CN1526807A - 洗涤液及使用其的洗涤方法 - Google Patents
洗涤液及使用其的洗涤方法 Download PDFInfo
- Publication number
- CN1526807A CN1526807A CNA200410005492XA CN200410005492A CN1526807A CN 1526807 A CN1526807 A CN 1526807A CN A200410005492X A CNA200410005492X A CN A200410005492XA CN 200410005492 A CN200410005492 A CN 200410005492A CN 1526807 A CN1526807 A CN 1526807A
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- China
- Prior art keywords
- acid
- washings
- record
- oxygenant
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000004140 cleaning Methods 0.000 title abstract description 9
- 239000003599 detergent Substances 0.000 title 1
- 239000002253 acid Substances 0.000 claims abstract description 56
- 239000004065 semiconductor Substances 0.000 claims abstract description 43
- 239000000758 substrate Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000005260 corrosion Methods 0.000 claims abstract description 16
- 230000007797 corrosion Effects 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 239000003112 inhibitor Substances 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims description 81
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 29
- 229910052802 copper Inorganic materials 0.000 claims description 29
- 239000010949 copper Substances 0.000 claims description 29
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 21
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 21
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 239000011737 fluorine Substances 0.000 claims description 15
- 229910052731 fluorine Inorganic materials 0.000 claims description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 11
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 239000013543 active substance Substances 0.000 claims description 10
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 8
- -1 polyoxyethylene Polymers 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 5
- 239000011707 mineral Substances 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 235000019260 propionic acid Nutrition 0.000 claims description 4
