JP4411624B2 - Non-organic solvent type resist remover composition - Google Patents
Non-organic solvent type resist remover composition Download PDFInfo
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- JP4411624B2 JP4411624B2 JP2003108961A JP2003108961A JP4411624B2 JP 4411624 B2 JP4411624 B2 JP 4411624B2 JP 2003108961 A JP2003108961 A JP 2003108961A JP 2003108961 A JP2003108961 A JP 2003108961A JP 4411624 B2 JP4411624 B2 JP 4411624B2
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- 239000000203 mixture Substances 0.000 title claims description 44
- 239000003960 organic solvent Substances 0.000 title claims description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 31
- 150000001875 compounds Chemical class 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 15
- 150000002222 fluorine compounds Chemical class 0.000 claims description 12
- LLPKQRMDOFYSGZ-UHFFFAOYSA-N 2,5-dimethyl-1h-imidazole Chemical compound CC1=CN=C(C)N1 LLPKQRMDOFYSGZ-UHFFFAOYSA-N 0.000 claims description 8
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- -1 hydrogen acid Chemical class 0.000 claims description 8
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims description 6
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 4
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 4
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 claims description 3
- 125000003172 aldehyde group Chemical group 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000003368 amide group Chemical group 0.000 claims description 3
- 125000004103 aminoalkyl group Chemical group 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical group 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims 2
- 238000003682 fluorination reaction Methods 0.000 claims 1
- 235000021384 green leafy vegetables Nutrition 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 18
- 239000004065 semiconductor Substances 0.000 description 16
- 238000005260 corrosion Methods 0.000 description 15
- 230000007797 corrosion Effects 0.000 description 15
- 239000000758 substrate Substances 0.000 description 15
- 239000010408 film Substances 0.000 description 11
- 206010040844 Skin exfoliation Diseases 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000004973 liquid crystal related substance Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 6
- 229920002120 photoresistant polymer Polymers 0.000 description 6
- 229910000838 Al alloy Inorganic materials 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 238000004380 ashing Methods 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 1
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 1
