JP4478908B2 - Resist stripper composition - Google Patents
Resist stripper composition Download PDFInfo
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- JP4478908B2 JP4478908B2 JP2001032243A JP2001032243A JP4478908B2 JP 4478908 B2 JP4478908 B2 JP 4478908B2 JP 2001032243 A JP2001032243 A JP 2001032243A JP 2001032243 A JP2001032243 A JP 2001032243A JP 4478908 B2 JP4478908 B2 JP 4478908B2
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- ammonium
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- 239000000203 mixture Substances 0.000 title claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 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 16
- 239000003960 organic solvent Substances 0.000 claims description 14
- 150000001875 compounds Chemical group 0.000 claims description 11
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 6
- 239000004251 Ammonium lactate Substances 0.000 claims description 6
- GEHMBYLTCISYNY-UHFFFAOYSA-N Ammonium sulfamate Chemical compound [NH4+].NS([O-])(=O)=O GEHMBYLTCISYNY-UHFFFAOYSA-N 0.000 claims description 6
- 229940059265 ammonium lactate Drugs 0.000 claims description 6
- 235000019286 ammonium lactate Nutrition 0.000 claims description 6
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 claims description 6
- RZOBLYBZQXQGFY-HSHFZTNMSA-N azanium;(2r)-2-hydroxypropanoate Chemical compound [NH4+].C[C@@H](O)C([O-])=O RZOBLYBZQXQGFY-HSHFZTNMSA-N 0.000 claims description 6
- 238000005260 corrosion Methods 0.000 description 22
- 230000007797 corrosion Effects 0.000 description 22
- 229910052782 aluminium Inorganic materials 0.000 description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 20
- 239000000758 substrate Substances 0.000 description 16
- 239000004065 semiconductor Substances 0.000 description 15
- 150000002222 fluorine compounds Chemical class 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000010408 film Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 229920002120 photoresistant polymer Polymers 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000004973 liquid crystal related substance Substances 0.000 description 7
- 239000011521 glass Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 206010040844 Skin exfoliation Diseases 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- -1 carboxylic acid ammonium salt Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 2
- 239000005695 Ammonium acetate Substances 0.000 description 2
- 229940126062 Compound A Drugs 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229940043376 ammonium acetate Drugs 0.000 description 2
- 235000019257 ammonium acetate Nutrition 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 238000004380 ashing Methods 0.000 description 2
- 239000012459 cleaning agent Substances 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 239000007788 liquid Substances 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
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- 229910018182 Al—Cu Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910015844 BCl3 Inorganic materials 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229940093476 ethylene glycol Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012458 free base Substances 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229960004063 propylene glycol Drugs 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