- YNYNWYITBQVUSQ-UHFFFAOYSA-N OCC[NH3+].C[NH+](C)C.[OH-].[OH-] Chemical compound OCC[NH3+].C[NH+](C)C.[OH-].[OH-] YNYNWYITBQVUSQ-UHFFFAOYSA-N 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 229920013701 VORANOL™ Polymers 0.000 claims description 3
- 150000001346 alkyl aryl ethers Chemical class 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 3
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- 150000001455 metallic ions Chemical class 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 239000003945 anionic surfactant Substances 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000001737 promoting effect Effects 0.000 claims 1
- 239000007800 oxidant agent Substances 0.000 abstract description 4
- 150000007514 bases Chemical class 0.000 abstract 2
- 150000002222 fluorine compounds Chemical class 0.000 abstract 2
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- 238000001312 dry etching Methods 0.000 description 7
- 239000011241 protective layer Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 229910052814 silicon oxide Inorganic materials 0.000 description 6
- 229910052581 Si3N4 Inorganic materials 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 4
- 229960001231 choline Drugs 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- HNXQXTQTPAJEJL-UHFFFAOYSA-N pterin lactim Natural products C1=CN=C2NC(N)=NC(=O)C2=N1 HNXQXTQTPAJEJL-UHFFFAOYSA-N 0.000 description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 150000002466 imines Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-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
- 238000003475 lamination Methods 0.000 description 2
- 238000001459 lithography Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N thiocyanic acid Chemical compound SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 2
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- RSEBUVRVKCANEP-UHFFFAOYSA-N 2-pyrroline Chemical compound C1CC=CN1 RSEBUVRVKCANEP-UHFFFAOYSA-N 0.000 description 1
