electric Industries, Ltd. | Stacked body including graphene film and electronic device including graphene film |
JP2019112237A (ja) * | 2016-04-28 | 2019-07-11 | 味の素株式会社 | グラフェンの製造方法 |
WO2017201632A1 (es) * | 2016-05-26 | 2017-11-30 | Reyes Salinas Mario Celedonio | Metodo para producir grafeno a escala industrial a partir de negro de humo y su utilizacion como materia prima para la obtencion de nanotubos con propiedad de autoensamblaje |
JP6723603B2 (ja) * | 2016-08-29 | 2020-07-15 | 国立大学法人 筑波大学 | 多層グラフェンの製造方法及び多層グラフェン積層体 |
WO2018148212A1 (en) * | 2017-02-07 | 2018-08-16 | Colorado State University Research Foundation | Thermoplastic carbon composite electrodes |
CN106809825B (zh) * | 2017-03-30 | 2018-09-25 | 胡明理 | 一种石墨烯及其制备方法 |
US20180308696A1 (en) * | 2017-04-25 | 2018-10-25 | Texas Instruments Incorporated | Low contact resistance graphene device integration |
US11578404B2 (en) | 2017-06-13 | 2023-02-14 | Massachusetts Institute Of Technology | Synthesis of carbon-based nanostructures using eutectic compositions |
EP3447026A1 (en) * | 2017-08-24 | 2019-02-27 | RD Graphene Limited | 3d graphene |
US10857774B2 (en) * | 2017-11-21 | 2020-12-08 | Vaon, Llc | Transferring graphitic thin films with a liquid gallium probe |
EP3761505A4 (en) * | 2018-03-01 | 2021-12-01 | Kaneka Corporation | MEMS VIBRATOR AND MEMS OSCILLATOR |
US11117801B2 (en) | 2018-04-24 | 2021-09-14 | Imam Abdulrahman Bin Faisal University | Transparent electrode with a composite layer of a graphene layer and nanoparticles |
US10373825B1 (en) * | 2018-05-29 | 2019-08-06 | Industry-University Cooperation Foundation Hanyang University | Method for manufacturing gallium nitride substrate using core-shell nanoparticle |
CN110040721A (zh) * | 2019-04-16 | 2019-07-23 | 中国科学院物理研究所 | 一种解理制备石墨烯的方法 |
TWI703921B (zh) * | 2019-10-01 | 2020-09-01 | 十銓科技股份有限公司 | 散熱裝置 |
KR102482649B1 (ko) * | 2020-07-09 | 2022-12-29 | (주)에프에스티 | 극자외선 리소그라피용 펠리클의 제조방법 |
KR102582289B1 (ko) * | 2020-10-26 | 2023-09-26 | 한국화학연구원 | 유연전극용 복합소재 및 이의 제조방법 |
KR20230133269A (ko) * | 2021-01-26 | 2023-09-19 | 린텍 가부시키가이샤 | 열전도성 점착제 조성물, 점착시트 및 그 제조방법 |
CN113078053B (zh) * | 2021-03-25 | 2024-02-27 | 中国科学院上海微系统与信息技术研究所 | 一种顶栅结构的制备方法及半导体结构 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009107921A (ja) * | 2007-10-29 | 2009-05-21 | Samsung Electronics Co Ltd | グラフェンシート及びその製造方法 |
JP2009200177A (ja) * | 2008-02-20 | 2009-09-03 | Denso Corp | グラフェン基板及びその製造方法 |
WO2010110153A1 (ja) * | 2009-03-27 | 2010-09-30 | 独立行政法人科学技術振興機構 | グラフェン膜の製造方法、電子素子の製造方法および基板へのグラフェン膜の転写方法 |
WO2010122928A1 (ja) * | 2009-04-25 | 2010-10-28 | 国立大学法人九州工業大学 | グラフェン膜の作製方法 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB0622150D0 (en) * | 2006-11-06 | 2006-12-20 | Kontrakt Technology Ltd | Anisotropic semiconductor film and method of production thereof |
KR100966486B1 (ko) * | 2007-08-28 | 2010-06-29 | (주)엘지하우시스 | 포름알데히드 흡착성능을 갖는 타일 및 이의 제조방법 |
JP5578639B2 (ja) | 2008-08-04 | 2014-08-27 | 住友電気工業株式会社 | グラファイト膜製造方法 |
US8309438B2 (en) * | 2009-03-03 | 2012-11-13 | Board Of Regents, The University Of Texas System | Synthesizing graphene from metal-carbon solutions using ion implantation |
-
2011
- 2011-11-25 US US13/995,809 patent/US8980217B2/en active Active
- 2011-11-25 WO PCT/JP2011/077879 patent/WO2012086387A1/ja active Application Filing
- 2011-11-25 JP JP2012549708A patent/JP5871213B2/ja active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009107921A (ja) * | 2007-10-29 | 2009-05-21 | Samsung Electronics Co Ltd | グラフェンシート及びその製造方法 |
JP2009200177A (ja) * | 2008-02-20 | 2009-09-03 | Denso Corp | グラフェン基板及びその製造方法 |
WO2010110153A1 (ja) * | 2009-03-27 | 2010-09-30 | 独立行政法人科学技術振興機構 | グラフェン膜の製造方法、電子素子の製造方法および基板へのグラフェン膜の転写方法 |
WO2010122928A1 (ja) * | 2009-04-25 | 2010-10-28 | 国立大学法人九州工業大学 | グラフェン膜の作製方法 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2017174802A (ja) * | 2016-03-17 | 2017-09-28 | 国立大学法人 名古屋工業大学 | 結晶性炭素ナノ材料を含む導電性材料の製造方法、導電性材料、透明電極、電極、配線、電子装置および半導体装置 |
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