- 125000006699 (C1-C3) hydroxyalkyl group Chemical group 0.000 description 1
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- JJWKKSUCSNDHNJ-UHFFFAOYSA-N 2-(2-methylimidazol-1-yl)ethanol Chemical compound CC1=NC=CN1CCO JJWKKSUCSNDHNJ-UHFFFAOYSA-N 0.000 description 1
- HOPOOSWMGTVLDJ-UHFFFAOYSA-N 2-[(2-chlorophenyl)methyl]-1H-pyrrole Chemical compound ClC1=C(CC2=CC=CN2)C=CC=C1 HOPOOSWMGTVLDJ-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- NZAARDFDMSTHAF-UHFFFAOYSA-N 2-prop-1-en-2-yl-1h-imidazole Chemical compound CC(=C)C1=NC=CN1 NZAARDFDMSTHAF-UHFFFAOYSA-N 0.000 description 1
- SDXAWLJRERMRKF-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazole Chemical compound CC=1C=C(C)NN=1 SDXAWLJRERMRKF-UHFFFAOYSA-N 0.000 description 1
- 229910018182 Al—Cu Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- JXDFEQONERDKSS-UHFFFAOYSA-N betazole Chemical compound NCCC=1C=CNN=1 JXDFEQONERDKSS-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012458 free base Substances 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Photosensitive Polymer And Photoresist Processing (AREA)
- Paints Or Removers (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、半導体集積回路、液晶パネルの半導体素子回路等の製造に用いられるレジスト剥離剤組成物に関する。さらに詳しくは、半導体基板上又は液晶ガラス基板上に配線を形成するときに生成するレジスト残渣の除去性能と基板上のアルミニウム防食性能との双方に優れた非有機溶剤型レジスト剥離剤組成物に関する。
【０００２】
【従来の技術】
レジスト剥離剤組成物は、半導体集積回路、液晶パネルの半導体素子回路等の製造に用いられるフォトレジストを剥離する際に用いられる。半導体素子回路又は付随する電極部の製造は、以下のように行われる。まず、シリコン、ガラス等の基板上に金属膜をＣＶＤやスパッタ等の方法で積層させる。その上面にフォトレジストを膜付けし、それを露光、現像等の処理でパターン形成する。パターン形成されたフォトレジストをマスクとして金属膜をエッチングする。その後、不要となったフォトレジストを剥離剤組成物を用いて剥離・除去した後、洗浄液で洗浄する。これらの操作を繰り返すことにより素子の形成が行われる。
【０００３】
従来、レジスト剥離剤組成物としては、アミン類と有機溶剤を主成分とする有機溶剤型剥離剤組成物が用いられている。通常、これらの剥離剤組成物を使用する場合は、高温で長時間処理を要する。
【０００４】
一方、フッ化水素酸などのフッ素化合物が半導体基板製造工程又は液晶用ガラス基板製造工程における配線形成時に生成するレジスト残渣除去に有効であることが知られている。例えば、フッ化水素酸、水溶性有機溶媒、並びに、芳香族ヒドロキシ化合物、アセチレンアルコール、カルボキシル基含有有機化合物、その無水物及びトリアゾール化合物から選ばれる少なくとも１種の防食剤を含有するレジスト剥離液組成物が知られている（例えば、特許文献１参照。）。また、フッ化水素酸と金属を含まない塩基との塩、水溶性有機溶媒及び水からなり、かつ水素イオン濃度(ｐＨ)が５〜８であるレジスト用剥離液組成物も知られている（例えば、特許文献２参照。）。
【０００５】
また、半導体装置製造工程において生成する保護堆積膜を、第四級アンモニウム塩とフッ素化合物を含有する水溶液、又は、第四級アンモニウム塩とフッ素化合物に、アミド類、ラクトン類、ニトリル類、アルコール類、エステル類から選ばれた有機溶媒を含有する水溶液、からなる半導体装置洗浄剤を用いて剥離する技術も知られている（例えば、特許文献３参照。）。また、特定の有機カルボン酸アンモニウム塩又は有機カルボン酸アミン塩、及びフッ素化合物を含有する水溶液からなるレジスト用剥離液も知られている（例えば、特許文献４参照。）。さらには、フッ素化合物及びベタイン化合物と、アミド類、ラクトン類、アルコール類から選ばれた１種以上の有機溶剤を含む半導体装置用洗浄剤が知られている（例えば、特許文献５参照。）。
【０００６】
ところで、レジスト剥離剤組成物にあっては、レジスト残渣除去性に優れていて、かつ、基板上に形成されたアルミニウム又はアルミニウム合金等の金属膜の腐食が良好に防止できることが要求される。しかし、上記の各種レジスト剥離剤組成物を用いても、レジスト残渣除去性とアルミニウム等の金属膜の防食性の両方を満足させることが出来ない。特に、上記組成物のうち、フッ素化合物を含有する剥離剤組成物は、アルミニウムもしくはアルミニウム合金の金属膜に対して、剥離工程中での腐食に加えて、剥離処理後の水洗工程における腐食も問題となっている。この水洗工程での腐食は、剥離処理後に基板に残存する剥離液が水により希釈され、腐食性を促進しているものと考えられる。従って、剥離工程中のみならず、剥離処理後の水洗工程においてもアルミニウムもしくはアルミニウム合金等の金属膜腐食を良好に抑制でき、かつ高いレジスト残渣除去性を兼ね備えた剥離剤組成物が望まれている。
