JP5974588B2 - 電界効果トランジスタ、表示用パネル及び重合体 - Google Patents
電界効果トランジスタ、表示用パネル及び重合体 Download PDFInfo
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- JP5974588B2 JP5974588B2 JP2012079128A JP2012079128A JP5974588B2 JP 5974588 B2 JP5974588 B2 JP 5974588B2 JP 2012079128 A JP2012079128 A JP 2012079128A JP 2012079128 A JP2012079128 A JP 2012079128A JP 5974588 B2 JP5974588 B2 JP 5974588B2
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Description
このような保護層としてポリスチレンやポリメチルメタクリレートなどの高分子材料を半導体層に接して形成することが知られている(特許文献1)。また、金属酸化物を保護層に用いることなども知られている(特許文献2)。
さらには、保護層についても所望のパターン形成が行えることが好ましく、その場合はエネルギー線、特に紫外線などの光による硬化、架橋が行える材料が望ましい。
式(x2)において、Rx3は置換基を有していても良い炭素数1から10の2価の炭化水素基を表す。)
図1(A),(B)に示されるようなボトムゲート型の電界効果トランジスタにおいて、保護層7は、半導体層1が外部環境と直接触れることがないように、また、半導体層1の汚染や、特性変動を抑制するため、ゲート絶縁層2と反対側に形成される。
本発明の電界効果トランジスタにおいて、支持基板6としては、電界効果トランジスタにおいて用いられている公知の基板を用いることができる。その材料としては、電界効果トランジスタおよびその上に作製される表示素子、表示パネル等を支持できるものであればよく、公知のガラス、酸化珪素、および珪素等の金属等の無機材料、並びに各種有機ポリマー等の有機材料等が挙げられ、これらは、例えば、無機材料の基板の表面に有機ポリマー等をコーティングして表面に絶縁層を形成した基板等の無機材料と有機材料との併用の場合も含めて2種以上を組み合わせて用いることもできる。尚、有機ポリマーとしては、例えば、ポリエステル、ポリカーボネート、ポリイミド、ポリアミド、ポリエーテルスルフォン、エポキシ樹脂、ポリベンゾオキサゾール、ポリベンゾチアゾール、ポリパラバン酸、ポリシルセスキオキサン、ポリビニルフェノール、およびポリオレフィン等が挙げられ、これらを成形したフィルム状もしくはシート状のものを用いることができる。また、これらの有機ポリマーは、必要に応じて、充填材、添加剤等を含んでいてもよい。
本発明の電界効果トランジスタにおいて、ゲート電極5としては、従来の電界効果トランジスタにおいて用いられている導電性材料を用いることができる。ゲート電極5の導電性材料としては、例えば、白金、金、アルミニウム、クロム、ニッケル、銅、チタン、マグネシウム、カルシウム、バリウム、ナトリウム等の金属の他、InO2、SnO2、ITO等の導電性金属酸化物、ポリアニリン、ポリピロール、ポリチオフェン、ポリアセチレン等の導電性高分子、および、それらに塩酸、硫酸、スルホン酸等の酸、PF6、AsF5、FeCl3等のルイス酸、沃素等のハロゲン原子、ナトリウム、カリウム等の金属原子等のドーパントを添加したもの、並びに、カーボンブラック、グラファイト粉、金属微粒子等を分散した導電性の複合材料等が挙げられる。また、支持基板とゲート電極を兼ねて、導電性n型シリコンウェハを用いてもよい。
