JP6954310B2 - n型半導体素子、n型半導体素子の製造方法、無線通信装置および商品タグ - Google Patents
n型半導体素子、n型半導体素子の製造方法、無線通信装置および商品タグ Download PDFInfo
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- JP6954310B2 JP6954310B2 JP2018556946A JP2018556946A JP6954310B2 JP 6954310 B2 JP6954310 B2 JP 6954310B2 JP 2018556946 A JP2018556946 A JP 2018556946A JP 2018556946 A JP2018556946 A JP 2018556946A JP 6954310 B2 JP6954310 B2 JP 6954310B2
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- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002074 nanoribbon Substances 0.000 description 1
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- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- KPADFPAILITQBG-UHFFFAOYSA-N non-4-ene Chemical compound CCCCC=CCCC KPADFPAILITQBG-UHFFFAOYSA-N 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- SLYCYWCVSGPDFR-UHFFFAOYSA-N octadecyltrimethoxysilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OC)(OC)OC SLYCYWCVSGPDFR-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 125000005824 oxyalkoxy group Chemical group 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
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- 239000005011 phenolic resin Substances 0.000 description 1
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
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- 150000004992 toluidines Chemical class 0.000 description 1
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- LLGVQQLZYJJDBZ-UHFFFAOYSA-N trimethoxy(2,2,2-trifluoroethyl)silane Chemical compound CO[Si](OC)(OC)CC(F)(F)F LLGVQQLZYJJDBZ-UHFFFAOYSA-N 0.000 description 1
- ZSOVVFMGSCDMIF-UHFFFAOYSA-N trimethoxy(naphthalen-1-yl)silane Chemical compound C1=CC=C2C([Si](OC)(OC)OC)=CC=CC2=C1 ZSOVVFMGSCDMIF-UHFFFAOYSA-N 0.000 description 1
- XQEGZYAXBCFSBS-UHFFFAOYSA-N trimethoxy-(4-methylphenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=C(C)C=C1 XQEGZYAXBCFSBS-UHFFFAOYSA-N 0.000 description 1
- LQZHZFUSFHLGHE-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)propyl]silane Chemical compound C1C(C(C)C[Si](OC)(OC)OC)CCC2OC21 LQZHZFUSFHLGHE-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