【０００７】
【特許文献１】
特許第３２５５５５１号公報
【特許文献２】
特許第３２５５６２３号公報
【特許文献３】
特開平７−２０１７９４号公報
【特許文献４】
特開平７−２７１０５６号公報
【特許文献５】
特開平９−６２０１３号公報
【０００８】
【発明が解決しようとする課題】
上述の現状に鑑み、本発明の目的は、配線形成時に生成するレジスト残渣を高性能で除去すると同時に、剥離処理後の水洗工程における基板上のアルミニウム又はアルミニウム合金等の金属膜の腐食を良好に防止することができる非有機溶剤型レジスト剥離剤組成物を提供することにある。
【０００９】
【課題を解決するための手段】
本発明者は上記課題を解決するため種々の実験を重ねた結果、フッ化水素酸と水とを含有する非有機溶剤型剥離剤組成物において、特定の窒素含有環状化合物を含有させることで、レジスト残渣物を高性能で除去できると共に、アルミニウム配線の防食性も得られることを見出し、本発明を完成させるに至った。
【００１０】
従って、本発明は、下記（Ａ）一般式（１）〜（３）で示される化合物及び１，２，４−トリアゾールからなる群から選択される少なくとも１種の化合物、（Ｂ）フッ化水素酸及びフッ化アンモニウムからなる群から選択される少なくとも１種のフッ素化合物、及び、（Ｃ）水を含有し、（Ａ）成分の含有量が０．００１〜１０重量％、（Ｂ）成分の含有量が０．０００１〜１重量％、残部が水である非有機溶剤型レジスト剥離剤組成物、前記（Ａ）成分を０．００１〜１０重量％、前記（Ｂ）成分を０．０００１〜１重量％、（Ｄ）成分として酸を０．０１〜１０重量％、残部が水である非有機溶剤型レジスト剥離剤組成物。（以下、これらを本発明の組成物ともいう）である。
【００１１】
【化３】
式中、Ｒ１〜Ｒ１３は、それぞれ同一または異なって、水素、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシル基、炭素数１〜３のヒドロキシアルキル基、アルデヒド基、ヒドロキシル基、フェニル基、炭素数２〜４のアルケニル基、アミド基、炭素数１〜３のアミノアルキル基、ハロゲン、又は、置換基を有していてもよい炭素数７〜９のアラルキル基を表す。
【００１３】
本発明の別の態様において、一般式（１）で示される化合物が、イミダゾール、１，２−ジメチルイミダゾール、２，４−ジメチルイミダゾール、及び、１−ビニルイミダゾールからなる群から選択される少なくとも１種の化合物である。
本発明の更に別の態様において、一般式（２）で示される化合物はピラゾールである。
本発明の他の態様において、一般式（３）で示される化合物はピロールである。
本発明の更に他の態様において、一般式（４）で示される化合物は１，２，４−トリアゾールである。
本発明の別の態様において、フッ素化合物（Ｂ）はフッ化水素酸である。
以下、本発明を詳細に説明する。
【００１４】
【発明の実施の形態】
本発明の組成物は、非有機溶剤型レジスト剥離剤組成物である。なお、本明細書中、非有機溶剤型レジスト剥離剤組成物とは、有機溶剤を含有しないレジスト剥離剤組成物をいう。
本発明の組成物に含まれる一般式（１）で表される化合物としては、例えば、イミダゾール、１−メチルイミダゾール、２−メチルイミダゾール、４−メチルイミダゾール、２−フェニルイミダゾール、１，２−ジメチルイミダゾール、２，４−ジメチルイミダゾール、１−（β−ヒドロキシエチル）−２−メチルイミダゾール、１−ビニルイミダゾール、１−メチルビニルイミダゾールなどが挙げられる。これらは１種又は２種以上を組み合わせて用いることができる。これらのうち、イミダゾール、１，２−ジメチルイミダゾール、２，４−ジメチルイミダゾール、及び１−ビニルイミダゾールからなる群から選択される少なくとも１種の化合物が好ましい。
【００１５】
一般式（２）で表される化合物としては、例えば、ピラゾール、３，５−ジメチルピラゾール、３−β−アミノエチルピラゾールなどが挙げられる。これらは１種又は２種以上を組み合わせて用いることができる。これらのうち、ピラゾールが好ましい。
【００１６】
一般式（３）で表される化合物としては、例えば、ピロール、Ｎ−メチルピロール、Ｎ−（２−クロロベンジルピロール）などが挙げられる。これらは１種又は２種以上を組み合わせて用いることができる。これらのうち、ピロールが好ましい。
【００１７】
一般式（４）で表される化合物としては、例えば、１，２，４−トリアゾールなどが挙げられる。
【００１８】
本発明においては、成分（Ａ）として、上記一般式（１）〜（３）のいずれかで表される化合物又は１，２，４−トリアゾールのいずれか１種若しくは２種以上であってもよく、又は、これらの任意の組み合わせであってもよい。
【００１９】
成分（Ａ）の含有量は、本発明の組成物中、アルミニウム又はアルミニウム合金に対する防食効果の観点から、０．００１重量％以上が好ましく、経済性の観点及び効果の観点から１０重量％以下が好ましい。より好ましくは０．０１〜５重量％である。
【００２０】
フッ素化合物（Ｂ）としては、例えば、フッ化水素酸、フッ化アンモニウム等が挙げられる。これらは１種又は２種以上を組み合わせて用いることができる。これらのうち、フッ化水素酸が好ましい。
【００２１】
成分（Ｂ）の含有量は、本発明の組成物中、アルミニウムやシリコン酸化膜に対する腐食防止の観点から、１重量％以下が好ましく、レジスト残渣除去能力の観点から０．０００１重量％以上が好ましい。上限は、より好ましくは０．１重量％以下、さらに好ましくは０．０１重量％以下である。
【００２２】
成分（Ｄ）である酸としては、例えば、硝酸、燐酸、硫酸、塩酸などの無機酸；シュウ酸、乳酸、マロン酸、酢酸、没食子酸、クエン酸などの有機酸が挙げられる。上記酸は、剥離性の助剤として必要に応じて添加される。