- 239000002904 solvent Substances 0.000 description 1
- WWIYWFVQZQOECA-UHFFFAOYSA-M tetramethylazanium;formate Chemical compound [O-]C=O.C[N+](C)(C)C WWIYWFVQZQOECA-UHFFFAOYSA-M 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Photosensitive Polymer And Photoresist Processing (AREA)
- Paints Or Removers (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (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フォト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との両方を向上させるフォトレジスト剥離剤組成物に関するものである。
【0002】
【従来の技術】
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、剥離剤組成物としては、有機アルカリ、無機アルカリ、有機酸、無機酸、極性溶剤等の単一溶剤、これらの混合溶液、又はこれらの水溶液が用いられている。また、半導体素子回路等の製造工程において、配線形成時に生成するレジスト残渣を除去するために、アルキルアミン及びアルキルアンモニウム水酸化物の少なくともいずれかと、有機溶剤と、水とを主成分とするレジスト剥離剤組成物も良く知られている。
【0004】
さらに、フッ素化合物を含有するレジスト剥離剤組成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、特開平8−202052号公報には、フッ化水素酸、フッ化アンモニウム、水溶性有機溶媒及び防食剤を含有するレジスト剥離液組成物が記載されている。また、特開平9−197681号公報には、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を含有し、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が記載されている。
【0005】
また、特開平7−201794号公報には、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4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ことが記載されている。特開平7−271056号公報には、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フォトレジスト用剥離液が記載されている。さらに、特開平9−62013号公報には、フッ素化合物及びベタイン化合物と水及び、アミド類、ラクトン類、アルコール類から選ばれた一種以上の有機溶剤を含む半導体装置用洗浄剤が記載されている。
【0006】
ところで、レジスト剥離剤組成物には、レジスト残渣除去性に優れており、かつ、基板上に形成されたアルミニウム、もしくはアルミニウム合金等の導電性金属膜の腐食が良好に防止できることが要求される。特に、フッ素化合物を含有する剥離液においては、基板を剥離液で処理した後の水洗工程におけるアルミニウム、もしくはアルミニウム合金の金属膜の腐食が問題となっている。
【0007】
しかし、上記公報に記載されている各種剥離液組成物を用いても、剥離性と剥離処理後の水洗工程におけるアルミニウム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、水洗工程でのアルミニウム、もしくはアルミニウム合金の金属膜の腐食が起こる。この腐食は、剥離処理後に基板に残存する剥離液が水によって希釈されることにより生じ、その腐食の度合いは剥離剤組成物中のフッ素化合物の含有量に比例すると考えられる。そのため、剥離剤組成物に含まれるフッ素化合物の含有量を極力抑えることが、剥離処理後の水洗工程におけるアルミニウム腐食を抑制する上では好ましい。
【0008】
しかし、単にフッ素化合物の含有量を減らすだけでは、レジスト残渣が十分に除去されないという不具合が生じる。
【0009】
【発明が解決しようとする課題】
そこで、レジスト残渣に対する高い除去性と、剥離処理後の水洗工程におけるアルミニウム防食性を兼ね備えた剥離剤組成物が望まれている。
【0010】
【課題を解決するための手段】
本発明者は種々の実験を重ねた結果、フッ化アンモニウムと水と水溶性有機溶剤とを含有する剥離剤組成物において、フッ化アンモニウムの含有量を極力抑制して剥離処理後の水洗工程におけるアルミニウムの腐食を抑制しながら、チオシアン酸アンモニウム、硝酸アンモニウム、アミド硫酸アンモニウム、および乳酸アンモニウムからなる群から選択される少なくとも一つの化合物を組成物に含有させることで、高いレジスト残渣除去性が得られることを見出した。本発明は、上記の知見に基づいてなされたものである。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の腐食を良好に防止することができるレジスト剥離剤組成物及びその使用方法を提供することにある。
【0011】
本発明は、A)チオシアン酸アンモニウム、硝酸アンモニウム、アミド硫酸アンモニウム、および乳酸アンモニウムからなる群から選択される少なくとも一つの化合物、B)フッ化アンモニウム、C)水、およびD)水溶性有機溶剤を含有する、レジスト剥離剤組成物に関する。
【0012】
好ましい実施態様においては、前記A)の化合物の含有量が0.01〜10重量%、B)フッ化アンモニウムの含有量が0.01〜3重量%、C)水の含有量が15〜45重量%、および残部がD)水溶性有機溶剤である。
【0013】
【発明の実施の形態】
本発明の組成物に含まれるA)の化合物は、チオシアン酸アンモニウム、硝酸アンモニウム、アミド硫酸アンモニウム、および乳酸アンモニウムからなる群から選択される少なくとも一つの化合物である。A)の化合物の含有量は、0.01〜10重量%、好ましくは0.1〜5重量%である。 A)の化合物の含有量が0.01重量%未満の場合は、レジスト残渣の除去性を向上させる効果が得られにくくなる。他方、10重量%を超える場合は、格別な利点はなく、経済的にも得策ではない。
【0014】
B)フッ化アンモニウムの含有量は0.01〜3重量%、好ましくは0.1〜1重量%、さらに好ましくは0.1〜0.5重量%である。B)フッ化アンモニウムの含有量が0.01重量%未満の場合は、レジスト残渣除去性が低下する傾向にある。他方、3重量%を超える場合は、アルミニウムやシリコン酸化膜に対する腐食が激しくなる傾向にある。
【0015】
また、C)水の含有量は15〜45重量%、好ましくは15〜40重量%である。C)水の含有量が15重量%未満の場合は、フッ化アンモニウムが析出することがあり、45重量%を超えるとアルミニウムに対する腐食が激しくなる傾向にある。
【0016】
D)水溶性有機溶剤としては、N,N−ジメチルアセトアミド、N,N−ジメチルホルムアミド、ジメチルスルホキシド、エチレングリコール、プロピレングリコール、ジエチレングリコールモノブチルエーテル、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モノメチルエーテルなどが単独でまたは組み合わせて用いられる。レジスト残渣の除去性および金属防食性の面からN,N−ジメチルアセトアミドが好ましく用いられる。D)水溶性有機溶媒は、残部添加される。
【0017】
