JP6164218B2 - 薄膜トランジスタ - Google Patents
薄膜トランジスタ Download PDFInfo
- Publication number
- JP6164218B2 JP6164218B2 JP2014530540A JP2014530540A JP6164218B2 JP 6164218 B2 JP6164218 B2 JP 6164218B2 JP 2014530540 A JP2014530540 A JP 2014530540A JP 2014530540 A JP2014530540 A JP 2014530540A JP 6164218 B2 JP6164218 B2 JP 6164218B2
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- JP
- Japan
- Prior art keywords
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- ene
- acid
- hept
- epoxy
- Prior art date
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- 239000010409 thin film Substances 0.000 title claims description 83
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- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
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- 239000001301 oxygen Substances 0.000 description 1
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- 125000002958 pentadecyl 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])[H] 0.000 description 1
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- 125000005003 perfluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
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- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
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- 239000007921 spray Substances 0.000 description 1
- 238000005477 sputtering target Methods 0.000 description 1
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- 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
- LVEOKSIILWWVEO-UHFFFAOYSA-N tetradecyl 3-(3-oxo-3-tetradecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCC LVEOKSIILWWVEO-UHFFFAOYSA-N 0.000 description 1
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- YCGAZNXXGKTASZ-UHFFFAOYSA-N thiophene-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)S1 YCGAZNXXGKTASZ-UHFFFAOYSA-N 0.000 description 1
- ZWWLLYJRPKYTDF-UHFFFAOYSA-N thiophene-3,4-dicarboxylic acid Chemical compound OC(=O)C1=CSC=C1C(O)=O ZWWLLYJRPKYTDF-UHFFFAOYSA-N 0.000 description 1
- NBOMNTLFRHMDEZ-UHFFFAOYSA-N thiosalicylic acid Chemical compound OC(=O)C1=CC=CC=C1S NBOMNTLFRHMDEZ-UHFFFAOYSA-N 0.000 description 1
- UIERETOOQGIECD-ONEGZZNKSA-N tiglic acid Chemical compound C\C=C(/C)C(O)=O UIERETOOQGIECD-ONEGZZNKSA-N 0.000 description 1
- UAXOELSVPTZZQG-UHFFFAOYSA-N tiglic acid Natural products CC(C)=C(C)C(O)=O UAXOELSVPTZZQG-UHFFFAOYSA-N 0.000 description 1