- MCGBIXXDQFWVDW-UHFFFAOYSA-N 4,5-dihydro-1h-pyrazole Chemical compound C1CC=NN1 MCGBIXXDQFWVDW-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QZHXKQKKEBXYRG-UHFFFAOYSA-N 4-n-(4-aminophenyl)benzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1NC1=CC=C(N)C=C1 QZHXKQKKEBXYRG-UHFFFAOYSA-N 0.000 description 1
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 1
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- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
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- CRAFBOZKMVZBDP-UHFFFAOYSA-N [OH-].C(C)[NH3+].C[NH+](C)C.[OH-] Chemical compound [OH-].C(C)[NH3+].C[NH+](C)C.[OH-] CRAFBOZKMVZBDP-UHFFFAOYSA-N 0.000 description 1
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- 229940095064 tartrate Drugs 0.000 description 1
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- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
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Abstract
本发明提供了能在短时间内将半导体基板上的蚀刻残渣完全除去,且不会将铜配线材料和绝缘膜材料等氧化或腐蚀,而且安全且对环境压力小的洗涤液。本发明涉及(1)半导体基体用洗涤液,其特征在于:含有氧化剂、酸及氟化合物,添加碱性化合物使pH调整为3~10,且水的浓度为80重量%以上;(2)半导体基体用洗涤液,其特征在于:含有氧化剂、酸、氟化合物及腐蚀抑制剂,通过添加碱性化合物使pH调整为3~10,且水的浓度为80重量%以上;及实施了金属配线的半导体基体的洗涤方法,其特征在于:使用前述的洗涤液。
Description
技术领域
本发明涉及将半导体基体表面的附着物除去的洗涤液及使用该洗涤液的洗涤方法。更具体说,本发明涉及在不对半导体基体上的金属配线、层间绝缘膜等产生损害的情况下,能够将半导体基体表面的牢固附着物除去的洗涤液及使用该洗涤液的洗涤方法。
背景技术
目前,作为高集成化的LSI等的半导体元件的制造方法,一般采用石印术。当采用该石印术制造半导体元件时,通常在硅片等的基板上形成成为导电用配线材料的金属膜等导电薄膜、和以进行导电薄膜与配线间绝缘为目的的硅氧化膜等层间绝缘膜后,在其表面均匀地涂布光致抗蚀剂、设置感光层,对其实施选择性的曝光及显像处理,形成所希望的保护图案。随后,以该保护图案作为面罩,通过对下层部的薄膜实施选择性的蚀刻处理,在该薄膜上形成所希望的保护图案。然后,进行将该保护图案完全除去的一连串工序。
近年来,半导体元件的高集成化不断发展,已需要形成0.18μm以下的图案了,伴随该加工尺寸的超微细化,在前述选择性的蚀刻处理中,干蚀刻法已成为主流。在干蚀刻处理中,已知在形成的图案周边部分生成由干蚀刻气体、保护层、被加工膜及干蚀刻装置内的处理室材料等产生的残渣(以下,将它们称为蚀刻残渣)。特别是如果蚀刻残渣残存在通孔内部及其周边部分,存在担心导致高电阻化,或产生电短路等不希望出现的情况。
以往,在半导体元件等上形成金属配线的工序中,作为用于将蚀刻残渣除去的洗涤液,例如,特开昭62-49355号公报、特开昭64-42653号公报等公开了由链烷醇胺和有机溶剂的混合系构成的有机胺系剥离液。
这些有机胺系剥离液在将蚀刻残渣及保护层等除去后进行了水洗时,由于吸湿的水分而使胺产生解离,成为碱性的结果是担心用于微细配线加工的配线材料的金属薄膜等会被腐蚀。因此,存在着为了避免前述腐蚀而必须在漂洗液中使用醇等有机溶剂的问题。