本発明の電界効果トランジスタにおいて、ゲート絶縁層2の構成材料としては、従来の電界効果トランジスタにおいて用いられている材料を用いることができる。例えば、ポリメチルメタクリレート、ポリスチレン、ポリビニルフェノール、ポリイミド、ポリカーボネート、ポリエステル、ポリビニルアルコール、ポリ酢酸ビニル、ポリウレタン、ポリスルホン、エポキシ樹脂、フェノール樹脂等の有機ポリマー等の有機材料、および、二酸化珪素、酸化アルミニウム、酸化チタン等の酸化物、窒化珪素等の窒化物、SrTiO3、BaTiO3等の強誘電性酸化物等の無機材料が挙げられる。また、有機材料と無機材料との混合物も用いられ、例えば、上記酸化物や窒化物、強誘電性酸化物等の粒子を分散させた上記有機ポリマー等が挙げられる。
本発明の電界効果トランジスタにおいて、半導体層1を形成する材料としては、公知の半導体材料を用いることができ、特に制限はない。例えば、シリコン類や酸化亜鉛、酸化スズ、酸化ガリウム、酸化テルル、酸化ゲルマニウム、酸化タングステン、酸化モリブデン、ITO、InGaOZnO4などのIGZO類、IHfZO、LaCuOS、LaCuOSe、SrCu2O2、酸化ニッケルに代表される酸化物半導体などの無機材料、および有機物半導体材料を用いることができる。
電界効果トランジスタにおいて、ソース電極3は、配線を通じて外部から電流が流入する電極であり、ドレイン電極4は、配線を通じて外部に電流を送り出す電極であり、前述した半導体層1に接して設けられている。
本発明の電界効果トランジスタにおいて、保護層は、下記式(a)および(b)で表される繰り返し単位を含み、好ましくは更に、下記式(c1)および(c2)で表される繰り返し単位のうちの少なくとも一つの繰り返し単位を含む本発明の重合体により形成される。
また、「(メタ)アクリル」は「アクリル」と「メタアクリル」の双方を表し、「(メタ)アクリロ」等についても同様である。
式(x2)において、Rx3は置換基を有していても良い炭素数1から10の2価の炭化水素基を表す。)
また、式(x1)及び(x2)は、どちらの構造を選択しても良いが、例えば、式中の二重結合周辺の立体障害を低減し反応性を向上させたい場合は、式(x2)の構造を導入することが効果的である。
これらの有機基の中では、光照射時、特に紫外線照射時の反応性が高いことから、フェニル基、ナフチル基などの芳香族炭化水素基が好ましい。
この中でメチレン基、エチレン基、プロピレン基、イソプロピレン基、ブチレン基、イソブチレン基、フェニレン基、ナフチレン基などが好ましい。
また、繰り返し単位(a)と繰り返し単位(b)の相対比は、エネルギー線の照射で架橋反応を円滑に進行させることができ、十分に硬化させることができる点では、繰り返し単位(a)が多いことが好ましいが、また、一方で、トランジスタ特性の経時での変動抑制の効果や保護層と隣接する層との接着力低減の効果を得ることができるようになる点では、繰り返し単位(b)が多いことが好ましい。具体的には、繰り返し単位(a):繰り返し単位(b)が1モル%:99モル%〜99モル%:1モル%であることが好ましく、5モル%:95モル%〜95モル%:5モル%であることが更に好ましい。なお、本発明の重合体の1分子中には、繰り返し単位(a)が1種のみが含まれていてもよく、複数種が含まれていてもよい。また、繰り返し単位(b)についても、その1種のみが含まれていてもよく、複数種が含まれていてもよい。
繰り返し単位(c1)と繰り返し単位(c2)は、重合体の溶媒溶解性や極性等に応じて適宜選択すればよい。重合体の耐熱性を向上させると同時に極性を上げたい場合は、繰り返し単位(c2)の構造を導入することが効果的であり、一方で耐熱性を向上させる一方で極性を低めにしたい場合などは繰り返し単位(c1)の構造を導入することが好ましい。
本発明の重合体が含有し得るその他の繰り返し単位としては、ビニル系モノマー、(メタ)アクリル酸エステル系モノマーなどに由来する構造単位が挙げられる。
