JP2016178146A - 半導体素子の製造方法 - Google Patents
半導体素子の製造方法 Download PDFInfo
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- JP2016178146A JP2016178146A JP2015055702A JP2015055702A JP2016178146A JP 2016178146 A JP2016178146 A JP 2016178146A JP 2015055702 A JP2015055702 A JP 2015055702A JP 2015055702 A JP2015055702 A JP 2015055702A JP 2016178146 A JP2016178146 A JP 2016178146A
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- XBFJAVXCNXDMBH-UHFFFAOYSA-N tetracyclo[6.2.1.1(3,6).0(2,7)]dodec-4-ene Chemical compound C1C(C23)C=CC1C3C1CC2CC1 XBFJAVXCNXDMBH-UHFFFAOYSA-N 0.000 description 1
- PVJHFVMRMWVWAX-UHFFFAOYSA-N tetradeca-2,7,9,11-tetraene Chemical compound CCC=CC=CC=CCCCC=CC PVJHFVMRMWVWAX-UHFFFAOYSA-N 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- ADLSSRLDGACTEX-UHFFFAOYSA-N tetraphenyl silicate Chemical compound C=1C=CC=CC=1O[Si](OC=1C=CC=CC=1)(OC=1C=CC=CC=1)OC1=CC=CC=C1 ADLSSRLDGACTEX-UHFFFAOYSA-N 0.000 description 1
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- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- YZVRVDPMGYFCGL-UHFFFAOYSA-N triacetyloxysilyl acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)OC(C)=O YZVRVDPMGYFCGL-UHFFFAOYSA-N 0.000 description 1
- 125000005409 triarylsulfonium group Chemical group 0.000 description 1
- GIHPVQDFBJMUAO-UHFFFAOYSA-N tributoxy(ethyl)silane Chemical compound CCCCO[Si](CC)(OCCCC)OCCCC GIHPVQDFBJMUAO-UHFFFAOYSA-N 0.000 description 1
- GYZQBXUDWTVJDF-UHFFFAOYSA-N tributoxy(methyl)silane Chemical compound CCCCO[Si](C)(OCCCC)OCCCC GYZQBXUDWTVJDF-UHFFFAOYSA-N 0.000 description 1
- ZQJYXISBATZORI-UHFFFAOYSA-N tributyl(ethoxy)silane Chemical compound CCCC[Si](CCCC)(CCCC)OCC ZQJYXISBATZORI-UHFFFAOYSA-N 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- YOKZJDRCZXTECO-UHFFFAOYSA-N tricyclo[5.2.1.02,6]deca-3,8-diene-2-carboxylic acid Chemical compound C1=CC2CC1C1(C(=O)O)C2CC=C1 YOKZJDRCZXTECO-UHFFFAOYSA-N 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- ZLGWXNBXAXOQBG-UHFFFAOYSA-N triethoxy(3,3,3-trifluoropropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)F ZLGWXNBXAXOQBG-UHFFFAOYSA-N 0.000 description 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 1