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- QENJZWZWAWWESF-UHFFFAOYSA-N tri-methylbenzoic acid Natural products CC1=CC(C)=C(C(O)=O)C=C1C QENJZWZWAWWESF-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
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- XUHUMYVYHLHMCD-UHFFFAOYSA-N tris(2-cyclohexylphenyl) phosphite Chemical compound C1CCCCC1C1=CC=CC=C1OP(OC=1C(=CC=CC=1)C1CCCCC1)OC1=CC=CC=C1C1CCCCC1 XUHUMYVYHLHMCD-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
- HBYRZSMDBQVSHO-UHFFFAOYSA-N tris(2-tert-butyl-4-methylphenyl) phosphite Chemical compound CC(C)(C)C1=CC(C)=CC=C1OP(OC=1C(=CC(C)=CC=1)C(C)(C)C)OC1=CC=C(C)C=C1C(C)(C)C HBYRZSMDBQVSHO-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
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- 239000010937 tungsten Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02118—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer carbon based polymeric organic or inorganic material, e.g. polyimides, poly cyclobutene or PVC
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
- H01L29/76—Unipolar devices, e.g. field effect transistors
- H01L29/772—Field effect transistors
- H01L29/78—Field effect transistors with field effect produced by an insulated gate
- H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
- H01L29/7869—Thin film transistors, i.e. transistors with a channel being at least partly a thin film having a semiconductor body comprising an oxide semiconductor material, e.g. zinc oxide, copper aluminium oxide, cadmium stannate
Landscapes
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Thin Film Transistor (AREA)
- Electrodes Of Semiconductors (AREA)
- Formation Of Insulating Films (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
好ましくは、前記樹脂組成物が、前記エポキシ系架橋剤(B)として、異なる2種類以上の化合物を含有する。
好ましくは、前記樹脂組成物が、メラミン系架橋剤(C)をさらに含有する。
好ましくは、前記樹脂組成物中における、前記メラミン系架橋剤(C)の含有量が、前記環状オレフィン重合体(A)100重量部に対して、10〜50重量部である。
あるいは、本発明においては、薄膜トランジスタを、基板上に設けられるゲート電極と、前記ゲート電極を覆うように設けられるゲート絶縁膜と、前記ゲート絶縁膜の表面のうち一部を覆うように設けられるソース電極およびドレイン電極と、前記ゲート絶縁膜、ソース電極およびドレイン電極の表面に跨って設けられる半導体層とを備え、前記半導体層が、In、Ga、およびZnのうち少なくとも1種の元素を含むアモルファス酸化物半導体からなるスパッタ膜から構成され、前記ゲート絶縁膜が、プロトン性極性基を有する環状オレフィン重合体(A)と、前記プロトン性極性基と反応するエポキシ基を分子内に2以上有するエポキシ系架橋剤(B)とを含有する樹脂組成物から構成されるものとすることができる。
さらに、本発明においては、薄膜トランジスタを、基板上に設けられるゲート電極と、前記ゲート電極を覆うように設けられるゲート絶縁膜と、前記ゲート絶縁膜の表面に設けられる半導体層と、前記半導体層の表面の一部に設けられるエッチストッパーと、前記半導体層の表面および前記エッチストッパーの表面の一部に設けられるソース電極およびドレイン電極とを備え、前記半導体層が、In、Ga、およびZnのうち少なくとも1種の元素を含むアモルファス酸化物半導体からなるスパッタ膜から構成され、前記ゲート絶縁膜が、プロトン性極性基を有する環状オレフィン重合体(A)と、前記プロトン性極性基と反応するエポキシ基を分子内に2以上有するエポキシ系架橋剤(B)とを含有する樹脂組成物から構成されるものとすることができる。