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- H01L29/76—Unipolar devices, e.g. field effect transistors
- H01L29/772—Field effect transistors
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Description
すなわち本発明は、
基材と、
ソース電極、ドレイン電極およびゲート電極と、
前記ソース電極およびドレイン電極と接する半導体層と、
前記半導体層を前記ゲート電極と絶縁するゲート絶縁層と、
前記半導体層に対して前記ゲート絶縁層とは反対側で前記半導体層と接する第2絶縁層と、を備えたn型半導体素子であって、
前記半導体層がナノカーボンを含有し、
前記第2絶縁層が、一般式(1)で表される構造を少なくとも側鎖の一部に有するポリマーを含有する、n型半導体素子である。
本発明の実施の形態に係るn型半導体素子は、基材と、ソース電極、ドレイン電極およびゲート電極と、前記ソース電極およびドレイン電極と接する半導体層と、前記半導体層を前記ゲート電極と絶縁するゲート絶縁層と、前記半導体層に対して前記ゲート絶縁層とは反対側で前記半導体層と接する第2絶縁層と、を備えたn型半導体素子であって、前記半導体層がナノカーボンを含有し、前記第2絶縁層が、一般式(1)で表される構造を少なくとも側鎖の一部に有するポリマーを含有する。
基材は、少なくとも電極系が配置される面が絶縁性を備える基材であれば、いかなる材質のものでもよい。基材としては、例えば、シリコンウエハ、ガラス、サファイア、アルミナ焼結体等の無機材料からなる基材、ポリイミド、ポリビニルアルコール、ポリビニルクロライド、ポリエチレンテレフタレート、ポリフッ化ビニリデン、ポリシロキサン、ポリビニルフェノール(PVP)、ポリエステル、ポリカーボネート、ポリスルホン、ポリエーテルスルホン、ポリエチレン、ポリフェニレンスルフィド、ポリパラキシレン等の有機材料からなる基材が好ましい。
ゲート電極、ソース電極およびドレイン電極に用いられる材料は、一般的に電極として使用されうる導電材料であれば、いかなるものでもよい。例えば、酸化錫、酸化インジウム、酸化錫インジウム(ITO)などの導電性金属酸化物;白金、金、銀、銅、鉄、錫、亜鉛、アルミニウム、インジウム、クロム、リチウム、ナトリウム、カリウム、セシウム、カルシウム、マグネシウム、パラジウム、モリブデン、アモルファスシリコン、ポリシリコンなどの金属やこれらの合金;ヨウ化銅、硫化銅などの無機導電性物質;ポリチオフェン、ポリピロール、ポリアニリン;ポリエチレンジオキシチオフェンとポリスチレンスルホン酸との錯体など;ヨウ素などのドーピングにより導電率を向上させた導電性ポリマーなど;炭素材料など;および有機成分と導電体とを含有する材料など、が挙げられるが、これらに限定されるものではない。
メチルアクリレート、アクリル酸、アクリル酸2−エチルヘキシル、メタクリル酸エチル、n−ブチルアクリレート、i−ブチルアクリレート、i−プロパンアクリレート、グリシジルアクリレート、N−メトキシメチルアクリルアミド、N−エトキシメチルアクリルアミド、N−n−ブトキシメチルアクリルアミド、N−イソブトキシメチルアクリルアミド、ブトキシトリエチレングリコールアクリレート、ジシクロペンタニルアクリレート、ジシクロペンテニルアクリレート、2−ヒドロキシエチルアクリレート、イソボニルアクリレート、2−ヒドロキシプロピルアクリレート、イソデキシルアクリレート、イソオクチルアクリレート、ラウリルアクリレート、2−メトキシエチルアクリレート、メトキシエチレングリコールアクリレート、メトキシジエチレングリコールアクリレート、オクタフロロペンチルアクリレート、フェノキシエチルアクリレート、ステアリルアクリレート、トリフロロエチルアクリレート、アクリルアミド、アミノエチルアクリレート、フェニルアクリレート、フェノキシエチルアクリレート、1−ナフチルアクリレート、2−ナフチルアクリレート、チオフェノールアクリレート、ベンジルメルカプタンアクリレートなどのアクリル系モノマーおよびこれらのアクリレートをメタクリレートに代えたもの;
スチレン、p−メチルスチレン、o−メチルスチレン、m−メチルスチレン、α−メチルスチレン、クロロメチルスチレン、ヒドロキシメチルスチレンなどのスチレン類;