- WUMSTCDLAYQDNO-UHFFFAOYSA-N triethoxy(hexyl)silane Chemical compound CCCCCC[Si](OCC)(OCC)OCC WUMSTCDLAYQDNO-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- BOVWGKNFLVZRDU-UHFFFAOYSA-N triethoxy(trifluoromethyl)silane Chemical compound CCO[Si](OCC)(OCC)C(F)(F)F BOVWGKNFLVZRDU-UHFFFAOYSA-N 0.000 description 1
- UDUKMRHNZZLJRB-UHFFFAOYSA-N triethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OCC)(OCC)OCC)CCC2OC21 UDUKMRHNZZLJRB-UHFFFAOYSA-N 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 description 1
- HILHCDFHSDUYNX-UHFFFAOYSA-N trimethoxy(pentyl)silane Chemical compound CCCCC[Si](OC)(OC)OC HILHCDFHSDUYNX-UHFFFAOYSA-N 0.000 description 1
- ORVBHOQTQDOUIW-UHFFFAOYSA-N trimethoxy(trifluoromethyl)silane Chemical compound CO[Si](OC)(OC)C(F)(F)F ORVBHOQTQDOUIW-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
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明において、前記冷却工程における冷却を、前記焼成工程の焼成時の焼成温度から、焼成時の焼成温度より50℃低い温度までの冷却速度を、0.5〜5℃/分の範囲で実質的に制御することが好ましい。
本発明において、前記パッシベーション膜を、環状オレフィン樹脂、アクリル樹脂、カルド樹脂、ポリシロキサン樹脂およびポリイミド樹脂からなる群から選ばれる少なくとも1種の樹脂を含む樹脂組成物を用いて形成することが好ましい。
パッシベーション膜7を形成するために用いる樹脂組成物としては、特に限定されないが、得られる半導体素子1を、過酷な雰囲気においても高い信頼性を有するものとすることができるという点より、環状オレフィン樹脂、アクリル樹脂、カルド樹脂、ポリシロキサン樹脂およびポリイミド樹脂からなる群から選ばれる少なくとも1種の樹脂(A)を含有するものが好ましく、信頼性の向上効果がより高いという点より、環状オレフィン樹脂がより好ましく、プロトン性極性基を有する環状オレフィン樹脂が特に好ましい。これらの樹脂は、それぞれ単独で用いてもよく、または2種以上を併用してもよい。
エポキシ基含有アクリレート化合物の具体例としては、アクリル酸グリシジル、メタクリル酸グリシジル、α−エチルアクリル酸グリシジル、α−n−プロピルアクリル酸グリシジル、α−n−ブチルアクリル酸グリシジル、アクリル酸−3,4−エポキシブチル、メタクリル酸−3,4−エポキシブチル、アクリル酸−6,7−エポキシヘプチル、メタクリル酸−6,7−エポキシヘプチル、α−エチルアクリル酸−6,7−エポキシヘプチル、アクリル酸−3,4−エポキシシクロヘキシルメチル、メタクリル酸−3,4−エポキシシクロヘキシルメチル等が挙げられる。