此外,作为比有机胺系剥离液具有更高蚀刻残渣、保护固化层除去能力的洗涤剂,例如,特开平7-201794号公报、特开平11-67632号公报等公开了由氟化合物、有机溶剂及缓蚀剂等构成的氟系洗涤液,但近年来,半导体元件的制造工序中干蚀刻的条件更为严格,由于干蚀刻时使用的气体或温度条件使保护层自身容易变质,使用前述有机胺系剥离液或氟系水溶液不能完全将蚀刻残渣除去。
此外,对于以往常用作配线材料的铝作为主成分的材料,电阻过高,因此以高速使回路运转变得困难,利用铜单体作为配线材料不断高涨。因此,为了制造高品质的半导体元件,在不对这样的配线材料产生损害的情况下有效地将蚀刻残渣除去也成为非常重要的课题。
此外,在半导体制造过程中,大量含有有机溶剂的有机胺系洗涤液或氟系洗涤液在安全对策或废液处理等环境方面的压力均很大,其对策变得很重要,例如,特开平10-72594号公报中公开了作为有机酸水溶液的酸系洗涤液,此外,特开2000-338686号公报中公开了作为硝酸、硫酸及磷酸的水溶液的酸系洗涤剂。但是,对于变得更牢固的蚀刻残渣,特别是含有层间绝缘膜成分的蚀刻残渣,其除去能力均不充分。
因此,强烈希望有一种洗涤液,是在半导体制造过程中,在不对配线材料产生损害的情况下可以将蚀刻残渣完全除去,且半导体制造过程中安全及环境方面的压力小的洗净液。
本发明的目的在于提供一种洗涤液,其在用于半导体集成电路的半导体元件或显示元件的配线工序中的干蚀刻后,或半导体基体的干蚀刻后残存的蚀刻残渣可以在短时间内除去,且对铜配线材料和绝缘膜材料等不产生氧化或腐蚀,本发明的目的还在于提供一种使用该洗涤液的实施了金属配线的半导体元件、显示元件、半导体基体的洗涤方法。
发明内容
本发明者们为了解决上述课题进行了锐意研究,其结果发现:通过在氧化剂、酸、氟化合物及碱性化合物中组合腐蚀抑制剂进行使用,得到优异的洗涤液。
即,本发明提供:
(1)半导体基体用洗涤液,其特征在于:含有氧化剂、酸及氟化合物,添加碱性化合物使pH调整为3~10,且水的浓度为80重量%以上;
(2)半导体基体用洗涤液,其特征在于:含有氧化剂、酸、氟化合物和腐蚀抑制剂,通过添加碱性化合物使pH调整为3~10,且水的浓度为80重量%以上;
(3)实施了金属配线的半导体基体的洗涤方法,其特征在于:使用前述(1)或(2)记载的洗涤液。
附图的简单说明
图1为在下层铜配线体上层压硅氮化膜和硅氧化膜后进行保护加工、其后进行蚀刻处理、将残存的保护层除去的半导体元件的一部分的断面图。
图中的符号如下所述。
1:下层铜配线体、2:硅氮化膜、3:硅氧化膜、4:蚀刻残渣
发明的最佳实施方案
作为本发明所使用的洗涤液中的氧化剂,可以例举碘、高碘酸、碘酸、过氧化氢、硝酸、亚硝酸。其中,更优选过氧化氢、硝酸,进一步优选硝酸。用于本发明的前述氧化剂可以单独使用,也可以2种以上组合使用。此外,本发明的洗涤液中氧化剂浓度优选0.001~10重量%,特别优选0.005~8重量%。
作为本发明所使用的洗涤液中的酸,可以例举无机酸、有机酸。作为无机酸,可以例举硼酸、氨基磺酸、磷酸、次磷酸、碳酸、盐酸、硫酸,其中,优选硼酸、氨基磺酸、磷酸、碳酸、硫酸,进一步优选硫酸。作为有机酸,可以例举草酸、柠檬酸、丙酸、乙酸、丙二酸、马来酸、葡糖酸、二甘醇酸、酒石酸、衣康酸、丙酮酸、苹果酸、己二酸、甲酸、琥珀酸、苯二甲酸、苯甲酸、水杨酸、氨基甲酸、硫氰酸、乳酸。其中,更优选草酸、柠檬酸、丙酸、乙酸。本发明所使用的前述酸可以单独使用,也可以2种以上组合使用。此外,本发明的洗涤液中的酸浓度,优选0.001~10重量%,特别优选0.005~8重量%。氧化剂和酸的浓度可以相同,也可以彼此不同,酸/氧化剂的重量比优选0.1~1000重量比,更优选1.0~100重量比,更优选1~60重量比。
此外,该洗涤液中的水的浓度为80重量%以上,优选85重量%以上。
通过使洗涤液中的氧化剂浓度、酸浓度、及水的浓度在前述范围,可以有效地将蚀刻残渣除去,并且可以有效地抑制对配线材料等的腐蚀。
另一方面,作为本发明中使用的氟化合物,可以例举氢氟酸、氟化铵、酸性氟化铵、及下述通式(1)所示的氟化季铵盐等。
(式中,R1、R2、R3及R4彼此独立,表示碳数为1~6的烷基、羟烷基、烷氧基烷基、或链烯基及碳数为6~12的芳基、芳烷基。)
作为用通式(1)所示的氟化季铵盐的具体例,可以例举氟化四甲铵、氟化四乙铵、氟化三乙基甲基铵、氟化三甲基羟乙基铵、氟化四乙醇铵、氟化甲基三乙醇铵等。其中优选氟化铵及氟化四甲铵。