γ−メタクリロキシプロピルトリメトキシシラン、1−ビニル−2−ピロリドン;
などが挙げられる。
ゲート絶縁層に用いられる材料は、特に限定されないが、酸化シリコン、アルミナ等の無機材料;ポリイミド、ポリビニルアルコール、ポリビニルクロライド、ポリエチレンテレフタレート、ポリフッ化ビニリデン、ポリシロキサン、ポリビニルフェノール(PVP)等の有機高分子材料;あるいは無機材料粉末と有機材料の混合物を挙げることができる。
中でもケイ素と炭素の結合を含む有機化合物を含むものが好ましい。
ここで、R14は、水素原子、アルキル基、複素環基、アリール基またはアルケニル基を示す。R14が複数存在する場合、それぞれのR14は同じでも異なっていてもよい。R15は、水素原子、アルキル基、アシル基またはアリール基を示す。R15が複数存在する場合、それぞれのR15は同じでも異なっていてもよい。mは1〜3の整数を示す。
ここで、R16は、1つ以上のエポキシ基を鎖の一部に有するアルキル基を示す。R16が複数存在する場合、それぞれのR16は同じでも異なっていてもよい。R17は、水素原子、アルキル基、複素環基、アリール基またはアルケニル基を示す。R17が複数存在する場合、それぞれのR17は同じでも異なっていてもよい。R18は、水素原子、アルキル基、アシル基またはアリール基を示す。R18が複数存在する場合、それぞれのR18は同じでも異なっていてもよい。lは0〜2の整数、nは1または2を示す。ただし、l+n≦3である。
ナノカーボンとは、ナノメートルサイズの構造を有する、炭素からなる物質であり、例えば、フラーレン、カーボンナノチューブ(CNT)、グラフェン、カーボンナノホーン、グラフェンナノリボン、内包CNT、内包フラーレンなどが挙げられる。半導体特性の観点から、ナノカーボンとしては、フラーレン、CNT、グラフェンが好ましく、CNTがより好ましい。
CNTとしては、1枚の炭素膜(グラフェン・シート)が円筒状に巻かれた単層CNT、2枚のグラフェン・シートが同心円状に巻かれた2層CNT、複数のグラフェン・シートが同心円状に巻かれた多層CNTのいずれを用いてもよい。高い半導体特性を得るためには、単層CNTを用いるのが好ましい。CNTは、アーク放電法、CVD、レーザー・アブレーション法等により得ることができる。
本発明に用いられるCNTにおいては、CNTの表面の少なくとも一部に共役系重合体を付着せしめて用いること(以下、共役系重合体が付着したCNTを「CNT複合体」と称する)が好ましい。ここで、共役系重合体とは、繰り返し単位が共役構造をとり、重合度が2以上である化合物を指す。
半導体層は、ナノカーボンを含有する。このとき、ナノカーボンはフラーレン、CNT、グラフェンが好ましく、CNTがより好ましい。さらにCNTは、共役系重合体を付着せしめてCNT複合体として用いることが好ましい。半導体層は電気特性を阻害しない範囲であれば、さらに有機半導体や絶縁材料を含んでもよい。
第2絶縁層は、半導体層に対してゲート絶縁層が形成された側の反対側に形成される。半導体層に対してゲート絶縁層が形成された側の反対側とは、例えば、半導体層の下側にゲート絶縁層を有する場合は、半導体層の上側を指す。第2絶縁層を形成することにより、半導体層を保護することができる。
本発明の実施の形態に係るn型半導体素子は、第2絶縁層上に、水蒸気透過度が20g/(m2・24h)以下である層(バリア層)を有することが好ましい。バリア層の水蒸気透過度は、より好ましくは10g/(m2・24h)以下であり、さらに好ましくは1g/(m2・24h)以下である。この範囲にあることで、大気中の水分の影響を受けにくく、安定したn型半導体特性を実現できる。
ただしIdはソース・ドレイン間電流(A)、Vsdはソース・ドレイン間電圧(V)、Vgはゲート電圧(V)、Dはゲート絶縁層の厚み(m)、Lはチャネル長(m)、Wはチャネル幅(m)、εrはゲート絶縁層の比誘電率(F/m)、εは真空の誘電率(8.85×10−12F/m)、δは該当の物理量の変化量を示す。
本発明の実施の形態に係る半導体素子の製造方法は、特に制限はないが、上記ポリマーおよび溶剤を含有する組成物を塗布および乾燥して前記第2絶縁層を形成する工程を含むことが好ましい。また、半導体層を塗布法により形成する工程を含むことが好ましい。半導体層を塗布法により形成するには、少なくとも、半導体層を形成するための材料を溶解させた溶液を塗布する工程と、その塗膜を乾燥する工程とを含む。
次に、上記n型半導体素子を有する、本発明の実施の形態に係る無線通信装置について説明する。この無線通信装置は、例えば、RFIDタグのような、リーダ/ライタに搭載されたアンテナから送信される搬送波を受信し、また、信号を送信することで、電気通信を行う装置である。