以下においては、まず、本発明で用いるゲート絶縁膜を形成するための樹脂組成物について説明する。
本発明で用いるゲート絶縁膜を形成するための樹脂組成物は、プロトン性極性基を有する環状オレフィン重合体(A)と、プロトン性極性基と反応するエポキシ基を分子内に2以上有するエポキシ系架橋剤(B)とを含有する。
本発明で用いるプロトン性極性基を有する環状オレフィン重合体(A)(以下、単に「環状オレフィン重合体(A)」とする。)は、1または2以上の環状オレフィン単量体の重合体、または、1または2以上の環状オレフィン単量体と、これと共重合可能な単量体との共重合体が挙げられるが、本発明においては、環状オレフィン重合体(A)を形成するための単量体として、少なくともプロトン性極性基を有する環状オレフィン単量体(a)を用いることが好ましい。
本発明において、プロトン性極性基を有する環状オレフィン樹脂に結合しているプロトン性極性基の数に特に限定はなく、また、相異なる種類のプロトン性極性基が含まれていてもよい。
これら単量体(b2)は、それぞれ単独で用いてもよく、2種以上を組み合わせて用いてもよい。
これら単量体(b3)は、それぞれ単独で用いてもよく、2種以上を組み合わせて用いてもよい。
プロトン性極性基を有しない重合体は、上述した単量体(b1)および(b2)のうち少なくとも一種と、必要に応じて単量体(b3)とを任意に組み合わせて重合することによって得ることができる。
このような化合物の具体例としては、アクリル酸、メタクリル酸、アンゲリカ酸、チグリン酸、オレイン酸、エライジン酸、エルカ酸、ブラシジン酸、マレイン酸、フマル酸、シトラコン酸、メサコン酸、イタコン酸、アトロパ酸、ケイ皮酸等の不飽和カルボン酸;アリルアルコール、メチルビニルメタノール、クロチルアルコール、メタリルアルコール、1−フェニルエテン−1−オール、2−プロペン−1−オール、3−ブテン−1−オール、3−ブテン−2−オール、3−メチル−3−ブテン−1−オール、3−メチル−2−ブテン−1−オール、2−メチル−3−ブテン−2−オール、2−メチル−3−ブテン−1−オール、4−ペンテン−1−オール、4−メチル−4−ぺンテン−1−オール、2−ヘキセン−1−オール等の不飽和アルコール;等が挙げられる。
これら変性剤を用いた重合体の変性反応は、常法に従えばよく、通常、ラジカル発生剤の存在下で行われる。
また、環状オレフィン重合体(A)の分子量分布は、重量平均分子量/数平均分子量(Mw/Mn)比で、通常、4以下、好ましくは3以下、より好ましくは2.5以下である。なお、環状オレフィン重合体(A)の重量平均分子量(Mw)や分子量分布(Mw/Mn)は、テトラヒドロフラン等の溶媒を溶離液としたゲル・パーミエーション・クロマトグラフィー(GPC)により、ポリスチレン換算値として求められる値である。
本発明で用いるゲート絶縁膜を形成するための樹脂組成物は、上述した環状オレフィン重合体(A)に加えて、環状オレフィン重合体(A)のプロトン性極性基と反応するエポキシ基を分子内に2以上有するエポキシ系架橋剤(B)(以下、単に「エポキシ系架橋剤(B)」とする。)を含有する。
本発明で用いるゲート絶縁膜を形成するための樹脂組成物は、上述した環状オレフィン重合体(A)およびエポキシ系架橋剤(B)に加えて、メラミン系架橋剤(C)をさらに含有していることが好ましい。メラミン系架橋剤(C)をさらに含有させることにより、得られるゲート絶縁膜の耐熱性および耐プラズマ性をより向上させることができ、これにより、半導体膜を形成するためにスパッタリングを行った際における、スパッタリングを行った際に発生する熱やプラズマに起因する、ゲート絶縁膜の劣化の抑制効果をより高めることができる。
本発明で用いる樹脂組成物には、さらに、溶剤が含有されていてもよい。溶剤としては、特に限定されず、樹脂組成物の溶剤として公知のもの、例えばアセトン、メチルエチルケトン、シクロペンタノン、2−ヘキサノン、3−ヘキサノン、2−ヘプタノン、3−ヘプタノン、4−ヘプタノン、2−オクタノン、3−オクタノン、4−オクタノンなどの直鎖のケトン類;n−プロピルアルコール、イソプロピルアルコール、n−ブチルアルコール、シクロヘキサノールなどのアルコール類;エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、ジオキサンなどのエーテル類;エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテルなどのアルコールエーテル類;ギ酸プロピル、ギ酸ブチル、酢酸プロピル、酢酸ブチル、プロピオン酸メチル、プロピオン酸エチル、酪酸メチル、酪酸エチル、乳酸メチル、乳酸エチルなどのエステル類;セロソルブアセテート、メチルセロソルブアセテート、エチルセロソルブアセテート、プロピルセロソルブアセテート、ブチルセロソルブアセテートなどのセロソルブエステル類;プロピレングリコール、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノブチルエーテルなどのプロピレングリコール類;ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールメチルエチルエーテルなどのジエチレングリコール類;γ−ブチロラクトン、γ−バレロラクトン、γ−カプロラクトン、γ−カプリロラクトンなどの飽和γ−ラクトン類;トリクロロエチレンなどのハロゲン化炭化水素類;トルエン、キシレンなどの芳香族炭化水素類;ジメチルアセトアミド、ジメチルホルムアミド、N−メチルアセトアミドなどの極性溶媒などが挙げられる。これらの溶剤は、単独でも2種以上を組み合わせて用いてもよい。溶剤の含有量は、環状オレフィン重合体(A)100重量部に対して、好ましくは10〜10000重量部、より好ましくは50〜5000重量部、さらに好ましくは100〜1000重量部の範囲である。なお、樹脂組成物に溶剤を含有させる場合には、溶剤は、通常、ゲート絶縁膜形成後に除去されることとなる。