本发明所使用的前述氟化合物可以单独使用,也可以2种以上组合使用。此外,本发明洗涤液中氟化合物的浓度优选为0.001~15重量%,特别优选0.005~10重量%。氟化合物的浓度在0.001重量%以上,可以有效地除去蚀刻残渣,如果超过15重量%,则担心产生对配线材料的腐蚀问题。
作为本发明中使用的腐蚀抑制剂并无特别限制,可以使用磷酸系、羧酸系、胺系、肟系、芳香族羟基化合物、三唑化合物、糖醇等各种物质。作为优选的腐蚀抑制剂,可以例举分子内含有至少一个氨基或硫醇基的聚乙烯亚胺、3-氨基三唑等三唑类,2,4-二氨基-6-甲基-1,3,5-三嗪等三嗪衍生物,2-氨基-4-羟基蝶呤、2-氨基-4,6-二羟基蝶呤等蝶呤衍生物,聚胺砜。其中,特别优选具有下述式(2)结构、平均分子量为200~100000,优选1000~80000的聚乙烯亚胺(PEI)。
作为本发明中使用的碱性化合物,优选无金属离子碱,可以例举例如氨、伯胺、仲胺、叔胺、亚胺、链烷醇胺、可以具有碳数1~8的烷基且具有氮原子的杂环化合物、及下述通式(3)所示的氢氧化季铵类。
(式中,R5、R6、R7及R8彼此独立,表示碳数1~6的烷基、羟烷基、烷氧基烷基、或链烯基及碳数6~12的芳基、芳烷基。)
作为伯胺的具体例,可以例举乙胺、正丙胺、丁胺、1-乙基丁胺、1,3-二氨基丙烷、环己胺等。
作为仲胺,可以例举二乙胺、二正丙胺、二正丁胺、4,4’-二氨基二苯胺等。
作为叔胺,可以例举二甲基乙基胺、二乙基甲基胺、三乙胺、三丁胺等。
作为亚胺,可以例举1-丙烷亚胺、二(二烷基氨基)亚胺等。
作为链烷醇胺,可以例举一乙醇胺、二乙醇胺、三乙醇胺、二乙基乙醇胺、丙醇胺等。
作为可以具有碳数为1~8的烷基、具有氮原子的杂环化合物,可以例举吡咯、咪唑、吡唑、吡啶、吡咯烷、2-吡咯啉、咪唑啉、2-吡唑啉、吡唑烷、哌啶、哌嗪、吗啉等。
作为用通式(3)所示的氢氧化季铵类的具体例,可以例举氢氧化四甲铵(TMAH)、氢氧化三甲基羟乙基铵(胆碱)、氢氧化甲基三羟乙基铵、氢氧化二甲基二羟乙基铵、氢氧化三甲基乙基铵、氢氧化四乙铵、氢氧化四丁铵、氢氧化四乙醇铵等。在这些碱性化合物中,优选作为强碱的氢氧化四甲铵、及氢氧化三甲基羟乙基铵(胆碱)。
用于本发明的前述碱性化合物可以单独使用,也可以2种以上适当组合使用。此外,洗涤液中碱性化合物的浓度通常使用0.01~15重量%的浓度,但对于碱性化合物的浓度,可以适当决定以使洗涤液的pH达到3~10的范围。
为了提高其浸润性,可以在本发明的洗涤液中添加表面活性剂使用。作为表面活性剂,可以使用阳离子性、阴离子性、非离子性及氟系表面活性剂的任何表面活性剂。其中,特别优选阴离子性表面活性剂,进而更优选聚氧乙烯烷基醚的磷酸酯、或聚氧乙烯烷基芳基醚的磷酸酯。作为聚氧乙烯烷基醚的磷酸酯,市售的有例如第一工业制药株式会社制造的商品名:PLYSURF A215C、东邦化学工业株式会社制造的商品名:PHOSPHANOL RS-710。此外,作为聚氧乙烯烷基芳基醚的磷酸酯,市售的有例如第一工业制药株式会社制造的商品名:PLYSURF A212E和A217E。
用于本发明的表面活性剂可以单独使用,也可以2种以上适当组合使用。洗涤液中表面活性剂的浓度优选0.0001~5重量%,更优选0.001~0.1重量%。
此外,在不损害本发明目的的范围内,可以根据需要在本发明的洗涤液中配合以往用于洗涤液的其他添加剂。
本发明的洗涤液的pH在3~10的范围,更优选3~7,进一步优选4~6的范围。洗涤液的pH在3~10的范围,可以有效地除去蚀刻残渣,因此可以在该范围内根据蚀刻的条件和所使用的半导体基体适当选择pH。
实施本发明的洗涤方法时的温度通常为常温到90℃的范围,可以根据蚀刻的条件和所使用的半导体基体适当选择。
作为适用本发明洗涤法的半导体基体,可以例举实施硅、无定形硅、聚硅、硅氧化膜、硅氮化膜、铜、钛、钛-钨、氮化钛、钨、钽、钽化合物、铬、铬氧化物、铬合金等金属配线材料或镓-砷、镓-磷、铟-磷等的化合物半导体等的半导体基板、聚酰亚胺树脂等的印刷基板、用于LCD等的玻璃基板等。
为了使实施金属配线的半导体元件或显示元件中的回路高速运转,在前述半导体基体中,本发明的洗涤液相对于实施了含有铜单体或铜和隔离金属(边界金属层)的层压结构的金属配线的半导体基体,可以更有效地使用。
在本发明的洗涤方法中,必要时可以并用超音波洗涤。作为除去实施了金属配线的半导体元件、显示元件、半导体基体上蚀刻残渣后的漂洗,也可以使用醇这样的有机溶剂、醇和超纯水的混合物,但根据本发明的洗涤方法,只用超纯水就能进行充分地漂洗。
实施例
以下结合实施例和比较例对本发明进行具体的说明,但本发明并不限于这些实施例。
实施例1~17及比较例1~14
图1为半导体元件的一部分的断面图,该半导体元件用CVD法在下层铜配线体1上按顺序层压硅氮化膜2和硅氧化膜3后,涂布保护层,使用通常的光化技术对保护层进行加工,其后使用干蚀刻技术将前述硅氧化膜蚀刻加工成所希望的图案,将残存的保护层除去。如图1所示,在蚀刻加工了的侧壁上残存有蚀刻残渣4。
