KR102008881B1 - Composition for cleaning of semiconductor wafer - Google Patents
Composition for cleaning of semiconductor wafer Download PDFInfo
- Publication number
- KR102008881B1 KR102008881B1 KR1020130093082A KR20130093082A KR102008881B1 KR 102008881 B1 KR102008881 B1 KR 102008881B1 KR 1020130093082 A KR1020130093082 A KR 1020130093082A KR 20130093082 A KR20130093082 A KR 20130093082A KR 102008881 B1 KR102008881 B1 KR 102008881B1
- Authority
- KR
- South Korea
- Prior art keywords
- acid
- cleaning
- semiconductor wafer
- cleaning composition
- hydroxide
- Prior art date
Links
- 238000004140 cleaning Methods 0.000 title claims abstract description 104
- 239000000203 mixture Substances 0.000 title claims abstract description 59
- 239000004065 semiconductor Substances 0.000 title claims abstract description 38
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 15
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 14
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 13
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 13
- 150000007524 organic acids Chemical class 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims description 21
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 15
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical group [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 8
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 6
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 6
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 6
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 6
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 6
- 239000011975 tartaric acid Substances 0.000 claims description 6
- 235000002906 tartaric acid Nutrition 0.000 claims description 6
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 5
- 235000005985 organic acids Nutrition 0.000 claims description 5
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 4
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 4
- 235000015165 citric acid Nutrition 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 claims description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 3
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 claims description 3
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000005642 Oleic acid Substances 0.000 claims description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 3
- 235000021314 Palmitic acid Nutrition 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- WJLUBOLDZCQZEV-UHFFFAOYSA-M hexadecyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CCCCCCCCCCCCCCCC[N+](C)(C)C WJLUBOLDZCQZEV-UHFFFAOYSA-M 0.000 claims description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 3
- 235000001968 nicotinic acid Nutrition 0.000 claims description 3
- 229960003512 nicotinic acid Drugs 0.000 claims description 3
- 239000011664 nicotinic acid Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 229960002446 octanoic acid Drugs 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 3
- 235000021313 oleic acid Nutrition 0.000 claims description 3
- CKMXAIVXVKGGFM-UHFFFAOYSA-N p-cumic acid Chemical compound CC(C)C1=CC=C(C(O)=O)C=C1 CKMXAIVXVKGGFM-UHFFFAOYSA-N 0.000 claims description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 3
- 235000019260 propionic acid Nutrition 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
- 229960004889 salicylic acid Drugs 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 claims description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 3
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- 229940005605 valeric acid Drugs 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 235000012431 wafers Nutrition 0.000 abstract description 66
- 230000000694 effects Effects 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000000356 contaminant Substances 0.000 description 16
- 238000005406 washing Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- 229910019142 PO4 Inorganic materials 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 235000021317 phosphate Nutrition 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 8
- 239000010452 phosphate Substances 0.000 description 8
- 125000006353 oxyethylene group Chemical group 0.000 description 7
- 239000002002 slurry Substances 0.000 description 6
- 238000011109 contamination Methods 0.000 description 5
- -1 hydroxide ions Chemical class 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 2
- 238000007517 polishing process Methods 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- ZLRANBHTTCVNCE-UHFFFAOYSA-N 2-phenyl-3-(trifluoromethyl)pyridine Chemical compound FC(F)(F)C1=CC=CN=C1C1=CC=CC=C1 ZLRANBHTTCVNCE-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920005682 EO-PO block copolymer Polymers 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- HXCHRJMJMALFHP-UHFFFAOYSA-N azanium;ethanol;hydroxide Chemical compound N.O.CCO HXCHRJMJMALFHP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 230000005226 mechanical processes and functions Effects 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000000733 zeta-potential measurement Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/34—Derivatives of acids of phosphorus
- C11D1/342—Phosphonates; Phosphinates or phosphonites
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/042—Acids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/30—Amines; Substituted amines ; Quaternized amines
-
- 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
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Abstract
본 발명은 반도체 웨이퍼 세정용 조성물에 관한 것으로, 보다 상세하게는 4급 암모늄 히드록시드; 화학식 1로 표시되는 음이온 계면활성제; 및 유기산, 무기산 또는 이들의 염을 포함함으로써, 세정 효과가 현저히 개선됨에 따라 장치의 수율 및 소자 특성이 우수한 반도체 디바이스를 제조할 수 있도록 하는 반도체 웨이퍼 세정용 조성물에 관한 것이다.The present invention relates to a composition for cleaning semiconductor wafers, more particularly quaternary ammonium hydroxide; Anionic surfactant represented by the formula (1); And an organic acid, an inorganic acid, or a salt thereof, the present invention relates to a semiconductor wafer cleaning composition which enables manufacturing a semiconductor device having excellent device yield and device characteristics as the cleaning effect is remarkably improved.