これらの酸化防止剤は、それぞれ単独でまたは2種以上を組み合わせて用いることができる。
ポリオキシアルキレン系界面活性剤としては、例えば、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル等のポリオキシエチレンアルキルエーテル類、ポリエチレングリコールジラウレート、ポリエチレングリコールジステアレートポリオキシエチレンジアルキルエステル類などを挙げることができる。
これらの界面活性剤は、それぞれ単独でまたは2種以上を組み合わせて用いることができる。
これらの酸性基又は熱潜在性酸性基を有する化合物は、それぞれ単独で又は2種以上を組み合わせて用いることができる。
酸性基としては、酸性の官能基であればよく、その具体例としては、スルホン酸基、リン酸基等の強酸性基;カルボキシ基、チオール基およびカルボキシメチレンチオ基等の弱酸性基;が挙げられる。これらの中でも、カルボキシ基、チオール基又はカルボキシメチレンチオ基が好ましく、カルボキシ基が特に好ましい。また、これらの酸性基の中でも、酸解離定数pKaが3.5以上5.0以下の範囲にあるものが好ましい。なお、酸性基が2つ以上ある場合は第一解離定数pKa1を酸解離定数とし、第一解離定数pKa1が上記範囲にあるものが好ましい。また、pKaは、希薄水溶液条件下で、酸解離定数Ka=[H3O+][B−]/[BH]を測定し、pKa=−logKaにしたがって、求められる。ここでBHは、有機酸を表し、B−は有機酸の共役塩基を表す。
なお、pKaの測定方法は、例えばpHメータを用いて水素イオン濃度を測定し、該当物質の濃度と水素イオン濃度から算出することができる。
このような置換基としては、アルキル基、アリール基等の炭化水素基のほか、ハロゲン原子;アルコキシ基、アリールオキシ基、アシルオキシ基、ヘテロ環オキシ基;アルキル基又はアリール基又は複素環基で置換されたアミノ基、アシルアミノ基、ウレイド基、スルファモイルアミノ基、アルコキシカルボニルアミノ基、アリールオキシカルボニルアミノ基;アルキルチオ基、アリールチオ基、ヘテロ環チオ基;等のプロトンを有しない極性基、これらのプロトンを有しない極性基で置換された炭化水素基、等を挙げることができる。
これらの中でも、得られるゲート絶縁膜の密着性をより高めることができるという観点から、酸性基を有する化合物における酸性基の数は、2つ以上であることが好ましい。
混合の方法は特に限定されないが、樹脂組成物を構成する各成分を溶剤に溶解又は分散して得られる溶液又は分散液を混合するのが好ましい。これにより、樹脂組成物は、溶液又は分散液の形態で得られる。
次いで、本発明の薄膜トランジスタについて、説明する。本発明の薄膜トランジスタは、上述した樹脂組成物からなるゲート絶縁膜と、該ゲート絶縁膜上に形成される半導体層とを有し、前記半導体層が、In、Ga、およびZnのうち少なくとも1種の元素を含むアモルファス酸化物半導体からなるスパッタ膜から構成されるものである。図1に、本発明の薄膜トランジスタの一例としての薄膜トランジスタ1の断面図を示す。図1に示すように、薄膜トランジスタ1は、基板2上に、ゲート電極3、上述した樹脂組成物からなるゲート絶縁膜4、半導体層5、ソース電極6およびドレイン電極7を有する、ボトムゲートトップコンタクト型の薄膜トランジスタである。なお、図1においては、単一の薄膜トランジスタ1を示したが、基板2上に複数の薄膜トランジスタ1が形成されているような構成(たとえば、アクティブマトリックス基板など)であってもよい。また、図1に示す薄膜トランジスタ1は、本発明の薄膜トランジスタの一例であり、以下においては、図1に示す薄膜トランジスタ1を例示して説明を行なうが、本発明の薄膜トランジスタは、図1に示す構成に何ら限定されるものではない。
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の電気特性を大気下・暗室中にて、半導体パラメーターアナライザー(Agilent社製、4156C)を用いて評価した。その結果、得られた薄膜トランジスタは、p型のトランジスタ素子としての特性を示した。そして、ドレイン電圧Vdを、Vd=10Vに固定し、ゲート電圧(Vg)をVg=+20V〜−20Vまで変化させることによって、半導体パラメーターアナライザーを用いて、伝達特性の評価を行った。なお、得られた薄膜トランジスタは飽和領域を有するものであり、本実施例においては、この飽和領域から電界効果移動度を求めた。
また、薄膜トランジスタの電界効果移動度の算出には、以下の式を用いた。なお、移動度は高いほど好ましい。
Id=μCinW(Vg−Vth)2/2L
(ただし、Cinはゲート絶縁膜の単位面積あたりの静電容量、Wはチャネル幅、Lはチャネル長、Vgはゲート電圧、Idはドレイン電流、μは移動度、Vthはチャネルが形成し始めるゲートの閾値電圧である。)
得られた薄膜トランジスタについて、半導体テスター(アドバンテスト社製、R6425)を用いて、オン時の電流と、オフ時の電流とを測定し、これらの比率を算出することにより、オン/オフ比(オン/オフ電流比率)の測定を行なった。オン/オフ比は高いほど好ましく、本実施例では、1×105以上を良好とした。