使用表1~8所示的洗涤液,在所定条件下将前述铜回路元件洗涤后,用超纯水漂洗、干燥。然后,用扫描型电子显微镜(SEM)观察表面状态,对蚀刻残渣的除去状态及铜配线体的腐蚀状态进行评价。其结果示于表1~4(第1发明)及表5~8(第2发明)。
此外,评价基准如下。
(1)关于蚀刻残渣的除去状态
◎:蚀刻残渣被完全除去。
○:蚀刻残渣大体上被完全除去。
△:蚀刻残渣一部分残存。
×:蚀刻残渣大部分残存。
(2)关于铜的腐蚀状态
◎:完全没有发现腐蚀。
○:几乎没有发现腐蚀。
△:发现有坑状或凹状的腐蚀。
×:在整个铜层发现变粗糙,进而发现铜层的变薄。
表1
实施例 | 1 | 2 | 3 | 4 |
洗涤液组成(重量%) | ||||
硝酸(氧化剂) | 0.6 | 0.1 | 2.0 | 0.3 |
硫酸(酸) | 3.0 | 4.0 | 3.0 | 3.0 |
酸/氧化剂重量比 | 5 | 40 | 1.5 | 10 |
氟化铵 | 0.3 | - | - | - |
氟化四甲铵 | - | 0.5 | 0.3 | 0.4 |
氢氧化四甲铵 | 6.3 | 7.5 | 8.4 | 5.8 |
水 | 89.8 | 87.9 | 86.3 | 90.5 |
pH | 4 | 5 | 4 | 5 |
洗涤条件 温度(℃) | 40 | 40 | 40 | 70 |
时间(分) | 3 | 3 | 3 | 1.5 |
蚀刻残渣除去性 | ◎ | ◎ | ◎ | ◎ |
铜的腐蚀性 | ◎ | ◎ | ◎ | ◎ |
表2
实施例 | 5 | 6 | 7 | 8 | 9 |
洗涤液组成(重量%) | |||||
过氧化氢(氧化剂) | - | - | - | 2.0 | 10.0 |
硝酸(氧化剂) | 0.6 | 0.2 | 0.2 | - | - |
硫酸(酸) | 2.0 | 4.0 | 4.0 | - | - |
硼酸(酸) | - | - | - | 1.0 | - |
丙酸(酸) | - | - | - | 1.0 | - |
醋酸(酸) | - | - | - | - | 2.0 |
酸/氧化剂重量比 | 3.3 | 20 | 20 | 1.0 | 0.2 |
氟化铵 | - | 0.5 | - | - | - |
氟化四甲铵 | 3.0 | - | 1.0 | 9.0 | 1.5 |
氢氧化四甲铵 | 4.6 | - | 7.3 | - | 2.1 |
胆碱 | - | 7.5 | - | 1.2 | - |
表面活性剂* | - | - | 0.5 | - | - |
水 | 89.8 | 87.8 | 87.0 | 85.8 | 84.4 |
pH | 6 | 4 | 4 | 9 | 6.5 |
洗涤条件 温度(℃) | 40 | 40 | 40 | 60 | 50 |
时间(分) | 3 | 3 | 2 | 2 | 3 |
蚀刻残渣除去性 | ◎ | ◎ | ◎ | ◎ | ◎ |
铜的腐蚀性 | ◎ | ◎ | ◎ | ◎ | ◎ |
*表面活性剂:东邦化学工业株式会社制造,商品名:PHOSPHANOL RS-710
表3
比较例 | 1 | 2 | 3 | 4 | 5 |
洗涤液组成(重量%) | |||||
硝酸(氧化剂) | - | 6.0 | 0.2 | 0.3 | 0.2 |
硫酸(酸) | 3.0 | 0.1 | 4.0 | 3.0 | 4.0 |
酸/氧化剂重量比 | - | 0.02 | 20 | 10 | 20 |
氟化铵 | 0.7 | - | - | 0.2 | 0.2 |
氟化四甲铵 | - | 0.3 | - | - | - |
氢氧化四甲铵 | 5.5 | 8.5 | 7.6 | - | 10.5 |
水 | 90.8 | 85.1 | 88.2 | 96.5 | 85.1 |
pH | 5 | 4 | 4 | 1 | 11 |
洗涤条件 温度(℃) | 40 | 40 | 50 | 40 | 40 |
时间(分) | 3 | 3 | 3 | 3 | 3 |
蚀刻残渣除去性 | △ | △ | △ | ◎ | × |
铜的腐蚀性 | ◎ | ◎ | ◎ | × | ◎ |
表4
比较例 | 6 | 7 |
洗涤液组成(重量%) | ||
过氧化氢(氧化剂) | 5.0 | - |
氨基磺酸(酸) | - | 1.5 |
硼酸(酸) | - | 2.0 |
酸/氧化剂重量比 | - | - |
氟化四甲铵 | 2.5 | 0.3 |
氢氧化四甲铵 | 2.2 | 2.1 |