【００２３】
成分（Ｄ）の含有量は、本発明の組成物中、０．１〜１０重量％が好ましく、より好ましくは０．１〜５重量％である。酸の含有量が０．１重量％未満の場合は、レジスト残渣に対する除去能力が低下することがある。他方１０重量％を超える場合は、アルミニウムに対する腐食が増す傾向にある。
【００２４】
水（Ｃ）は、残部添加される。
【００２５】
本発明の組成物は、水素イオン濃度が６以下、より好ましくは５以下、に調整されることが好ましい。水素イオン濃度の調節は、酸、無機アンモニウム塩、有機アンモニウム塩等の添加により行うことができる。
【００２６】
上記成分（Ａ）〜（Ｃ)又は成分（Ａ）、（Ｂ）、（Ｄ）を含む本発明の非有機溶剤型レジスト剥離剤組成物は、半導体基板上または液晶用ガラス基板上に配線を形成する際に生成するレジスト残渣を剥離・除去して配線を形成することができ、半導体集積回路、液晶パネルの半導体素子回路等の製造に好適に使用することができる。
【００２７】
本発明の組成物の使用方法の一例について説明する。半導体基板上又は液晶用ガラス基板上に金属薄膜をＣＶＤやスパッタ等により形成させる。その上面にフォトレジストを膜付けした後、露光、現像等の処理でパターン形成する。パターン形成されたフォトレジストをマスクとして金属薄膜をエッチングする。その後、アッシングによりレジストを灰化する。最後に灰化したレジスト残渣を本発明の組成物を用いて剥離・除去して配線等が形成された半導体素子が製造される。
【００２８】
【実施例】
以下に実施例を示して、本発明をさらに詳細に説明するが、本発明はこれらに限定されるものではない。
【００２９】
実施例１〜６、比較例１〜１０
シリコン酸化膜上にＴｉ、さらにその上にＴｉＮ、さらにその上にＡｌ-Ｃｕを膜付けした基板を、パターニングされたレジストをマスクとしてＣｌ２とＢＣｌ３を用いてドライエッチングし、続いて酸素プラズマアッシングした時に配線側壁又は上部に生成するレジスト残渣を剥離対象物とした。表１に示す剥離剤組成物の中に上述の対象物を２４℃で５分浸漬した後、２４℃の純水中に１分浸漬、さらに新たな２４℃の純水中に１分浸漬後、２４℃の純水シャワーにて１分水洗し、最後に窒素ガスで乾燥させた。走査電子顕微鏡（ＳＥＭ）にて剥離性（残渣除去性の程度）及びアルミニウムの腐食の程度を観察し、比較を行った。結果を表1に示す。なお、表１の剥離性において、◎は「残渣が全くない」、○は「残渣が殆どない」、△は「残渣が残っている」、×は「処理前の残渣状態とほとんど同じ」を示す。また、表１のアルミニウム防食性において、○は「腐食なし」、×は「配線が細る又は表面が荒れている」を示す。
【００３０】
表１中、略号は以下のとおりである。
ＤＭＳＯ：ジメチルスルホキシド
ＢＺＴ：ベンゾトリアゾール
【００３１】
【表１】
表１の実施例１〜６において、フッ化水素酸、水、及び、成分（Ａ）の化合物を添加することにより、又は、フッ化水素酸、水、成分（Ａ）の化合物、及び、成分（Ｄ）を添加することにより、アルミニウム配線に対する防食性と高いレジスト残渣剥離性を両立する結果が得られた。比較例１は、フッ化水素酸及び水からなる組成であるが、成分（Ａ）の化合物が添加されていないためアルミニウム配線の腐食が大きかった。比較例２は、フッ化水素酸及び水からなる組成に、水溶性有機溶剤を含有させた組成物であるが、レジスト残渣除去性が低下し、さらにアルミニウム配線の腐食が見られた。比較例３〜５は、フッ化水素酸を含有していないため、レジスト残渣除去性が悪かった。比較例６〜１０は、フッ化水素酸と水からなる組成物に、公知のアルミニウム防食剤を添加した例であるが、レジスト残渣除去性は良かったものの、アルミニウム配線の腐食を防止できなかった。
【００３３】
【発明の効果】
本発明は上述の構成により、本発明の非有機溶剤型レジスト剥離剤組成物を半導体または液晶用の素子回路等の製造工程における配線形成時に生成するレジスト残渣の除去に用いることにより、レジスト残渣が高性能で除去されるとともに、剥離工程中及び剥離処理後の水洗工程における、基板上のアルミニウム等の金属配線の腐食を良好に防止することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a resist remover composition used in the production of semiconductor integrated circuits, semiconductor element circuits of liquid crystal panels, and the like. More specifically, the present invention relates to a non-organic solvent-type resist remover composition that is excellent in both removal performance of resist residues generated when forming wiring on a semiconductor substrate or a liquid crystal glass substrate and aluminum anticorrosion performance on the substrate.
[0002]
[Prior art]