Description
본 발명은 반도체 웨이퍼 세정용 조성물에 관한 것이다.
The present invention relates to a composition for semiconductor wafer cleaning.
오늘날 반도체 소자 제조용 재료로서 광범위하게 사용되고 있는 웨이퍼(wafer)는 다결정의 실리콘을 원재료로 하여 만들어진 단결정 실리콘 박판을 말한다.A wafer widely used as a material for manufacturing a semiconductor device today refers to a single crystalline silicon thin film made of polycrystalline silicon as a raw material.
이러한 웨이퍼는, 다결정의 실리콘을 단결정 실리콘 잉곳(ingot)으로 성장시키는 성장 공정, 성장된 단결정 실리콘 잉곳을 웨이퍼의 형태로 자르는 슬라이싱 공정, 웨이퍼의 두께를 균일화하여 평면화하는 래핑(lapping) 공정, 기계적인 연마에 의하여 발생한 손상을 제거 또는 완화하는 에칭(etching) 공정, 웨이퍼 표면을 경면화하는 폴리싱(polishing) 공정, 그리고 웨이퍼를 세정하는 세정 공정(cleaning) 등을 거쳐 제조된다.Such wafers include a growth process for growing polycrystalline silicon into a single crystal silicon ingot, a slicing process for cutting the grown single crystal silicon ingot into wafer form, a lapping process to uniformly flatten the thickness of the wafer, and a mechanical process. It is manufactured through an etching process to remove or alleviate damage caused by polishing, a polishing process to mirror the surface of the wafer, and a cleaning process to clean the wafer.
이러한 방법으로 제조된 웨이퍼를 폴리시드 웨이퍼(polished wafer)라 한다. 한편, 에피택셜 웨이퍼(epitaxial wafer)는 폴리시드 웨이퍼 표면에 또 다른 단결정막(또는 "에피층")을 성장시킨 웨이퍼를 말하며, 폴리시드 웨이퍼보다 표면 결함이 적고, 불순물의 농도나 종류의 제어가 가능한 특성을 갖는 웨이퍼이다. 상기 에피층은 순도가 높고 결정 특성이 우수하여 고집적화되고 있는 반도체 장치의 수율 및 소자 특성 향상에 유리한 장점을 갖는다.Wafers manufactured in this manner are referred to as polished wafers. An epitaxial wafer, on the other hand, refers to a wafer in which another single crystal film (or “epitaxial layer”) is grown on the surface of a polysid wafer, and has less surface defects than the polysid wafer, and controls the concentration or type of impurities. It is a wafer with possible properties. The epi layer has an advantage of improving the yield and device characteristics of a semiconductor device that is highly integrated due to its high purity and excellent crystal characteristics.
상기 웨이퍼 제조 공정 중 슬라이싱 공정 및 폴리싱 공정 중에, 다수의 실리콘 파티클들이 웨이퍼 표면에 흡착하여 오염 원인이 되므로, 세정 공정에서 세정액으로 웨이퍼 표면을 세정하게 된다.During the slicing process and the polishing process of the wafer manufacturing process, a plurality of silicon particles are adsorbed onto the wafer surface to cause contamination, and thus the wafer surface is cleaned with the cleaning liquid in the cleaning process.
파티클 오염의 제거에 통상적으로 사용되는 세정액으로는, 알칼리성 수용액이 유효한 것이 알려져 있다. 반도체 웨이퍼 표면의 세정에는 암모니아 수용액, 수산화 칼륨 수용액, 수산화 테트라메틸암모늄 수용액 등의 알칼리성 수용액이 사용되고 있다. 또한 암모니아, 과산화수소, 물을 포함하는 세정액 ("SC-1 세정액" 또는 "APM 세정액"이라 칭한다)에 의한 세정("SC-1 세정" 또는 "APM 세정"이라 칭한다)도 널리 사용되고 있다. 그리고 최근에는 이와 같은 알칼리성 세정액의 성능을 개선하기 위하여, 다양한 계면활성제를 첨가하는 것이 제안되어 있다. It is known that alkaline aqueous solution is effective as a washing | cleaning liquid normally used for removal of particle contamination. Alkaline aqueous solutions, such as aqueous ammonia, potassium hydroxide, and tetramethylammonium hydroxide, are used to clean the semiconductor wafer surface. In addition, cleaning with a cleaning liquid containing ammonia, hydrogen peroxide, and water (called "SC-1 cleaning liquid" or "APM cleaning liquid") (called "SC-1 cleaning" or "APM cleaning") is also widely used. In recent years, in order to improve the performance of such an alkaline cleaning liquid, it is proposed to add various surfactants.