オキセタン基含有アクリレート化合物の具体例としては、(メタ)アクリル酸(3−メチルオキセタン−3−イル)メチル、(メタ)アクリル酸(3−エチルオキセタン−3−イル)メチル、(メタ)アクリル酸(3−メチルオキセタン−3−イル)エチル、(メタ)アクリル酸(3−エチルオキセタン−3−イル)エチル、(メタ)アクリル酸(3−クロロメチルオキセタン−3−イル)メチル、(メタ)アクリル酸(オキセタン−2−イル)メチル、(メタ)アクリル酸(2−メチルオキセタン−2−イル)メチル、(メタ)アクリル酸(2−エチルオキセタン−2−イル)メチル、(1−メチル−1−オキセタニル−2−フェニル)−3−(メタ)アクリレート、(1−メチル−1−オキセタニル)−2−トリフロロメチル−3−(メタ)アクリレート、および(1−メチル−1−オキセタニル)−4−トリフロロメチル−2−(メタ)アクリレート等が挙げられる。これらのうち、(メタ)アクリル酸、無水マレイン酸、(メタ)アクリル酸グリシジル、メタクリル酸−6,7−エポキシヘプチル等が好ましい。
環状構造を構成している4級炭素原子に二つの環状構造が結合した骨格構造の具体例としては、フルオレン骨格、ビスフェノールフルオレン骨格、ビスアミノフェニルフルオレン骨格、エポキシ基を有するフルオレン骨格、アクリル基を有するフルオレン骨格等が挙げられる。
本発明で用いるカルド樹脂は、このカルド構造を有する骨格がそれに結合している官能基間の反応等により重合して形成される。カルド樹脂は、主鎖と嵩高い側鎖が一つの元素で繋がれた構造(カルド構造)をもち、主鎖に対してほぼ垂直方向に環状構造を有している。
カルド樹脂は、カルド構造を有する単量体を重合して得られる重合体であるが、その他の共重合可能な単量体との共重合体であってもよい。
上記単量体の重合方法は、常法に従えばよく、たとえば、開環重合法や付加重合法等が採用される。
(R4)m−Si−(OR5)4−m (4)
これらの中でも、1,2−ナフトキノンジアジド−5−スルホン酸クロライドとフェノール性水酸基を有する化合物との縮合物が好ましく、1,1,3−トリス(2,5−ジメチル−4−ヒドロキシフェニル)−3−フェニルプロパン(1モル)と1,2−ナフトキノンジアジド−5−スルホン酸クロライド(1.9モル)との縮合物がより好ましい。
テトラメトキシシラン、テトラエトキシシラン、テトラ−n−プロポキシシラン、テトラ−i−プロポキシシラン、テトラ−n−ブトキシシランなどのテトラアルコキシシラン類、
メチルトリメトキシシラン、メチルトリエトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、n−プロピルトリメトキシシラン、n-プロピルトリエトキシシラン、i−プロピルトリメトキシシラン、i−プロピルトリエトキシシラン、n−ブチルトリメトキシシラン、n−ブチルトリエトキシシラン、n−ペンチルトリメトキシシラン、n−ヘキシルトリメトキシシラン、n−ヘプチルトリメトキシシラン、n−オクチルトリメトキシシラン、n−デシルトリメトキシシラン、p−スチリルトリメトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、シクロヘキシルトリメトキシシラン、シクロヘキシルトリメトキシシラン、シクロヘキシルトリエトキシシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン、3−クロロプロピルトリメトキシシラン、3−クロロプロピルトリエトキシシラン、3,3,3−トリフルオロプロピルトリメトキシシラン、3,3,3−トリフルオロプロピルトリエトキシシラン、3−アミノプロピルトリメトキシシラン、3−アミノプロピルトリエトキシシラン、N−2−(アミノエチル)−3−アミノプロピルトリメトキシシラン、N−フェニル−3−アミノプロピルトリメトキシシラン、2−ヒドロキシエチルトリメトキシシラン、2−ヒドロキシエチルトリエトキシシラン、2−ヒドロキシプロピルトリメトキシシラン、2−ヒドロキシプロピルトリエトキシシラン、3−ヒドロキシプロピルトリメトキシシラン、3−ヒドロキシプロピルトリエトキシシラン、3−メルカプトプロピルトリメトキシシラン、3−メルカプトプロピルトリエトキシシラン、3−イソシアナートプロピルトリメトキシシラン、3−イソシアナートプロピルトリエトキシシラン、3−グリシドキシプロピルトリメトキシシラン、3−グリシドキシプロピルトリエトキシシラン、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、2−(3,4−エポキシシクロヘキシル)エチルトリエトキシシラン、3−(メタ)アクリルオキシプロピルトリメトキシシラン、3−(メタ)アクリルオキシプロピルトリエトキシシラン、3−ウレイドプロピルトリメトキシシラン、3−ウレイドプロピルトリエトキシシラン、3−エチル(トリメトキシシリルプロポキシメチル)オキセタン、3−エチル(トリエトキシシリルプロポキシメチル)オキセタン、3−トリエトキシシリル−N−(1,3−ジメチル−ブチリデン)プロピルアミン、ビス(トリエトキシシリルプロピル)テトラスルフィドなどのトリアルコキシシラン類、