The resist remover composition is used when removing a photoresist used for manufacturing a semiconductor integrated circuit, a semiconductor element circuit of a liquid crystal panel, and the like. Manufacture of a semiconductor element circuit or an accompanying electrode part is performed as follows. First, a metal film is laminated on a substrate such as silicon or glass by a method such as CVD or sputtering. A photoresist is formed on the upper surface, and a pattern is formed by processing such as exposure and development. The metal film is etched using the patterned photoresist as a mask. Thereafter, the unnecessary photoresist is stripped and removed using a stripper composition, and then washed with a cleaning liquid. Elements are formed by repeating these operations.
[0003]
Conventionally, as a resist stripper composition, an organic solvent-type stripper composition containing amines and an organic solvent as main components has been used. Usually, when these release agent compositions are used, treatment at a high temperature for a long time is required.
[0004]
On the other hand, it is known that a fluorine compound such as hydrofluoric acid is effective for removing a resist residue generated during wiring formation in a semiconductor substrate manufacturing process or a liquid crystal glass substrate manufacturing process. For example, a resist stripping solution composition containing hydrofluoric acid, a water-soluble organic solvent, and at least one anticorrosive agent selected from aromatic hydroxy compounds, acetylene alcohols, carboxyl group-containing organic compounds, anhydrides thereof, and triazole compounds The thing is known (for example, refer patent document 1). Also known is a resist stripping composition comprising a salt of hydrofluoric acid and a metal-free base, a water-soluble organic solvent, and water, and having a hydrogen ion concentration (pH) of 5 to 8 ( For example, see Patent Document 2.)
[0005]
In addition, the protective deposition film generated in the semiconductor device manufacturing process may be an aqueous solution containing a quaternary ammonium salt and a fluorine compound, or a quaternary ammonium salt and a fluorine compound, amides, lactones, nitriles, alcohols. There is also known a technique of peeling using a semiconductor device cleaner comprising an aqueous solution containing an organic solvent selected from esters (see, for example, Patent Document 3). Further, a resist stripping solution made of an aqueous solution containing a specific organic carboxylic acid ammonium salt or organic carboxylic acid amine salt and a fluorine compound is also known (for example, see Patent Document 4). Furthermore, a semiconductor device cleaning agent containing a fluorine compound and a betaine compound and one or more organic solvents selected from amides, lactones, and alcohols is known (for example, see Patent Document 5).