上記A)〜D)を含む本発明の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る。
【0018】
以下に実施例及び比較例を示し、本発明の特徴とするところをより一層明確にする。
【0019】
実施例1〜7、比較例1〜8
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、続いて酸素と水とを用いてアッシングした時に配線側壁また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3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「残渣なし」、×は「残渣が残っている」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。
【0020】
【表1】
【0021】
表1の実施例1〜7において、A)の化合物、B)フッ化アンモニウム、C)水、およびD)水溶性有機溶剤からなる組成物において、B)フッ化アンモニウムの含有量が0.01〜3重量%の範囲にあるので、水洗工程におけるアルミニウムの腐食を抑え、A)のチオシアン酸アンモニウム、硝酸アンモニウム、アミド硫酸アンモニウム、および乳酸アンモニウムからなる群から選択される少なくとも一つの化合物を添加することにより、レジスト残渣に対する良好な除去性が得られ、アルミニウム防食性とレジスト残渣に対する高い除去性を両立する結果が得られた。
【0022】
比較例1は、B)フッ化アンモニウムの含有量が3重量%を超えるので、アルミニウムの腐食が激しかった。比較例2はB)フッ化アンモニウムの含有量が0.01未満であったので、レジスト残渣に対する除去性が得られなかった。
【0023】
比較例3、4は、B)フッ化アンモニウムの含有量が0.01〜3重量%の範囲にあるのでアルミニウム防食性は良好であったが、A)の化合物を含まないので、レジスト残渣に対する除去性が不足する結果となった。
【0024】
比較例5は、組成物中のC)水の含有量が15重量%未満(10重量%)であるので、B)フッ化アンモニウムが析出した。
【0025】
比較例6は、組成物中のC)水の含有量が45重量%を超える(60重量%)ので、アルミニウムの腐食が激しかった。
【0026】
比較例7は、本発明の特定のA)の化合物(アンモニウム塩)の代わりに、酢酸アンモニウム用いた組成物であるが、酢酸アンモニウムには剥離性を向上させる効果は見られなかった。
【0027】
比較例8も、本発明の特定のA)アンモニウム塩の代わりにテトラメチルアンモニウムギ酸塩を用いた組成物であるが、剥離性とアルミニウム防食性は得られなかった。
【0028】
つぎに、本発明のレジスト剥離剤組成物の使用方法の一例について説明する。半導体基板上また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レジスト剥離剤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。
【0029】
【発明の効果】
本発明は上記のように構成されているので、つぎのような効果を奏する。
A)チオシアン酸アンモニウム、硝酸アンモニウム、アミド硫酸アンモニウム、および乳酸アンモニウムからなる群から選択される少なくとも一つの化合物、B)フッ化アンモニウム、C)水、およびD)水溶性有機溶剤からなるレジスト剥離剤組成物を提供する。本発明の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薄膜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 photoresist stripping composition used in the manufacture of semiconductor integrated circuits, semiconductor element circuits of liquid crystal panels, and the like. More specifically, the present invention relates to a photoresist stripping composition that improves both the removal performance of resist residues generated when forming wiring on a semiconductor substrate or a liquid crystal glass substrate, and aluminum corrosion resistance on the substrate. .
[0002]
[Prior art]
The stripping composition is used when stripping 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 release agent composition, a single solvent such as an organic alkali, an inorganic alkali, an organic acid, an inorganic acid, a polar solvent, a mixed solution thereof, or an aqueous solution thereof is used. In addition, in the manufacturing process of semiconductor element circuits, etc., in order to remove the resist residue generated at the time of wiring formation, the resist stripping mainly composed of at least one of alkylamine and alkylammonium hydroxide, an organic solvent, and water Agent compositions are also well known.
[0004]
Furthermore, it is known that a resist remover composition containing a fluorine compound is effective for removing a resist residue produced during wiring formation in a semiconductor substrate manufacturing process or a liquid crystal glass substrate manufacturing process. For example, JP-A-8-202052 describes a resist stripping solution composition containing hydrofluoric acid, ammonium fluoride, a water-soluble organic solvent, and an anticorrosive agent. Japanese Patent Laid-Open No. 9-197681 discloses a resist containing 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. A stripping composition is described.
