JP6839355B2 - グラフェンナノリボン、グラフェンナノリボンの製造方法及び半導体装置 - Google Patents
グラフェンナノリボン、グラフェンナノリボンの製造方法及び半導体装置 Download PDFInfo
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- JP6839355B2 JP6839355B2 JP2017021020A JP2017021020A JP6839355B2 JP 6839355 B2 JP6839355 B2 JP 6839355B2 JP 2017021020 A JP2017021020 A JP 2017021020A JP 2017021020 A JP2017021020 A JP 2017021020A JP 6839355 B2 JP6839355 B2 JP 6839355B2
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- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
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Description
また、一観点によれば、上記のようなグラフェンナノリボンの製造方法、及び上記のようなグラフェンナノリボンを備える半導体装置が提供される。
第1の実施の形態に係るグラフェンナノリボンは、式(1)に示すような構造を有する。
まず、第2の実施の形態について説明する。
図2には、上記図1(C)に示したグラフェンナノリボン30Aのキラル型エッジ34のほか、比較のため、その他のキラル型エッジ32,33,35,36、アームチェア型エッジ31及びジグザグ型エッジ37を併せて図示している。
図3(A)には、(2,1)−DCI−GNRの構造を示し、図3(B)には、そのバンド構造を密度汎関数法で見積もった結果を示している。比較のため、図4(A)には、炭素原子7個分相当の幅を持ったAGNR(7−AGNR)の構造を示し、図4(B)には、そのバンド構造を密度汎関数法で見積もった結果を示している。
ジカルボイミド構造10bによる前駆体分子10Aの反応中間体の安定化により、反応中間体の基板上での拡散長の増大、それによるグラフェンナノリボン30Aのリボン長の増大が図られる。
例えば、アームチェア型エッジのグラフェンナノリボンは、比較的大きなバンドギャップを実現し易く、例えば光電変換デバイスに適用する際には優れた材料となる。その一方で、電界効果トランジスタ(Field Effect Transistor:FET)に適用する際にはバンドギャップが大き過ぎ、良好な電極接合を形成することが難しい。グラフェンナノリボンには、幅が大きくなるとバンドキャップが小さくなる傾向があるため、原理的には、ボトムアップ合成で用いる前駆体分子(そのアセン構造部)を大きくし、幅の大きいアームチェア型エッジのグラフェンナノリボンを形成すればよい。しかし、大きな前駆体分子は、真空蒸着に高温を要し、また元々反応性が高くなるように設計されていることもあり、蒸着の過程で分解してしまうことが多い。そのため、適度に大きな前駆体分子を用いて、幅が大きくバンドギャップが小さいアームチェア型エッジのグラフェンナノリボンを得ることは、必ずしも容易でない。
図6はグラフェンナノリボンの別例について説明する図である。図6(A)には、グラフェンナノリボンの前駆体分子の別例を示している。図6(B)には、前駆体分子の重合体(ポリマー鎖)の別例を示している。図6(C)には、グラフェンナノリボンの別例を示している。
また、カルボン酸無水物構造10cに水素結合のアクセプタである酸素原子Oが含まれることで、水素結合による自己組織化によってグラフェンナノリボン30B群の配向性の向上が図られる。
次に、第4の実施の形態について説明する。
図7に示す半導体装置50は、ボトムゲート型FETの一例である。半導体装置50は、ゲート電極51、ゲート絶縁膜52、グラフェンナノリボン53、電極54a及び電極54bを有する。
図7に示すような半導体装置50は、グラフェンナノリボン53の、分子吸着時に抵抗が変化する性質を利用し、FET型ガスセンサーとして用いることもできる。FET型ガスセンサーとして用いられる半導体装置50では、グラフェンナノリボン53にガスが吸着した時の、電極54aと電極54bとの間に流れる電流と、ゲート電極51の電圧との関係の変化が、測定される。グラフェンナノリボン53を用いることで、高感度のFET型ガスセンサーが実現される。
図8に示す半導体装置60は、トップゲート型FETの一例である。半導体装置60は、支持基板61、グラフェンナノリボン62、電極63a、電極63b、ゲート絶縁膜64及びゲート電極65を有する。