오염 중에서도 특히 실리카입자, 알루미나 입자나 유기물 입자와 같은 미소입자(파티클)에 의한 오염은 디바이스의 수율을 저하시키기 때문에, 다음 공정에 들어가기 전에 최대한 저감시킬 필요가 있으므로, 우수한 세정 효과를 갖는 세정제의 개발이 요구되는 실정이다.Among the contaminations, in particular, contamination by microparticles (particles) such as silica particles, alumina particles or organic particles lowers the yield of the device, so it is necessary to reduce as much as possible before entering the next step, thus developing a cleaner having excellent cleaning effect. This is required.
한국공개특허 제2009-77137호에는 웨이퍼 세정액이 개시되어 있다.
Korean Patent Publication No. 2009-77137 discloses a wafer cleaning liquid.
본 발명은 우수한 세정 효과를 갖는 웨이퍼 세정용 조성물을 제공하는 것을 목적으로 한다.
An object of the present invention is to provide a composition for wafer cleaning having an excellent cleaning effect.
1. 4급 암모늄 히드록시드; 화학식 1로 표시되는 포스페이트; 및 유기산, 무기산 또는 이들의 염을 포함하는 반도체 웨이퍼 세정용 조성물:Quaternary ammonium hydroxide; Phosphates represented by Formula 1; And organic acids, inorganic acids or salts thereof.
[화학식 1][Formula 1]
(식 중, R은 탄소수 1 내지 15의 직쇄 또는 분지쇄인 알킬기 또는 알케닐기이고, x는 1 내지 30의 정수임).(Wherein R is a linear or branched alkyl or alkenyl group having 1 to 15 carbon atoms and x is an integer of 1 to 30).
2. 위 1에 있어서, 상기 4급 암모늄 히드록시드는 테트라메틸암모늄 히드록시드, 테트라에틸암모늄 히드록시드, 테트라프로필암모늄 히드록시드, 테트라부틸암모늄 히드록시드, 세틸트리메틸암모늄 히드록시드 및 테트라에탄올암모늄 히드록시드로 이루어진 군에서 선택된 적어도 하나인, 반도체 웨이퍼 세정용 조성물.2. according to the above 1, wherein the quaternary ammonium hydroxide is tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, cetyltrimethylammonium hydroxide and tetra At least one selected from the group consisting of ethanol ammonium hydroxide, a semiconductor wafer cleaning composition.
3. 위 1에 있어서, 상기 4급 암모늄 히드록시드는 세정용 조성물 총 중량 중 0.001 내지 50중량%로 포함되는, 반도체 웨이퍼 세정용 조성물.3. In the above 1, wherein the quaternary ammonium hydroxide is contained in 0.001 to 50% by weight of the total weight of the cleaning composition, the semiconductor wafer cleaning composition.
4. 위 1에 있어서, 상기 화학식 1에서 R은 탄소수 6 내지 12인, 반도체 웨이퍼 세정용 조성물.4. In the above 1, wherein in Formula 1 R is 6 to 12 carbon atoms, the semiconductor wafer cleaning composition.
5. 위 1에 있어서, 상기 음이온 계면활성제는 세정용 조성물 총 중량 중 0.001 내지 10중량%로 포함되는, 반도체 웨이퍼 세정용 조성물.5. according to the above 1, wherein the anionic surfactant is contained in 0.001 to 10% by weight of the total weight of the cleaning composition, the semiconductor wafer cleaning composition.
6. 위 1에 있어서, 제타 전위의 절대값이 40mV 이상인, 반도체 웨이퍼 세정용 조성물.6. In the above 1, the absolute value of the zeta potential is 40mV or more, the semiconductor wafer cleaning composition.