[0005]
Japanese Patent Application Laid-Open No. 7-201794 discloses a protective deposition film formed in a semiconductor device manufacturing process as an aqueous solution containing a quaternary ammonium salt and a fluorine compound, or a quaternary ammonium salt and a fluorine compound. And peeling using a semiconductor device cleaning agent comprising an aqueous solution containing an organic solvent selected from lactones, nitriles, alcohols and esters. Japanese Patent Application Laid-Open No. 7-271056 describes a photoresist stripping solution comprising an aqueous solution containing a specific organic carboxylic acid ammonium salt or organic carboxylic acid amine salt and a fluorine compound. Furthermore, JP-A-9-62013 discloses a semiconductor device cleaning agent containing a fluorine compound and a betaine compound, water, and one or more organic solvents selected from amides, lactones, and alcohols. .
[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 conductive metal film such as aluminum or aluminum alloy formed on the substrate. In particular, in a stripping solution containing a fluorine compound, corrosion of aluminum or a metal film of an aluminum alloy in the water washing step after treating the substrate with the stripping solution is a problem.
[0007]
However, even if the various stripping liquid compositions described in the above publication are used, it is not possible to satisfy both the peelability and the aluminum corrosion resistance in the water washing step after the peeling treatment. In particular, among the above compositions, the release agent composition containing a fluorine compound causes corrosion of the aluminum or aluminum alloy metal film in the water washing step. This corrosion occurs when the stripping solution remaining on the substrate after the stripping treatment is diluted with water, and the degree of the corrosion is considered to be proportional to the content of the fluorine compound in the stripping composition. Therefore, it is preferable to suppress the content of the fluorine compound contained in the release agent composition as much as possible in order to suppress aluminum corrosion in the water washing step after the release treatment.
[0008]
However, simply reducing the content of the fluorine compound causes a problem that the resist residue is not sufficiently removed.
[0009]
[Problems to be solved by the invention]
Therefore, a release agent composition that has both high removability for resist residues and aluminum corrosion resistance in the water washing step after the release treatment is desired.
[0010]
[Means for Solving the Problems]
As a result of repeating various experiments, the present inventor found that in a release agent composition containing ammonium fluoride, water, and a water-soluble organic solvent, the content of ammonium fluoride was suppressed as much as possible in the water washing step after the release treatment. By containing at least one compound selected from the group consisting of ammonium thiocyanate, ammonium nitrate, ammonium amidosulfate, and ammonium lactate in the composition while suppressing corrosion of aluminum, high resist residue removability can be obtained. I found it. The present invention has been made based on the above findings. An object of the present invention is to remove a resist residue generated at the time of wiring formation with high performance, and at the same time, a resist stripper composition that can satisfactorily prevent corrosion of aluminum on a substrate in a water washing step after the stripping treatment, and use thereof It is to provide a method.
[0011]
The present invention contains A) at least one compound selected from the group consisting of ammonium thiocyanate, ammonium nitrate, ammonium amidosulfate, and ammonium lactate, B) ammonium fluoride, C) water, and D) a water-soluble organic solvent. And relates to a resist stripper composition.
[0012]
In a preferred embodiment, the content of the compound of A) is 0.01 to 10% by weight, B) the content of ammonium fluoride is 0.01 to 3% by weight, and C) the content of water is 15 to 45%. % By weight and the balance is D) water-soluble organic solvent.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
The compound of A) contained in the composition of the present invention is at least one compound selected from the group consisting of ammonium thiocyanate, ammonium nitrate, ammonium amidosulfate, and ammonium lactate. The content of the compound A) is 0.01 to 10% by weight, preferably 0.1 to 5% by weight. When the content of the compound A) is less than 0.01% by weight, it is difficult to obtain the effect of improving the removability of the resist residue. On the other hand, when it exceeds 10% by weight, there is no particular advantage and it is not economically advantageous.
[0014]
B) The content of ammonium fluoride is 0.01 to 3% by weight, preferably 0.1 to 1% by weight, more preferably 0.1 to 0.5% by weight. B) When the content of ammonium fluoride is less than 0.01% by weight, the resist residue removability tends to be lowered. On the other hand, when it exceeds 3% by weight, the corrosion of aluminum or silicon oxide film tends to become severe.