次に、本発明の実施の形態に係る無線通信装置を含有する商品タグについて説明する。この商品タグは、例えば基体と、この基体によって被覆された上記無線通信装置とを有している。
化合物[60]を式1に示す方法で合成した。
1H−NMR(CD2Cl2,(d=ppm)):8.00(s,2H),7.84(s,2H),7.20―7.15(m,8H),7.04(d,2H),6.95(d,2H),2.88(t,4H),2.79(t,4H),1.77−1.29(m,48H),0.88(m,12H)。
メチルトリメトキシシラン61.29g(0.45モル)、2−(3,4−エポキシシクロヘキシル)エチルトリメトキシシラン12.31g(0.05モル)、およびフェニルトリメトキシシラン99.15g(0.5モル)を、プロピレングリコールモノブチルエーテル(沸点170℃)203.36gに溶解し、これに、水54.90g、リン酸0.864gを、撹拌しながら加えた。得られた溶液をバス温105℃で2時間加熱し、内温を90℃まで上げて、主として副生するメタノールからなる成分を留出させた。次いで、バス温130℃で2.0時間加熱し、内温を118℃まで上げて、主として水とプロピレングリコールモノブチルエーテルからなる成分を留出させた。その後、室温まで冷却し、固形分濃度26.0重量%のポリシロキサン溶液Aを得た。得られたポリシロキサンの分子量を上記の方法で測定したところ、重量平均分子量は6000であった。
DISPERBYK2022(ビックケミー・ジャパン社製、一般式(3)で表される単位構造を有し、さらに一般式(4)で表される単位構造を有するポリマー。一般式(4)で表される単位構造と一般式(3)で表される単位構造との比率=78/22)10.0gをPGMEA10.0gに溶解し、第2絶縁層作製用の溶液Aを得た。
BYK6919(ビックケミー・ジャパン社製、一般式(3)で表される単位構造を有し、さらに一般式(4)で表される単位構造を有するポリマー。一般式(4)で表される単位構造と一般式(3)で表される単位構造との比率=55/45)10.0gをPGMEA10.0gに溶解し、第2絶縁層作製用の溶液Bを得た。
第2絶縁層作製用の溶液B10.0gにジシクロヘキシルメチルアミン(東京化成工業製)0.60gを添加し、第2絶縁層作製用の溶液Cを得た。
第2絶縁層作製用の溶液B10.0gにキヌクリジン(東京化成工業製)0.60gを添加し、第2絶縁層作製用の溶液Dを得た。
第2絶縁層溶液B10.0gにDBU(東京化成工業製)0.60gを添加し、第2絶縁層作製用の溶液Eを得た。
ポリメチルメタクリレート(PMMA,三菱レイヨン社製)3.0gをPGMEA10.0gに溶解し、第2絶縁層作製用の溶液Fを得た。
シクロオレフィンポリマー(日本ゼオン製)2.5gをデカヒドロナフタレン(和光純薬工業製)7.5gに溶解し、バリア層作製用の溶液Aを得た。
シクロオレフィンポリマー(日本ゼオン製)0.13gをデカヒドロナフタレン(和光純薬工業製)9.8gに溶解し、バリア層作製用の溶液Bを得た。
図1に示す構成の半導体素子を作製した。ガラス製の基板1(膜厚0.7mm)上に、抵抗加熱法により、マスクを通して、クロムを厚さ5nmおよび金を厚さ50nm真空蒸着し、ゲート電極2を形成した。次に、ゲート絶縁層溶液Aを上記基板上にスピンコート塗布(2000rpm×30秒)し、窒素気流下、200℃で1時間熱処理することによって、膜厚600nmのゲート絶縁層3を形成した。次に、抵抗加熱法により、マスクを通して、金を厚さ50nm真空蒸着し、ソース電極5およびドレイン電極6を形成した。次に、ソース電極5とドレイン電極6との間に、上記半導体溶液Aを1μL滴下し、30℃で10分風乾した後、ホットプレート上で、窒素気流下、150℃で30分の熱処理を行い、半導体層4を形成した。次に、ポリアリルアミン(PAA−05、日東紡製)溶液5μLを、半導体層4上に、半導体層4を覆うように滴下し、窒素気流下、110℃で15分熱処理して、第2絶縁層を形成した。こうして、半導体素子を得た。この半導体素子のソース・ドレイン電極の幅(チャネル幅)は200μm、ソース・ドレイン電極の間隔(チャネ4長)は20μmとした。この半導体素子における、第2絶縁層の膜厚は38μmであった。
ポリアリルアミン溶液の代わりに第2絶縁層作製用の溶液Aを用いたこと以外は、実施例1と同様にして、半導体素子を作製し、移動度を評価した。この半導体素子における、第2絶縁層の膜厚は42μmであった。
ポリアリルアミン溶液の代わりに第2絶縁層作製用の溶液Bを用いたこと以外は、実施例1と同様にして、半導体素子を作製し、移動度を評価した。この半導体素子における、第2絶縁層の膜厚は41μmであった。