ジメチルジメトキシシラン、ジメチルジエトキシシラン、ジエチルジメトキシシラン、ジエチルジエトキシシラン、ジ−n−プロピルジメトキシシラン、ジ−n−プロピルジエトキシシラン、ジ−i−プロピルジメトキシシラン、ジ−i−プロピルジエトキシシラン、ジ−n−ブチルジメトキシシラン、ジ−n−ペンチルジメトキシシラン、ジ−n−ペンチルジエトキシシラン、ジ−n−ヘキシルジメトキシシラン、ジ−n−ヘキシルジエトキシシラン、ジ−n−へプチルジメトキシシラン、ジ−n−ヘプチルジエトキシシラン、ジ−n−オクチルジメトキシシラン、ジ−n−オクチルジエトキシシラン、ジ−n−シクロヘキシルジメトキシシラン、ジ−n−シクロヘキシルジエトキシシラン、ジフェニルジメトキシシラン、ジフェニルジエトキシシラン、3−グリシドキシプロピルメチルジエトキシシラン、3−メタクリルオキシプロピルメチルジメトキシシラン、3−アクリルオキシプロピルメチルジメトキシシラン、3−メタクリルオキシプロピルメチルジエトキシシラン、3−アクリルオキシプロピルメチルジエトキシシラン、N−2−(アミノエチル)−3−アミノプロピルメチルジメトキシシランなどのジアルコキシシラン類の他、
メチルトリアセチルオキシシラン、ジメチルジアセチルオキシシラン等のケイ素原子含有化合物;
アセトアルコキシアルミウムジイソプロピレート等のアルミニウム原子含有化合物;
テトラノルマルプロポキシジルコニウム、テトラノルマルブトキシジルコニウム、ジルコニウムテトラアセチルアセトネート、ジルコニウムトリブトキシアセチルアセトネート、ジルコニウムモノブトキシアセチルアセトネートビス(エチルアセトアセテート)、ジルコニウムジブトキシビス(エチルアセトアセテート)、ジルコニウムテトラアセチルアセトネート、ジルコニウムトリブトキシステアレート等のジルコニウム原子含有化合物;が挙げられる。
潜像パターンを有するパッシベーション膜7に現像液を接触させる方法としては、たとえば、パドル法、スプレー法、ディッピング法等の方法が用いられる。現像は、通常、0〜100℃、好ましくは5〜55℃、より好ましくは10〜30℃の範囲で、通常、30〜180秒間の範囲とされる。
なお、各特性の定義および評価方法は、以下のとおりである。
得られた薄膜トランジスタについて、大気下・暗室中にて半導体パラメータアナライザー(Agilent社製、4156C)を用いて、ゲート電圧を−60Vから+20Vまで変化させることによって、ゲート電圧の変化に対するソース・ドレイン間に流れる電流の変化を測定した。そして、測定の結果、ソース・ドレイン間に流れる電流の値が、Id=100nA×(W/L)(ただし、Wはチャネル幅、Lはチャネル長、Idはドレイン電流)となった時の電圧を、閾値電圧Vthとした。そして、測定の結果得られた閾値電圧Vthについて、以下の基準で評価を行った。
◎:閾値電圧Vthが、±1V以内
○:閾値電圧Vthが、−10V以上、−1V未満、または+1V超、+10V未満
×:閾値電圧Vthが、−10V未満、または+10V超
得られた薄膜トランジスタについて、ゲートに+30Vの電圧を印加するとともに、ドレインの電圧を0Vとした、正バイアスストレス(PBS)を2000秒間印加した。そして、正バイアスストレスを印加した薄膜トランジスタについて、大気下・暗室中にて半導体パラメータアナライザー(Agilent社製、4156C)を用いて、ゲート電圧を−60Vから+20Vまで変化させることによって、ゲート電圧の変化に対するソース・ドレイン間に流れる電流の変化を測定した。そして、測定の結果、ソース・ドレイン間に流れる電流の値が、Id=100nA×(W/L)(ただし、Wはチャネル幅、Lはチャネル長、Idはドレイン電流)となった時の電圧を、正バイアスストレス印加後の閾値電圧Vthとした。
◎:正バイアスストレス印加後の閾値電圧Vthが、±1V以内
○:正バイアスストレス印加後の閾値電圧Vthが、−15V以上、−1V未満、または+1V超、+15V未満