図9は半導体装置の第3の例を示す図である。図9には、半導体装置の要部断面を模式的に図示している。
支持基板71には、サファイヤ等の絶縁性の各種基板、少なくとも表層に無機系又は有機系の絶縁材料が設けられた各種基板が用いられる。このような支持基板71の上に、グラフェンナノリボン72が設けられる。
図10に示す半導体装置80は、積層型太陽電池の一例である。半導体装置80は、下部電極81、グラフェンナノリボン82、キャリア輸送層83及び上部電極84を有する。
上記第4の実施の形態で述べたような半導体装置50,60,70,80等は、各種電子デバイス(電子装置又は電子機器)に搭載することができる。例えば、コンピュータ(パーソナルコンピュータ、スーパーコンピュータ、サーバ等)、スマートフォン、携帯電話、タブレット端末、センサ、カメラ、オーディオ機器、測定装置、検査装置、製造装置といった、各種電子デバイスに用いることができる。
図11に示すように、例えば上記図7に示したような半導体装置50が、各種電子デバイス90に搭載(内蔵)される。上記のように半導体装置50では、電子求引性基が結合したキラル型エッジを有するグラフェンナノリボン53が用いられる。そのキラル型エッジ及びそれに結合する電子求引性基により、半導体装置50のグラフェンナノリボン53として要求されるバンドギャップ、仕事関数、リボン長、配向性及び接触抵抗等の特性を満足することができる。これにより、グラフェンナノリボン53を用いた、高性能の半導体装置50が実現され、そのような半導体装置50を搭載した、高性能の電子デバイス90が実現される。
10a ナフタレン構造部
10b ジカルボイミド構造
10c カルボン酸無水物構造
10d ダイオキシン構造
20A,20B 重合体
30A,30B,53,62,72,82 グラフェンナノリボン
31 アームチェア型エッジ
32,33,34,35,36 キラル型エッジ
37 ジグザグ型エッジ
40A アントラセン
40B ジカルボイミド構造が結合したアントラセン
40C フッ素原子が結合したアントラセン
40D ダイオキシン構造が結合したアントラセン
50,60,70,80 半導体装置
51,65 ゲート電極
52,64 ゲート絶縁膜
54a,54b,63a,63b,73,74 電極
61,71 支持基板
81 下部電極
83 キャリア輸送層
84 上部電極
90 電子デバイス
Claims (9)
- 電子求引性基が結合したキラル型エッジを有し、前記電子求引性基が、前記キラル型エッジに結合した酸無水物構造を含むことを特徴とするグラフェンナノリボン。
- 前記電子求引性基は、前記キラル型エッジに、複数の炭素原子を介して周期的に結合することを特徴とする請求項1に記載のグラフェンナノリボン。
- アームチェア型エッジの角度を0°とした時の前記キラル型エッジの角度が10.8°であることを特徴とする請求項1又は2に記載のグラフェンナノリボン。
- 第1方向に並ぶベンゼン環群をそれぞれ含むアセン構造部群が、前記第1方向と直交する第2方向に重合し、末端の前記アセン構造部の、前記第1方向端にハロゲン原子が結合し、前記第2方向端に電子求引性基が結合した分子構造を有する前駆体分子群を、脱ハロゲン化水素反応及び脱水素反応により重合する工程を含み、前記電子求引性基が、前記第2方向端に結合した酸無水物構造を含むことを特徴とするグラフェンナノリボンの製造方法。
- 電子求引性基が結合したキラル型エッジを有し、前記電子求引性基が、前記キラル型エッジに結合した酸無水物構造を含むグラフェンナノリボンを備えることを特徴とする半導体装置。
- 下記一般式(1)で表される構造を有し、電子求引性基が結合したキラル型エッジを有することを特徴とするグラフェンナノリボン。
- アームチェア型エッジの角度を0°とした時の前記キラル型エッジの角度が10.8°であることを特徴とする請求項6に記載のグラフェンナノリボン。
- 第1方向に並ぶベンゼン環群をそれぞれ含むアセン構造部群が、前記第1方向と直交する第2方向に重合し、末端の前記アセン構造部の、前記第1方向端にハロゲン原子が結合し、前記第2方向端に電子求引性基が結合した分子構造を有する前駆体分子群を、脱ハロゲン化水素反応及び脱水素反応により重合する工程を含み、前記前駆体分子群はそれぞれ、下記一般式(2)で表される構造を有することを特徴とするグラフェンナノリボンの製造方法。
- 下記一般式(3)で表される構造を有し、電子求引性基が結合したキラル型エッジを有するグラフェンナノリボンを備えることを特徴とする半導体装置。
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