[0006]
By the way, the resist remover composition is required to have excellent resist residue removability and to be able to satisfactorily prevent corrosion of a metal film such as aluminum or aluminum alloy formed on the substrate. However, even if the above-mentioned various resist remover compositions are used, it is not possible to satisfy both resist residue removal properties and corrosion resistance of a metal film such as aluminum. In particular, among the above compositions, the release agent composition containing a fluorine compound has a problem of corrosion in the water washing step after the peeling treatment, in addition to the corrosion in the peeling step, on the metal film of aluminum or aluminum alloy. It has become. Corrosion in this water washing step is considered to promote the corrosiveness because the stripping solution remaining on the substrate after the stripping treatment is diluted with water. Accordingly, there is a demand for a release agent composition that can satisfactorily suppress corrosion of a metal film such as aluminum or an aluminum alloy and has high resist residue removability not only during the peeling step but also in the water washing step after the peeling treatment. .
[0007]
[Patent Document 1]
Japanese Patent No. 3255551 [Patent Document 2]
Japanese Patent No. 3255623 [Patent Document 3]
JP-A-7-201794 [Patent Document 4]
Japanese Patent Laid-Open No. 7-271056 [Patent Document 5]
Japanese Patent Laid-Open No. 9-62013
[Problems to be solved by the invention]
In view of the above-mentioned present situation, the object of the present invention is to remove resist residues generated at the time of wiring formation with high performance, and at the same time, to satisfactorily corrode metal films such as aluminum or aluminum alloy on the substrate in the water washing step after the peeling treatment. An object of the present invention is to provide a non-organic solvent resist stripper composition that can be prevented.
[0009]
[Means for Solving the Problems]
As a result of repeating various experiments to solve the above-mentioned problems, the present inventor contains a specific nitrogen-containing cyclic compound in a non-organic solvent-type release agent composition containing hydrofluoric acid and water. The present inventors have found that the resist residue can be removed with high performance and the corrosion resistance of the aluminum wiring can be obtained, and the present invention has been completed.
[0010]
Accordingly, the present invention provides (A) at least one compound selected from the group consisting of compounds represented by the following general formulas (1) to (3) and 1,2,4-triazole, (B) hydrogen fluoride Containing at least one fluorine compound selected from the group consisting of an acid and ammonium fluoride, and (C) water, wherein the content of component (A) is 0.001 to 10% by weight, Non-organic solvent-type resist remover composition having a content of 0.0001 to 1% by weight, the balance being water, 0.001 to 10% by weight of the component (A), and 0.0001 to the component (B) A non-organic solvent-type resist remover composition comprising 1% by weight, 0.01 to 10% by weight of acid as component (D), and the balance being water. (Hereinafter, these are also referred to as the compositions of the present invention).
[0011]
[Chemical 3]
In formula, R < 1 > -R < 13 > is the same or different, respectively, hydrogen, a C1-C3 alkyl group, a C1-C3 alkoxyl group, a C1-C3 hydroxyalkyl group, an aldehyde group, hydroxyl Represents a group, a phenyl group, an alkenyl group having 2 to 4 carbon atoms, an amide group, an aminoalkyl group having 1 to 3 carbon atoms, a halogen, or an aralkyl group having 7 to 9 carbon atoms which may have a substituent. .
[0013]
In another embodiment of the present invention, the compound represented by the general formula (1) is at least one selected from the group consisting of imidazole, 1,2-dimethylimidazole, 2,4-dimethylimidazole, and 1-vinylimidazole. A kind of compound.
In still another embodiment of the present invention, the compound represented by the general formula (2) is pyrazole.
In another embodiment of the present invention, the compound represented by the general formula (3) is pyrrole.
In still another embodiment of the present invention, the compound represented by the general formula (4) is 1,2,4-triazole.
In another embodiment of the present invention, the fluorine compound (B) is hydrofluoric acid.
Hereinafter, the present invention will be described in detail.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
The composition of the present invention is a non-organic solvent resist stripper composition. In addition, in this specification, a non-organic solvent type resist remover composition means a resist remover composition that does not contain an organic solvent.