×:正バイアスストレス印加後の閾値電圧Vthが、−15V未満、または+15V超
得られた薄膜トランジスタについて、ゲートに−30Vの電圧を印加するとともに、ドレインの電圧を0Vとした、負バイアスストレス(NBS)を2000秒間印加した。そして、負バイアスストレスを印加した薄膜トランジスタについて、大気下・暗室中にて半導体パラメータアナライザー(Agilent社製、4156C)を用いて、ゲート電圧を−60Vから+20Vまで変化させることによって、ゲート電圧の変化に対するソース・ドレイン間に流れる電流の変化を測定した。そして、測定の結果、ソース・ドレイン間に流れる電流の値が、Id=100nA×(W/L)(ただし、Wはチャネル幅、Lはチャネル長、Idはドレイン電流)となった時の電圧を、負バイアスストレス印加後の閾値電圧Vthとした。
◎:負バイアスストレス印加後の閾値電圧Vthが、±1V以内
○:負バイアスストレス印加後の閾値電圧Vthが、−15V以上、−1V未満、または+1V超、+15V未満
×:負バイアスストレス印加後の閾値電圧Vthが、−15V未満、または+15V超
<環状オレフィン重合体(A−1)の調製>
N−フェニル−ビシクロ[2.2.1]ヘプト−5−エン−2,3−ジカルボキシイミド(NBPI)40モル%、および4−ヒドロキシカルボニルテトラシクロ[6.2.1.13,6.02,7]ドデカ−9−エン(TCDC)60モル%からなる単量体混合物100部、1,5−ヘキサジエン2.0部、(1,3−ジメシチルイミダゾリン−2−イリデン)(トリシクロヘキシルホスフィン)ベンジリデンルテニウムジクロリド(「Org.Lett.,第1巻,953頁,1999年」に記載された方法で合成した)0.02部、およびジエチレングリコールエチルメチルエーテル200部を、窒素置換したガラス製耐圧反応器に仕込み、攪拌しつつ80℃にて4時間反応させて重合反応液を得た。
<樹脂組成物の調製>
樹脂(A)として、合成例1で得られた環状オレフィン重合体(A−1)の重合体溶液291部(環状オレフィン重合体(A−1)として100部)、アルコキシシリル基含有(メタ)アクリレート化合物(B)として、3−アクリロキシプロピルトリメトキシシラン(製品名「KBM−5103」、信越化学工業社製)1部、4官能以上の(メタ)アクリレート化合物(C)として、ジペンタエリスリトールペンタ/ヘキサアクリレート(製品名「アロニックスM−406 ペンタ25−35%」、東亜合成社製)3部、光重合開始剤(D)として、2−ヒドロキシ−1−{4−[4−(2−ヒドロキシ−2−メチル−プロピオニル)−ベンジル]フェニル}−2−メチル−プロパン−1−オン(製品名「Irgacure127」、BASF社製)1部、架橋剤(E)として、エポキシ化ブタンテトラカルボン酸テトラキス(3−シクロヘキセニルメチル)修飾ε−カプロラクトン(脂肪族環状4官能性のエポキシ樹脂、製品名「エポリードGT401」、ダイセル化学工業社製)15部、シリコーン系界面活性剤(製品名「KP−341」、信越化学工業社製)0.03部、および、溶剤として、エチレングリコールエチルメチルエーテル270部を混合し、溶解させた後、孔径0.45μmのポリテトラフルオロエチレン製フィルターでろ過して、樹脂組成物を調製した。
次いで、以下の方法により、図1に示す構成を有する薄膜トランジスタを作製した。すなわち、まず、基板2としてのp型シリコン基板を準備し、p型シリコン基板について、酸素と水素の雰囲気下、1000℃、13分の条件で熱処理を行うことで、p型シリコン基板上に、ゲート絶縁膜となる100nmの熱酸化膜を形成した。次いで、その上に50nmのIn−Ga−Zn−O系非単結晶膜を、成膜時の雰囲気を、酸素濃度100体積%としたスパッタリング法により、形成した。次いで、In−Ga−Zn−O系非単結晶膜をパターニングするため、エッチングのマスク用のポジ型フォトレジストをスピンコート法により半導体層上に塗布し、ホットプレートを用いて溶媒を除去することでレジスト膜を形成し、これに続いて、露光工程、現像工程を経てレジスト膜をパターニングした。次いで、形成したマスクを使用して、燐酸によるウェットエッチングにより、In−Ga−Zn−O系非単結晶膜をアイランド状にパターニングし、これに続いて、剥離液を用いてレジスト膜を除去することで、半導体層4を形成した(図2(A)参照)。次いで、水蒸気雰囲気下(H2O/O2:10%H2O)で、220℃、1時間の条件で加熱処理を行った。