[0015]
C) The water content is 15 to 45% by weight, preferably 15 to 40% by weight. C) When the water content is less than 15% by weight, ammonium fluoride may be precipitated, and when it exceeds 45% by weight, corrosion to aluminum tends to become severe.
[0016]
D) As the water-soluble organic solvent, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, ethylene glycol, propylene glycol, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, etc. are used alone or in combination. Used. N, N-dimethylacetamide is preferably used from the standpoint of resist residue removal and metal corrosion resistance. D) The remainder of the water-soluble organic solvent is added.
[0017]
The resist remover composition of the present invention including the above A) to D) may form a wiring by peeling and removing a resist residue generated when a wiring is formed on a semiconductor substrate or a glass substrate for liquid crystal. it can.
[0018]
Examples and Comparative Examples are shown below to further clarify the features of the present invention.
[0019]
Examples 1-7, Comparative Examples 1-8
A substrate on which Ti is formed on a silicon oxide film, further TiN is formed thereon, and Al-Cu is formed thereon is dry-etched using Cl2 and BCl3 with a patterned resist as a mask, followed by oxygen and water. The resist residue generated on the side wall or the upper part of the wiring when ashing was used as an object to be peeled. After immersing the above-mentioned object in the release agent composition shown in Table 1 at 24 ° C. for 3 minutes, immersed in pure water at 24 ° C. for 1 minute, and further immersed 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 Table 1, peelability indicates that “no residue” and × indicates that “residue remains”. Further, in the aluminum anticorrosive properties in Table 1, “◯” indicates “no corrosion”, and “×” indicates “the wiring is thin or the surface is rough”.
[0020]
[Table 1]
[0021]
In Examples 1 to 7 in Table 1, in a composition comprising the compound of A), B) ammonium fluoride, C) water, and D) a water-soluble organic solvent, the content of B) ammonium fluoride is 0.01. By adding at least one compound selected from the group consisting of ammonium thiocyanate, ammonium nitrate, ammonium amidosulfate, and ammonium lactate of A) because it is in the range of ˜3 wt%, suppressing corrosion of aluminum in the washing step. Thus, good removability with respect to the resist residue was obtained, and a result that achieved both aluminum corrosion resistance and high removability with respect to the resist residue.
[0022]
In Comparative Example 1, since the content of B) ammonium fluoride exceeded 3% by weight, corrosion of aluminum was severe. In Comparative Example 2, since the content of B) ammonium fluoride was less than 0.01, the removability to the resist residue was not obtained.
[0023]
In Comparative Examples 3 and 4, B) the content of ammonium fluoride was in the range of 0.01 to 3% by weight, so the aluminum anticorrosion was good, but the compound of A) was not included, so The result was insufficient removability.
[0024]
In Comparative Example 5, since the content of C) water in the composition was less than 15% by weight (10% by weight), B) ammonium fluoride was precipitated.
[0025]
In Comparative Example 6, since the C) water content in the composition exceeded 45% by weight (60% by weight), corrosion of aluminum was severe.
[0026]
Comparative Example 7 is a composition using ammonium acetate instead of the specific A) compound (ammonium salt) of the present invention, but ammonium acetate did not show an effect of improving peelability.
[0027]
Comparative Example 8 was also a composition using tetramethylammonium formate in place of the specific A) ammonium salt of the present invention, but peelability and aluminum corrosion resistance were not obtained.
[0028]
Next, an example of a method for using the resist remover 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 stripped and removed using the resist stripper composition of the present invention to produce a semiconductor element in which wirings and the like are formed.
[0029]
【The invention's effect】
Since this invention is comprised as mentioned above, there exist the following effects.
A) At least one compound selected from the group consisting of ammonium thiocyanate, ammonium nitrate, ammonium amidosulfate, and ammonium lactate, B) ammonium fluoride, C) water, and D) a resist stripper composition comprising a water-soluble organic solvent I will provide a. By using the resist remover composition of the present invention for removing a resist residue generated at the time of forming a wiring in a manufacturing process of a semiconductor or liquid crystal device circuit, etc., the resist residue is removed with high performance, and after the peeling treatment Corrosion of a metal thin film such as aluminum on the substrate can be satisfactorily prevented in the water washing step.
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