水 | 90.3 | 94.1 |
pH | 10 | 4 |
洗涤条件 温度(℃) | 40 | 40 |
时间(分) | 5 | 3 |
蚀刻残渣除去性 | △ | △ |
铜的腐蚀性 | ◎ | ◎ |
如表1及表2所示,在使用了本发明的洗涤液及洗涤法的实施例1~9中,完全没有发生铜被腐蚀,蚀刻残渣的除去性也很彻底。此外,如表3及表4所示,在比较例1~7中,蚀刻残渣的除去均不完全,或产生了铜的腐蚀。
表5
实施例 | 10 | 11 | 12 | 13 |
洗涤液组成(重量%) | ||||
硝酸(氧化剂) | 0.5 | 0.1 | 0.1 | 2.0 |
硫酸(酸) | 3.5 | 4.0 | 4.0 | 2.0 |
酸/氧化剂重量比 | 7 | 40 | 40 | 1.0 |
氟化铵 | 0.5 | - | - | - |
氟化四甲铵 | - | 0.5 | 0.5 | 0.7 |
氢氧化四甲铵 | 6.2 | 7.5 | 7.5 | 3.0 |
聚乙烯亚胺* | 0.5 | 0.01 | 0.01 | 2.0 |
水 | 88.8 | 87.89 | 87.89 | 90.3 |
pH | 5 | 5 | 5 | 4 |
洗涤条件 温度(℃) | 40 | 40 | 50 | 50 |
时间(分) | 3 | 3 | 10 | 3 |
蚀刻残渣除去性 | ◎ | ◎ | ◎ | ◎ |
铜的腐蚀性 | ◎ | ◎ | ◎ | ◎ |
*聚乙烯亚胺:平均分子量10000
表6
实施例 | 14 | 15 | 16 | 17 | 18 |
洗涤液组成(重量%) | |||||
硝酸(氧化剂) | 0.1 | 0.2 | 0.3 | 1.5 | 1.0 |
硫酸(酸) | 6.0 | 5.0 | 3.0 | - | - |
磷酸(酸) | - | - | - | 3.0 | - |
草酸(酸) | - | - | - | - | 2.5 |
柠檬酸(酸) | - | - | - | - | 1.5 |
酸/氧化剂重量比 | 60 | 25 | 10 | 2 | 4 |
氟化铵 | - | 1.0 | 0.7 | - | 0.5 |
氟化四甲铵 | 3.0 | - | - | 6.0 | - |
氢氧化四甲铵 | 10.7 | - | 5.1 | 8.8 | 5.9 |
胆碱 | - | 9.0 | - | - | - |
聚乙烯亚胺* | 0.1 | 0.2 | 0.3 | 0.05 | 1.0 |
表面活性剂** | - | - | 0.05 | - | - |
水 | 80.1 | 84.6 | 90.6 | 80.65 | 87.6 |
pH | 6 | 5 | 4 | 9 | 3 |
洗涤条件 温度(℃) | 60 | 40 | 30 | 70 | 30 |
时间(分) | 2 | 3 | 4 | 2 | 4 |
蚀刻残渣除去性 | ◎ | ◎ | ◎ | ◎ | ◎ |
铜的腐蚀性 | ◎ | ◎ | ◎ | ◎ | ◎ |
*聚乙烯亚胺:平均分子量10000
**表面活性剂:东邦化学工业株式会社制造,商品名:PHOSPHANOL RS-710
表7
比较例 | 8 | 9 | 10 | 11 | 12 |
洗涤液组成(重量%) | |||||
硝酸(氧化剂) | - | 0.1 | 2.0 | 1.0 | 0.2 |
硫酸(酸) | 5.0 | 4.0 | 4.0 | 2.5 | 1.0 |
酸/氧化剂重量比 | - | 40 | 2 | 2.5 | 5 |
氟化铵 | - | - | - | 0.5 | - |
氟化四甲铵 | 2.0 | 0.5 | - | - | 3.0 |
氢氧化四甲铵 | 8.9 | 7.5 | 6.7 | - | 2.3 |
聚乙烯亚胺* | 0.01 | - | 2.0 | - | 0.2 |
水 | 84.09 | 87.9 | 88.2 | 96.0 | 87.9 |
pH | 5 | 5 | 4 | 1 | 12 |
洗涤条件 温度(℃) | 40 | 50 | 70 | 30 | 50 |
时间(分) | 3 | 10 | 3 | 3 | 3 |
蚀刻残渣除去性 | △ | ◎ | △ | ◎ | × |
铜的腐蚀性 | ◎ | △ | ◎ | △ | ◎ |
*聚乙烯亚胺:平均分子量10000
表8
比较例 | 13 | 14 |
洗涤液组成(重量%) | ||
硝酸(氧化剂) | - | 0.05 |
柠檬酸(酸) | 5.0 | 8.0 |
酸/氧化剂重量比 | - | 160 |
氟化四甲铵 | 2.0 | - |
氢氧化四甲铵 | 7.4 | 9.4 |