In−Ga−Zn−O系非単結晶膜を、成膜時の雰囲気を、酸素濃度50体積%、アルゴン濃度50体積%(Ar/O2=50/50)としたスパッタリング法により、形成した以外は、実施例1と同様にして、薄膜トランジスタを得て、同様に評価を行った。結果を表1に示す。
In−Ga−Zn−O系非単結晶膜を、成膜時の雰囲気を、酸素濃度2体積%、アルゴン濃度98体積%(Ar/O2=98/2)としたスパッタリング法により、形成した以外は、実施例1と同様にして、薄膜トランジスタを得て、同様に評価を行った。結果を表1に示す。
パッシベーション膜7を形成しなかった以外は、実施例1と同様にして、薄膜トランジスタを得て、同様に評価を行った。すなわち、比較例2においては、樹脂組成物を用いた樹脂膜の形成を行わずに、実施例1と同様の条件でIn−Ga−Zn−O系非単結晶膜の形成、焼成および冷却を行うことで、薄膜トランジスタを得た(後述する比較例3,4も同様。)。結果を表1に示す。
パッシベーション膜7を形成しなかった以外は、実施例2と同様にして、薄膜トランジスタを得て、同様に評価を行った。結果を表1に示す。
パッシベーション膜7を形成しなかった以外は、比較例1と同様にして、薄膜トランジスタを得て、同様に評価を行った。結果を表1に示す。
パッシベーション膜7を形成しなかった点、ならびに、ソース電極5およびドレイン電極6形成後の焼成を行わなかった点以外は、実施例1と同様にして、薄膜トランジスタを得て、同様に評価を行った。
パッシベーション膜7を形成しなかった点、ならびに、ソース電極5およびドレイン電極6形成後の焼成を行わなかった点以外は、実施例2と同様にして、薄膜トランジスタを得て、同様に評価を行った。
パッシベーション膜7を形成しなかった点、ならびに、ソース電極5およびドレイン電極6形成後の焼成を行わなかった点以外は、比較例1と同様にして、薄膜トランジスタを得て、同様に評価を行った。
半導体層上にパッシベーション膜を形成しなかった場合には、得られる薄膜トランジスタは、閾値電圧Vthがゼロから乖離したものとなり、また、負バイアスストレスに対する耐性にも劣るものであった(比較例2〜4)。
また、半導体層上にパッシベーション膜を形成せず、しかも、その後の焼成も行わなかった場合には、表1に示すように、正バイアスストレスに対する耐性に劣るものとなったり(比較例5,6)、閾値電圧Vthがゼロから乖離したものとなる結果となった(比較例6,7)。
なお、比較例2,3,5,6については、半導体層としてのIn−Ga−Zn−O系非単結晶膜の形成を、酸素濃度30〜100体積%の雰囲気下で行った実験例であるが、半導体層上にパッシベーション膜を形成しなかったため、焼成時に、含有酸素に続いて、結合酸素も半導体層から多量に離脱してしまったため、表1に示すような結果となったと考えられる。
2…基板
3…ゲート電極
4…半導体層
5…ソース電極
6…ドレイン電極
7…パッシベーション膜
10…リフトオフ用レジスト
20…導電性材料からなる層
Claims (5)
- 基板上に、無機酸化物半導体を含む半導体層を形成する半導体層形成工程と、
前記半導体層を覆うように、有機材料からなるパッシベーション膜を成膜するパッシベーション膜形成工程と、
前記パッシベーション膜を焼成する焼成工程と、
焼成後、冷却する冷却工程とを備える半導体素子の製造方法であって、
前記半導体層形成工程における前記半導体層の形成を、酸素濃度30〜100体積%の雰囲気下で行うことを特徴とする半導体素子の製造方法。 - 前記半導体層形成工程における前記半導体層の形成を、酸素濃度30〜100体積%の雰囲気下で、スパッタリング法により行うことを特徴とする請求項1に記載の半導体素子の製造方法。
- 前記冷却工程における冷却を、前記焼成工程の焼成時の焼成温度から、焼成時の焼成温度より50℃低い温度までの冷却速度を、0.5〜5℃/分の範囲で実質的に制御することを特徴とする請求項1または2に記載の半導体素子の製造方法。
- 前記パッシベーション膜を、環状オレフィン樹脂、アクリル樹脂、カルド樹脂、ポリシロキサン樹脂およびポリイミド樹脂からなる群から選ばれる少なくとも1種の樹脂を含む樹脂組成物を用いて形成することを特徴とする請求項1〜3のいずれかに記載の半導体素子の製造方法。
- 請求項1〜4のいずれかに記載の方法により得られる半導体素子。
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