7. 위 1에 있어서, 상기 유기산은 포름산, 아세트산, 프로피온산, 부티르산, 팔미트산, 스테아르산, 올레산, 옥살산, 말론산, 숙신산, 타타르산, 말레산, 글리콜산, 글루타르산, 아디프산, 술포숙신산, 발레르산, 카프로산, 카프릴산, 카프릭산, 로르산, 미리스트산, 젖산, 사과산, 시트르산, 주석산, 벤조산, 살리실산, 파라톨루엔술폰산, 나프토산, 니코틴산, 톨루엔산, 아니스산, 쿠민산 및 프탈산으로 이루어진 군에서 선택된 적어도 하나이고; 상기 무기산은 염산, 황산, 질산, 인산 및 탄산으로 이루어진 군에서 선택된 적어도 하나인, 반도체 웨이퍼 세정용 조성물.7. In the above 1, the organic acid is formic acid, acetic acid, propionic acid, butyric acid, palmitic acid, stearic acid, oleic acid, oxalic acid, malonic acid, succinic acid, tartaric acid, maleic acid, glycolic acid, glutaric acid, adipic acid , Sulfosuccinic acid, valeric acid, caproic acid, caprylic acid, capric acid, loric acid, myristic acid, lactic acid, malic acid, citric acid, tartaric acid, benzoic acid, salicylic acid, paratoluenesulfonic acid, naphthoic acid, nicotinic acid, toluic acid, ani At least one selected from the group consisting of succinic acid, cuminic acid and phthalic acid; The inorganic acid is at least one selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and carbonic acid, a semiconductor wafer cleaning composition.
8. 위 1에 있어서, 상기 유기산, 무기산 또는 이들의 염은 세정용 조성물 총 중량 중 0.01 내지 10중량%로 포함되는, 반도체 웨이퍼 세정용 조성물.8. according to the above 1, wherein the organic acid, inorganic acid or salt thereof is contained in 0.01 to 10% by weight of the total weight of the cleaning composition, the semiconductor wafer cleaning composition.
9. 위 1 내지 8 중 어느 한 항의 세정용 조성물로 반도체 웨이퍼를 세정하는, 반도체 웨이퍼의 세정 방법.
9. The cleaning method of a semiconductor wafer for cleaning the semiconductor wafer with the cleaning composition of any one of the above 1 to 8.
본 발명의 세정용 조성물은 반도체 웨이퍼 표면에 부착된 오염물질에 대하여 현저히 개선된 세정력을 갖는다. 이에 따라 웨이퍼 표면을 고도로 청정화하여, 장치의 수율 및 소자 특성이 우수한 반도체 디바이스를 제조할 수 있도록 한다.
The cleaning composition of the present invention has a remarkably improved cleaning power against contaminants adhering to the semiconductor wafer surface. As a result, the wafer surface is highly cleaned, allowing the manufacture of a semiconductor device having excellent device yield and device characteristics.
본 발명은 4급 암모늄 히드록시드; 화학식 1로 표시되는 음이온 계면활성제; 및 유기산, 무기산 또는 이들의 염을 포함함으로써, 세정 효과가 현저히 개선됨에 따라 장치의 수율 및 소자 특성이 우수한 반도체 디바이스를 제조할 수 있도록 하는 반도체 웨이퍼 세정용 조성물에 관한 것이다.The present invention is quaternary ammonium hydroxide; Anionic surfactant represented by the formula (1); And an organic acid, an inorganic acid, or a salt thereof, the present invention relates to a semiconductor wafer cleaning composition which enables manufacturing a semiconductor device having excellent device yield and device characteristics as the cleaning effect is remarkably improved.
이하 본 발명을 상세히 설명하기로 한다.
Hereinafter, the present invention will be described in detail.
본 발명의 반도체 웨이퍼 세정용 조성물은 4급 암모늄 히드록시드를 포함한다.The composition for cleaning semiconductor wafers of the present invention comprises quaternary ammonium hydroxide.
4급 암모늄 히드록시드는 히드록시드 이온을 배출하고, 웨이퍼 표면을 세정하고 오염물질 내로 침투하여 오염물질의 용해를 촉진한다.Quaternary ammonium hydroxides release hydroxide ions, clean the wafer surface and penetrate into the contaminants to promote dissolution of the contaminants.
4급 암모늄 히드록시드는 특별히 한정되지 않으며, 예를 들면 테트라메틸암모늄 히드록시드, 테트라에틸암모늄 히드록시드, 테트라프로필암모늄 히드록시드, 테트라부틸암모늄 히드록시드, 세틸트리메틸암모늄 히드록시드, 테트라에탄올암모늄 히드록시드 등을 들 수 있고, 바람직하게는 테트라메틸암모늄 히드록시드일 수 있다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다. The quaternary ammonium hydroxide is not particularly limited, and for example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, cetyltrimethylammonium hydroxide, tetra Ethanol ammonium hydroxide and the like, and preferably tetramethylammonium hydroxide. These can be used individually or in mixture of 2 or more types.