聚乙烯亚胺* | 0.01 | 0.1 |
水 | 85.59 | 82.45 |
pH | 10 | 4 |
洗涤条件 温度(℃) | 40 | 50 |
时间(分) | 3 | 4 |
蚀刻残渣除去性 | △ | △ |
铜的腐蚀性 | ◎ | ◎ |
如表5及表6所示,在使用了本发明的洗涤液及洗涤方法的实施例10~18中,完全没有发生铜被腐蚀,蚀刻残渣的除去性也很优异。此外,如实施例12那样,与实施例11相比,即使将洗涤条件变为高温、长时间,也没有产生铜被腐蚀,但在没有添加聚乙烯亚胺(腐蚀抑制剂)时(比较例9),发现铜被腐蚀。在其他的比较例8~14中,蚀刻残渣的除去均不完全,或产生了铜的腐蚀。
产业上的利用可能性
本发明的洗涤液为对安全及环境方面压力小的洗涤液。使用本发明的洗涤液,可以在短时间内容易地将半导体基体上的蚀刻残渣除去,因此可以在完全不对配线材料腐蚀的情况下进行半导体基体的微细加工。此外,由于不必使用醇这样的有机溶剂作为漂洗液,可以只用水进行漂洗,因此可以进行高精度、高品质的回路配线的制造。
Claims (19)
1、半导体基体用洗涤液,其特征在于:含有氧化剂、酸和氟化合物,通过添加碱性化合物使pH调整为3~10,且水的浓度为80重量%以上。
2、半导体基体用洗涤液,其特征在于:含有氧化剂、酸、氟化合物和腐蚀抑制剂,通过添加碱性化合物使pH调整为3~10,且水的浓度为80重量%以上。
3、根据权利要求1或2记载的洗涤液,其中,所述洗涤液中的酸/氧化剂重量比为0.1~1000。
4、根据权利要求1~3的任一项记载的洗涤液,其中,所述氧化剂为过氧化氢。
5、根据权利要求1~3的任一项记载的洗涤液,其中,所述氧化剂为硝酸。
6、根据权利要求1~5的任一项记载的洗涤液,其中,所述酸为无机酸。
7、根据权利要求1~6的任一项记载的洗涤液,其中,所述无机酸为从硼酸、氨基磺酸、磷酸、碳酸中选取的至少一种。
8、根据权利要求1~6的任一项记载的洗涤液,其中,所述无机酸为硫酸。
9、根据权利要求1~5的任一项记载的洗涤液,其中,所述酸为有机酸。
10、根据权利要求1~5及9的任一项记载的洗涤液,其中,所述有机酸为从草酸、柠檬酸、丙酸、醋酸中选取的至少一种。
11、根据权利要求1~10的任一项记载的洗涤液,其中,所述氟化合物为氟化铵或氟化四甲铵。
12、根据权利要求1~11的任一项记载的洗涤液,其中,所述碱性化合物为无金属离子强碱。
13、根据权利要求1~12的任一项记载的洗涤液,其中,所述无金属离子强碱为氢氧化四甲铵或氢氧化三甲基羟乙基铵。
14、根据权利要求2~13的任一项记载的洗涤液,其中,所述腐蚀抑制剂为聚乙烯亚胺。
15、根据权利要求1~14的任一项记载的洗涤液,其中,在所述洗涤液中还配合表面活性剂。
16、根据权利要求15记载的洗涤液,其中,所述表面活性剂为阴离子性表面活性剂。
17、根据权利要求16记载的洗涤液,其中,所述阴离子性表面活性剂为聚氧乙烯烷基醚的磷酸酯或聚氧乙烯烷基芳基醚的磷酸酯。
18、根据权利要求1~17的任一项记载的洗涤液,其中,所述半导体基体为实施了含有铜单体或铜和隔离金属的层压结构的金属配线的半导体基体。
19、实施了金属配线的半导体基体的洗涤方法,其特征在于:使用权利要求1~18的任一项记载的洗涤液。
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JP382738/2003 | 2003-11-12 | ||
JP2003382738A JP4374989B2 (ja) | 2003-11-12 | 2003-11-12 | 洗浄液およびそれを用いた洗浄方法 |
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Also Published As
Publication number | Publication date |
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KR101047776B1 (ko) | 2011-07-07 |
TWI403579B (zh) | 2013-08-01 |
CN100526450C (zh) | 2009-08-12 |
US20040224866A1 (en) | 2004-11-11 |
KR20040074611A (ko) | 2004-08-25 |
TW200500458A (en) | 2005-01-01 |
SG129274A1 (en) | 2007-02-26 |
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