この方法は、繰り返し単位(a)および繰り返し単位(b)を与える単量体として、例えば下記式(xx1),(xx2),(yy1),(yy2)で示すような単量体を混合し、通常のラジカル重合法、カチオン重合法、アニオン重合法などで重合させて重合体を得る方法である。
重合体主鎖を合成した後に、繰り返し単位(a)、(b)中のRa2,Rb2に相当する構造を主鎖に導入する手法により、本発明の重合体を製造することもできる。
そのような重合体としては、ポリ(メタ)アクリル酸メチル、ポリ(メタ)アクリル酸エチル、ポリ(メタ)アクリル酸ブチルなどの(メタ)アクリル酸エステルの重合体、およびそれらの共重合体、ポリアクリロニトリル、アクリロニトリルスチレン共重合体、ポリスチレン、ポリカーボネート類、脂肪族ポリエステル類、ポリアミド類、ポリシロキサン類などが挙げられる。これらの他の重合体は、1種を用いてもよく、2種以上を用いてもよいが、本発明の重合体による効果を十分に得る上で、本発明の重合体は、本発明の重合体と他の重合体との合計に対して10重量%以上の範囲で用いることが好ましい。また、上限は通常100重量%である。
以下に、これらの好ましい具体例を挙げる。
(3) ベンズアンスロン誘導体としては、具体的には、3−ニトロベンズアンスロンなどが挙げられる。
(4) ベンゾフェノン誘導体としては、具体的には、ベンゾフェノン、ミヒラーケトン、2−メチルベンゾフェノン、3−メチルベンゾフェノン、4−メチルベンゾフェノン、2−クロロベンゾフェノン、4−ブロモベンゾフェノン、2−カルボキシベンゾフェノンなどが挙げられる。
(7) 安息香酸エステル誘導体としては、具体的には、p−ジメチルアミノ安息香酸エチル、p−ジエチルアミノ安息香酸エチルなどが挙げられる。
(8) アクリジン誘導体としては、具体的には、9−フェニルアクリジン、9−(p−メトキシフェニル)アクリジンなどが挙げられる。
(9) フェナジン誘導体としては、具体的には、9,10−ジメチルベンズフェナジンなどが挙げられる。
このような本発明の電界効果トランジスタは、各種の表示用パネルやセンサー等に有用であり、具体的には液晶ディスプレイ、電子ペーパー、有機ELディスプレイのバックプレーン、センサーにおける電圧変動感知部などに用いられる。
<移動度、しきい値電圧>
電界効果トランジスタの移動度は、測定対象のトランジスタ(電子デバイス)の出力特性を「Agilent4155c半導体パラメータアナライザー」を用いて測定することによって求めた。測定時の雰囲気は、乾燥窒素とし、ドレイン電圧は−30V、ゲート電圧は、+10V〜−30Vとした。そして、得られた伝達特性から、以下の式を用いて、√(Id sat)とVgの直線の傾きから移動度を求め、その直線のId sat切片から、しきい値電圧Vthを求めた。
なお、チャンネル長とは、ソース電極とドレイン電極との間の最短距離を言う。
On/Off比は、Vg=−30VおよびVg=+10Vにおけるドレイン電流の比を求めた。
(1)重合体溶液の調製
冷却器を装備したフラスコ内に2.0g(15.4ミリモル)のメタクリル酸ヒドロキシエチル、2.75g(18.1ミリモル)のアセナフチレン、0.3g(17.8ミリモル)のアクリル酸2,2,2−トリフルオロエチル、および0.025gのアゾイソブチロニトリルを仕込み、7.0gのテトラヒドロフランに溶解した後系内を窒素置換した。
その後、70℃に加熱しながら、12時間攪拌を継続して、以下構造式の重合体の溶液を得た。
冷却器を装着したフラスコ内に3.66g(18.5ミリモル)のナフチルプロペン酸とトルエンを仕込み、ジメチルホルムアミドを1滴加えた。系内を窒素置換した後、40℃に加熱しながら2.64g(22.2ミリモル)の塩化チオニルを5分かけて滴下し、そのまま4時間攪拌を続けた。その後、余分の塩化チオニルおよびトルエンを減圧下に留去し、留去残渣に新たに10gの脱水したテトラヒドロフランを加え、酸クロリド溶液とした。