得られた薄膜トランジスタについて、大気下・暗室中にて、ソース電極とドレイン電極の間に20Vの電圧を印加し、ゲート電極に印加する電圧を+20V〜−20Vに変化させて、ソース電極とドレイン電極との間に流れる電流を、マニュアルプローバーおよび半導体パラメータアナライザー(Agilent社製、4156C)を用いて測定することで、リーク電流の測定を行なった。リーク電流は低いほど好ましく、本実施例では、1×10−12以下を良好とした。
<環状オレフィン重合体(A−1)の調製>
N−(2−エチルヘキシル)−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60モル%からなる単量体混合物100部、1,5−ヘキサジエン2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>
環状オレフィン重合体(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)、エポキシ系架橋剤(B)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(商品名「エポリードGT401」、ダイセル化学工業社製、環式エポキシ基を有する脂肪族環状4官能性のエポキシ樹脂、分子量(Mw)=730)30部、酸化剤として、ペンタエリズリトール−テトラキス[3−(3,5−ジ−tert−ブチル−4−ヒドロキシフェニル)プロピオナート](商品名「Irganox1010」、BASF社製)1.5部、界面活性剤として、シリコーン系界面活性剤(商品名「KP341」、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ジメチルエーテル100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、上記にて得られた樹脂組成物を用いて図1に示す薄膜トランジスタ1を得た。なお、図3は、薄膜トランジスタ1の製造方法を示す図である。
(1)前処理
ガラス基板を準備し、準備したガラス基板を純水中で超音波洗浄し、エアーブロー乾燥後、100℃で1時間ベーキングした。
(2)ゲート電極の形成
次いで、図3(A)に示すように、上記にて前処理したガラス基板(基板2)上に、真空蒸着法によりアルミニウム層を形成し、このアルミニウム層をパターニングすることにより、ゲート電極3を形成した。なお、ゲート電極3の厚みは50nmとした。
(3)ゲート絶縁膜の形成
次いで、ゲート電極3を形成した基板2をスピンコータに設置し、ガラス基板2上に、上記にて得られた樹脂組成物を所定量滴下し、基板2を約2000rpmの回転速度で約60秒間回転させることにより、塗膜を形成した。その後、塗膜が形成された基板2をホットプレートで150℃の温度で約60分間ベーキングすることにより、図3(B)に示すように、ゲート絶縁膜4を形成した。なお、ゲート絶縁膜4の厚みは200nmとした。
(4)半導体活性層の形成
次いで、図3(C)に示すように、ゲート電極3およびゲート絶縁膜4を形成した基板2のゲート絶縁膜4上に、スパッタリング法により、インジウムガリウム亜鉛酸化物(IGZO)のスパッタ膜からなる半導体層5を40nmの厚みで形成した。インジウムガリウム亜鉛酸化物(IGZO)のスパッタ膜は、スパッタリング装置(製品名「CFS−4EP−LL」、芝浦メカトロニクス社製」)を用いて、アルゴンガス存在下にて、出力300W、アルゴン流量10sccm、酸素流量10sccm、製膜圧0.6Paの条件にて形成した。なお、スパッタリングのターゲットとしては、インジウムガリウム亜鉛酸化物(IGZO)を用いた。
(5) ソース電極およびドレイン電極の形成
次いで、ゲート電極3、ゲート絶縁膜4および半導体層5を形成した基板2の半導体層5上に、真空蒸着法によって金を堆積し、この金層をパターニングすることにより、ソース電極6およびドレイン電極7を形成することで、図3(D)に示す薄膜トランジスタ1を得た。なお、ソース電極6およびドレイン電極7の厚みは50nmとした。
ゲート絶縁膜4を形成するための樹脂組成物を調製する際に、エポキシ系架橋剤(B)としての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−カプロラクトンの配合量を30部から50部に変更した以外は、実施例1と同様にして、樹脂組成物および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。
ゲート絶縁膜4を形成するための樹脂組成物を調製する際に、エポキシ系架橋剤(B)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30部の代わりに、2,2−ビス(ヒドロキシメチル)1−ブタノールの1,2−エポキシ−4−(2−オキシラニル)シクロヘキサン付加物(商品名「EHPE3150」、ダイセル化学工業社製、シクロヘキサン骨格および末端エポキシ基を有する15官能性の脂環式エポキシ樹脂、分子量(Mw)=2234)30部を使用した以外は、実施例1と同様にして、樹脂組成物および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。
ゲート絶縁膜4を形成するための樹脂組成物を調製する際に、エポキシ系架橋剤(B)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30部に加えて、2,2−ビス(ヒドロキシメチル)1−ブタノールの1,2−エポキシ−4−(2−オキシラニル)シクロヘキサン付加物30部をさらに使用した以外は、実施例1と同様にして、樹脂組成物および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。