ポリアリルアミン溶液の代わりに第2絶縁層作製用の溶液Cを用いたこと以外は、実施例1と同様にして、半導体素子を作製し、移動度を評価した。この半導体素子における、第2絶縁層の膜厚は40μmであった。
ポリアリルアミン溶液の代わりに第2絶縁層作製用の溶液Dを用いたこと以外は、実施例1と同様にして、半導体素子を作製し、移動度を評価した。この半導体素子における、第2絶縁層の膜厚は43μmであった。
ポリアリルアミン溶液の代わりに第2絶縁層作製用の溶液Eを用いたこと以外は、実施例1と同様にして、半導体素子を作製し、移動度を評価した。この半導体素子における、第2絶縁層の膜厚は42μmであった。
実施例6と同様にして、第2絶縁層を形成した。次いで、バリア層作製用の溶液A10μLを、第2絶縁層を覆うように滴下し、窒素気流下、90℃で15分熱処理して、バリア層を形成した。こうして、半導体素子を得た。この半導体素子における、第2絶縁層の膜厚は45μm、バリア層の膜厚は98μmであった。
バリア層作製用の溶液Aの代わりにフッ素樹脂溶液(CYTOP809A、旭硝子製)を用いたこと以外は、実施例7と同様にして、半導体素子を作製し、移動度を評価した。この半導体素子における、第2絶縁層の膜厚は41μm、バリア層の膜厚は9μmであった。
実施例6と同様にして、第2絶縁層を形成した。次いで、バリア層作製用の溶液B10μLを、第2絶縁層を覆うように滴下し、窒素気流下、90℃で15分熱処理して、バリア層を形成した。こうして、半導体素子を得た。この半導体素子における、第2絶縁層の膜厚は43μm、バリア層の膜厚は5μmであった。
ポリアリルアミン溶液の代わりに第2絶縁層作製用の溶液Fを用いたこと以外は、実施例1と同様にして、半導体素子を作製し、移動度を評価した。この半導体素子における、第2絶縁層の膜厚は40μmであった。
2 ゲート電極
3 ゲート絶縁層
4 半導体層
5 ソース電極
6 ドレイン電極
7 ナノカーボン
8 第2絶縁層
9 バリア層
50 アンテナ
Claims (15)
- 基材と、
ソース電極、ドレイン電極およびゲート電極と、
前記ソース電極およびドレイン電極と接する半導体層と、
前記半導体層を前記ゲート電極と絶縁するゲート絶縁層と、
前記半導体層に対して前記ゲート絶縁層とは反対側で前記半導体層と接する第2絶縁層と、を備えたn型半導体素子であって、
前記半導体層がナノカーボンを含有し、
前記第2絶縁層が、一般式(1)で表される構造を少なくとも側鎖の一部に有するポリマーを含有することを特徴とする、n型半導体素子。
- 前記一般式(1)で表される構造を側鎖に有するポリマーがさらに一般式(4)で表される単位構造を有する、請求項2に記載のn型半導体素子。
- 前記第2絶縁層の膜厚が500nm以上である、請求項1〜3いずれか記載のn型半導体素子。
- 前記第2絶縁層が、窒素原子およびリン原子から選ばれる1種以上の原子を有する電子供与性化合物をさらに含有する、請求項1〜4いずれか記載のn型半導体素子。
- 前記電子供与性化合物が、窒素原子を有する化合物である、請求項5記載のn型半導体素子。
- 前記電子供与性化合物が、窒素原子を含む環構造を含有する化合物である、請求項6記載のn型半導体素子。
- 前記第2絶縁層上に、水蒸気透過度が20g/(m2・24h)以下である層(かかる層をバリア層と称する)を有する、請求項1〜7いずれか記載の半導体素子。
- 前記バリア層が、フッ素系樹脂、塩素系樹脂、二トリル樹脂、ポリエステル樹脂およびポリオレフィン樹脂からなる群から選ばれるいずれか1種類以上を含有する、請求項8記載のn型半導体素子。
- 前記ナノカーボンがカーボンナノチューブである、請求項1〜9いずれか記載のn型半導体素子。
- 前記カーボンナノチューブにおいて、その表面の少なくとも一部に共役系重合体が付着していることを特徴とする、請求項10記載のn型半導体素子。
- 請求項1〜11いずれか記載のn型半導体素子の製造方法であって、前記一般式(1)で表される構造を少なくとも側鎖の一部に有するポリマーおよび溶剤を含有する組成物を塗布し、および乾燥して前記第2絶縁層を形成する工程を含む、n型半導体素子の製造方法。
- 前記半導体層の形成において、該半導体層の構成成分および溶剤とからなる溶液を塗布し、および乾燥して形成する工程を含む、請求項12記載のn型半導体素子の製造方法。
- 請求項1〜11いずれか記載の半導体素子と、アンテナと、を少なくとも有する無線通信装置。
- 請求項14記載の無線通信装置を用いた商品タグ。
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