上記(1)で得られた重合体溶液に5gのピリジンを加え、よく攪拌した。さらに、その中に上記(2)で得られた酸クロリド溶液を攪拌しながら少しずつ加えた。40℃で2時間攪拌を続けた後、反応組成物を吸引濾過し発生した塩を取り除いた。濾液を500mlのメタノール中に攪拌しながら徐々に投入し、以下の構造式の重合体を析出させた。析出した固形物を吸引濾過で濾別、真空乾燥して重合体αを得た。得られた重合体αの分子量はGPCにおけるポリスチレン換算の数平均分子量で29000であった。
また、重合体αの全繰り返し単位中の繰り返し単位(a)の割合は30モル%、繰り返し単位(b)の割合は35モル%、繰り返し単位(c1)の割合は35モル%であった。
図1(A)に示す電界効果トランジスタを以下の手順で作製した。
支持基板6とゲート電極5を兼ねた導電性n型シリコンウェハーの表面に、ゲート絶縁層2として膜厚300nmの熱酸化シリコン膜を形成した。次に、この熱酸化シリコン膜上にポリメチルグルタルイミド(PMGI)のレジスト(化薬マイクロケム社製「SF−9」)を0.5μmの厚さにスピンコートし、180℃で5分間加熱した。このレジスト膜上に、ネガ型のフォトレジスト(日本ゼオン社製「ZPN−1150」)を厚さ4μmにスピンコートし、80℃で180秒間加熱した後、露光し、110℃で120秒加熱し、その後、有機アルカリ現像液(ナガセケムテックス社製「NPD−18」)によって現像することにより、ソース電極およびドレイン電極の形状にレジストのパターンを形成した。得られたレジストのパターン上に、Moを厚さ100nmとなるようにスパッタした。その後、リフトオフ法により上記2層レジストパターンごと、不要なMoを除去することによって、ソース電極3およびドレイン電極4を、チャネル長L=10μm、チャンネル幅W=500μmで形成した。
また、この素子を、室温21℃、相対湿度約25%の室内に24時間放置した後は、移動度μsat=1.0cm2/Vs、しきい値電圧Vth=5.2Vであった。
この素子の作製直後の伝達特性と、室温21℃、相対湿度約25%の室内に24時間放置後の伝達特性のグラフを図2(A)に示した。
重合体αの代わりに、ポリスチレン(アルドリッチ社、分子量35000)の10重量%トルエン溶液をスピンコートした以外は実施例2と同様にして保護層付き電界効果トランジスタ素子を作製した。
得られた作製直後の素子特性は、移動度移動度μsat=0.45cm2/Vs、しきい値電圧Vth=−6.5Vであった。
また、この素子を室温21℃、相対湿度約25%の室内に24時間放置した後は、移動度μsat=0.5cm2/Vs、しきい値電圧Vth=+2.5Vであった。
この素子の作製直後の伝達特性と、室温21℃、相対湿度約25%の室内に24時間放置後の伝達特性を図2(B)に示した。
2 ゲート絶縁層
3 ソース電極
4 ドレイン電極
5 ゲート電極
6 支持基板
7 保護層
Claims (4)
- 基板に配設されたゲート電極と、前記ゲート電極に接して形成されたゲート絶縁層と、ソース電極およびドレイン電極と、前記ソース電極と前記ドレイン電極に接して形成された半導体層と、該半導体層に対して、前記ゲート絶縁層とは反対側に形成された保護層とを備え、前記保護層は下記式(a)および(b)で表される繰り返し単位を含む重合体を含むことを特徴とする電界効果トランジスタ。
式(x2)において、Rx3は置換基を有していても良い炭素数1から10の2価の炭化水素基を表す。)
- 前記半導体層が前駆体変換型の有機半導体からなることを特徴とする請求項1又は2に記載の電界効果トランジスタ。
- 請求項1ないし3のいずれか1項に記載の電界効果トランジスタを用いた表示用パネル。
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