ゲート絶縁膜4を形成するための樹脂組成物を調製する際に、メラミン系架橋剤(C)として、N,N,N’,N’,N’’,N’’−(ヘキサアルコキシアルキル)メラミンの部分メチロール置換体(商品名「サイメル350」、サイテックインダストリーズ社製)30部をさらに使用した以外は、実施例1と同様にして、樹脂組成物および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。
ゲート絶縁膜4を形成するための樹脂組成物を調製する際に、メラミン系架橋剤(C)として、N,N,N’,N’,N’’,N’’−(ヘキサアルコキシアルキル)メラミンの部分メチロール置換体(商品名「サイメル370」、サイテックインダストリーズ社製)30部をさらに使用した以外は、実施例1と同様にして、樹脂組成物および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。
ゲート絶縁膜4を形成するための樹脂組成物を調製する際に、エポキシ系架橋剤(B)としての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−カプロラクトンを配合しなかった以外は、実施例1と同様にして、樹脂組成物および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。
ゲート絶縁膜4を形成するための樹脂組成物を調製する際に、エポキシ系架橋剤(B)としての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−カプロラクトンを配合しなかった以外は、実施例5と同様にして、樹脂組成物および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。
ゲート絶縁膜4を形成するための樹脂組成物を調製する際に、エポキシ系架橋剤(B)としての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−カプロラクトンを配合しなかった以外は、実施例6と同様にして、樹脂組成物および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。
半導体層5を、インジウムガリウム亜鉛酸化物(IGZO)のスパッタ膜に代えて、a−Si層(アモルファスシリコン層)で形成した以外は、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。なお、a−Si層(アモルファスシリコン層)は、CVD装置を用いて、100nmの厚みで形成した(後述する比較例5,6も同様。)。結果を表1に示す。
半導体層5を、インジウムガリウム亜鉛酸化物(IGZO)のスパッタ膜に代えて、a−Si層(アモルファスシリコン層)で形成した以外は、比較例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。
半導体層5を、インジウムガリウム亜鉛酸化物(IGZO)のスパッタ膜に代えて、a−Si層(アモルファスシリコン層)で形成した以外は、比較例3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。
さらに、ゲート絶縁膜4を、エポキシ系架橋剤(B)を含有しない樹脂組成物を用いて形成し、かつ、半導体層5を、a−Si層(アモルファスシリコン層)で形成した比較例4〜6では、得られる薄膜トランジスタは、移動度が低く、オン/オフ比およびリーク電流に劣るものであった。
2…基板
3…ゲート電極
4…ゲート絶縁膜
5…半導体層
6…ソース電極
7…ドレイン電極
Claims (6)
- ゲート絶縁膜と、前記ゲート絶縁膜上に形成される半導体層とを備える薄膜トランジスタであって、
前記半導体層が、In、Ga、およびZnのうち少なくとも1種の元素を含むアモルファス酸化物半導体からなるスパッタ膜から構成され、
前記ゲート絶縁膜が、プロトン性極性基を有する環状オレフィン重合体(A)と、前記プロトン性極性基と反応するエポキシ基を分子内に2以上有するエポキシ系架橋剤(B)とを含有する樹脂組成物から構成され、
前記樹脂組成物が、前記エポキシ系架橋剤(B)として、異なる2種類以上の化合物を含有することを特徴とする薄膜トランジスタ。 - 前記樹脂組成物中における、前記エポキシ系架橋剤(B)の含有量が、前記環状オレフィン重合体(A)100重量部に対して、10〜100重量部であることを特徴とする請求項1に記載の薄膜トランジスタ。
- 前記樹脂組成物が、前記エポキシ系架橋剤(B)として、分子量(Mw)が1,000未満の化合物と、分子量(Mw)が1,000以上の化合物とを含有することを特徴とする請求項1または2に記載の薄膜トランジスタ。
- 前記樹脂組成物が、前記エポキシ系架橋剤(B)として、末端エポキシ基を有する化合物と、脂環式エポキシ基を有する化合物とを含有することを特徴とする請求項1〜3のいずれかに記載の薄膜トランジスタ。
- 前記樹脂組成物が、メラミン系架橋剤(C)をさらに含有することを特徴とする請求項1〜4のいずれかに記載の薄膜トランジスタ。
- 前記樹脂組成物中における、前記メラミン系架橋剤(C)の含有量が、前記環状オレフィン重合体(A)100重量部に対して、10〜50重量部であることを特徴とする請求項5に記載の薄膜トランジスタ。
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