Examples of the compound represented by the general formula (1) contained in the composition of the present invention include imidazole, 1-methylimidazole, 2-methylimidazole, 4-methylimidazole, 2-phenylimidazole, and 1,2-dimethyl. Examples include imidazole, 2,4-dimethylimidazole, 1- (β-hydroxyethyl) -2-methylimidazole, 1-vinylimidazole, 1-methylvinylimidazole and the like. These can be used alone or in combination of two or more. Among these, at least one compound selected from the group consisting of imidazole, 1,2-dimethylimidazole, 2,4-dimethylimidazole, and 1-vinylimidazole is preferable.
[0015]
Examples of the compound represented by the general formula (2) include pyrazole, 3,5-dimethylpyrazole, and 3-β-aminoethylpyrazole. These can be used alone or in combination of two or more. Of these, pyrazole is preferred.
[0016]
Examples of the compound represented by the general formula (3) include pyrrole, N-methylpyrrole, N- (2-chlorobenzylpyrrole) and the like. These can be used alone or in combination of two or more. Of these, pyrrole is preferred.
[0017]
Examples of the compound represented by the general formula (4) include 1,2,4-triazole.
[0018]
In the present invention, the component (A) may be a compound represented by any one of the general formulas (1) to ( 3 ) or any one or more of 1,2,4-triazole. Or any combination thereof.
[0019]
The content of the component (A) is preferably 0.001% by weight or more from the viewpoint of the anticorrosive effect on aluminum or aluminum alloy in the composition of the present invention, and is preferably 10% by weight or less from the viewpoint of economy and effect. preferable. More preferably, it is 0.01 to 5 weight%.
[0020]
Examples of the fluorine compound (B) include hydrofluoric acid and ammonium fluoride. These can be used alone or in combination of two or more. Of these, hydrofluoric acid is preferred.
[0021]
The content of the component (B) is preferably 1% by weight or less from the viewpoint of preventing corrosion of aluminum or silicon oxide film in the composition of the present invention, and preferably 0.0001% by weight or more from the viewpoint of resist residue removing ability. . The upper limit is more preferably 0.1% by weight or less, and still more preferably 0.01% by weight or less.
[0022]
Examples of the acid that is component (D) include inorganic acids such as nitric acid, phosphoric acid, sulfuric acid, and hydrochloric acid; and organic acids such as oxalic acid, lactic acid, malonic acid, acetic acid, gallic acid, and citric acid. The acid is added as necessary as a peeling aid.
[0023]
The content of component (D) is preferably 0.1 to 10% by weight, more preferably 0.1 to 5% by weight in the composition of the present invention. When the acid content is less than 0.1% by weight, the ability to remove resist residues may be reduced. On the other hand, when it exceeds 10% by weight, corrosion to aluminum tends to increase.
[0024]
The balance of water (C) is added.
[0025]
The composition of the present invention is preferably adjusted to have a hydrogen ion concentration of 6 or less, more preferably 5 or less. The hydrogen ion concentration can be adjusted by adding an acid, an inorganic ammonium salt, an organic ammonium salt, or the like.
[0026]
The non-organic solvent-type resist remover composition of the present invention containing the above components (A) to (C) or components (A) , (B), (D) is provided on a semiconductor substrate or a liquid crystal glass substrate. The resist residue generated at the time of formation can be peeled and removed to form a wiring, which can be suitably used for manufacturing a semiconductor integrated circuit, a semiconductor element circuit of a liquid crystal panel, and the like.
[0027]
An example of how to use the composition of the present invention will be described. A metal thin film is formed on a semiconductor substrate or a glass substrate for liquid crystal by CVD or sputtering. After a photoresist film is formed on the upper surface, a pattern is formed by processing such as exposure and development. The metal thin film is etched using the patterned photoresist as a mask. Thereafter, the resist is ashed by ashing. Finally, the ashed resist residue is peeled and removed using the composition of the present invention to produce a semiconductor element in which wirings and the like are formed.
[0028]
【Example】
The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.
[0029]
Examples 1-6, Comparative Examples 1-10
A substrate on which Ti is deposited on a silicon oxide film, TiN is further deposited thereon, and Al-Cu is further deposited thereon is dry-etched using Cl 2 and BCl 3 with a patterned resist as a mask, followed by oxygen plasma. The resist residue generated on the wiring side wall or the upper part when ashing was used as a peeling target. After immersing the above-mentioned object in the release agent composition shown in Table 1 at 24 ° C. for 5 minutes, then immersing in pure water at 24 ° C. for 1 minute, and further immersing in new pure water at 24 ° C. for 1 minute. Washed with a pure water shower at 24 ° C. for 1 minute, and finally dried with nitrogen gas. The peelability (degree of residue removal) and the degree of corrosion of aluminum were observed and compared with a scanning electron microscope (SEM). The results are shown in Table 1. In the peelability of Table 1, ◎ means “no residue”, ○ means “little residue”, △ means “residue remains”, and × means “almost the same as the residue state before treatment”. Show. Further, in the aluminum anticorrosive properties in Table 1, “◯” indicates “no corrosion”, and “×” indicates “the wiring is thin or the surface is rough”.
[0030]
In Table 1, abbreviations are as follows.
DMSO: dimethyl sulfoxide BZT: benzotriazole
[Table 1]
In Examples 1 to 6 of Table 1, by adding hydrofluoric acid, water, and the compound of component (A), or hydrofluoric acid, water, compound of component (A), and component By adding (D), a result that achieved both anticorrosiveness against aluminum wiring and high resist residue peelability was obtained. Although the comparative example 1 is a composition which consists of hydrofluoric acid and water, since the compound of the component (A) was not added, corrosion of aluminum wiring was large. Comparative Example 2 is a composition in which a water-soluble organic solvent is contained in a composition composed of hydrofluoric acid and water, but the resist residue removability is reduced, and further corrosion of aluminum wiring is observed. Since Comparative Examples 3 to 5 did not contain hydrofluoric acid, the resist residue removability was poor. Comparative Examples 6 to 10 are examples in which a known aluminum anticorrosive was added to a composition comprising hydrofluoric acid and water, but although resist residue removal was good, corrosion of aluminum wiring could not be prevented. .
[0033]
【The invention's effect】
With the above-described configuration, the present invention uses the non-organic solvent-type resist stripper composition of the present invention to remove a resist residue generated during wiring formation in a manufacturing process of an element circuit for a semiconductor or liquid crystal. While being removed with high performance, corrosion of metal wiring such as aluminum on the substrate can be satisfactorily prevented during the peeling process and in the water washing process after the peeling process.
Claims (6)
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| Application Number | Priority Date | Filing Date | Title |
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| JP2003108961A JP4411624B2 (en) | 2003-04-14 | 2003-04-14 | Non-organic solvent type resist remover composition |
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|---|---|---|---|
| JP2003108961A JP4411624B2 (en) | 2003-04-14 | 2003-04-14 | Non-organic solvent type resist remover composition |
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| JP2004317641A JP2004317641A (en) | 2004-11-11 |
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| US7550075B2 (en) | 2005-03-23 | 2009-06-23 | Tokyo Electron Ltd. | Removal of contaminants from a fluid |
| US7399708B2 (en) * | 2005-03-30 | 2008-07-15 | Tokyo Electron Limited | Method of treating a composite spin-on glass/anti-reflective material prior to cleaning |
| US7442636B2 (en) | 2005-03-30 | 2008-10-28 | Tokyo Electron Limited | Method of inhibiting copper corrosion during supercritical CO2 cleaning |
| JP4758187B2 (en) * | 2005-09-26 | 2011-08-24 | 関東化学株式会社 | Photoresist residue and polymer residue remover |
| WO2008090418A1 (en) * | 2007-01-22 | 2008-07-31 | Freescale Semiconductor, Inc. | Liquid cleaning composition and method for cleaning semiconductor devices |
| JPWO2010041333A1 (en) * | 2008-10-10 | 2012-03-01 | アクアサイエンス株式会社 | Stripping solution and object cleaning method |
| JP5498768B2 (en) * | 2009-12-02 | 2014-05-21 | 東京応化工業株式会社 | Lithographic cleaning liquid and wiring forming method |
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