본 발명에 따른 4급 암모늄 히드록시드는 그 기능을 다 할 수 있는 범위 내에서는 그 함량이 특별히 한정되지 않으며, 예를 들면 세정용 조성물 총 중량 중 0.001 내지 50중량%로 포함될 수 있다. 4급 암모늄 히드록시드의 함량이 0.001중량% 미만인 경우 오염물질의 제거력이 충분하지 않을 수 있고, 50중량% 초과인 경우에는 웨이퍼 표면에 손상이 발생할 수 있다. 그러한 측면에서 바람직하게는 0.1 내지 20중량%로 포함될 수 있다.The quaternary ammonium hydroxide according to the present invention is not particularly limited in its content within the range capable of performing its function, for example, may be included in 0.001 to 50% by weight of the total weight of the cleaning composition. If the content of the quaternary ammonium hydroxide is less than 0.001% by weight, the removal power of the contaminants may not be sufficient, and if the content of the quaternary ammonium hydroxide is more than 50% by weight, damage to the wafer surface may occur. In such aspect, it may be included preferably 0.1 to 20% by weight.
본 발명의 반도체 웨이퍼 세정용 조성물은 음이온 계면활성제를 포함한다.The composition for semiconductor wafer cleaning of the present invention contains an anionic surfactant.
본 발명에 따른 음이온 계면활성제는 하기 화학식 1로 표시된다:Anionic surfactants according to the invention are represented by the following general formula (1):
[화학식 1][Formula 1]
(식 중, R은 탄소수 1 내지 15의 직쇄 또는 분지쇄인 알킬기 또는 알케닐기이고, x는 1 내지 30의 정수임).(Wherein R is a linear or branched alkyl or alkenyl group having 1 to 15 carbon atoms and x is an integer of 1 to 30).
상기 화학식 1에서 친수성 부분의 산소가 물 분자와 수소결합하고, 소수성 부분이 물 분자들 사이로 침투하여 물 분자 간의 인력을 약화시켜 표면장력을 감소시켜 계면활성제로서 역할한다.In Formula 1, the oxygen of the hydrophilic portion is hydrogen-bonded with the water molecule, and the hydrophobic portion penetrates between the water molecules to weaken the attraction between the water molecules to reduce the surface tension to serve as a surfactant.
통상적으로 계면활성제의 친수성 부분이 오염물질과 결합하고 이를 소수성 부분이 감싸서 웨이퍼로부터 제거하는데, 화학식 1로 표시되는 음이온 계면활성제는 소수성 부분에 알킬페닐 그룹을 가지므로 보다 소수성이 강화되어 웨이퍼 상의 오염물질의 제거력을 높여, 이에 따라 세정력을 현저히 개선한다.Typically, the hydrophilic portion of the surfactant binds to the contaminant and is removed from the wafer by wrapping it in a hydrophobic portion. Since the anionic surfactant represented by Formula 1 has an alkylphenyl group in the hydrophobic portion, the hydrophobicity is enhanced to contaminants on the wafer. It is possible to increase the removal power of, thereby significantly improving the cleaning power.
상기 화학식 1에서 R의 탄소수가 상기 범위 내인 경우, 친수성 부분의 오염물질과의 결합을 저해하지 않으면서 소수성 강화에 의한 세정력 개선 효과를 극대화 할 수 있다. 그러한 측면에서 바람직하게는 탄소수가 6 내지 12일 수 있다.When the carbon number of R in the formula (1) is within the above range, it is possible to maximize the effect of improving the cleaning power by strengthening hydrophobicity without inhibiting the binding of the hydrophilic portion with contaminants. In such aspect, it may preferably be 6 to 12 carbon atoms.
또한, 웨이퍼 표면의 오염물질은 통상적으로 전기적으로 음의 전하를 갖는데, 본 발명에 따른 음이온 계면활성제는 인산기를 포함하여 조성물 내에서 다량의 음전하를 나타내므로 오염물질과의 사이에서 반발력이 작용하므로, 오염물질이 웨이퍼로부터 더 잘 이탈하도록 하여 세정력을 더욱 개선한다.In addition, the contaminants on the wafer surface usually have a negative electric charge, because the anionic surfactant according to the present invention exhibits a large amount of negative charges in the composition including a phosphate group, so the repulsive force acts between the contaminants, It further improves cleaning power by allowing contaminants to escape better from the wafer.
이러한 반발력의 정도는 제타전위를 측정하여 알 수 있는데, 본 발명의 세정액 조성물은 제타전위(zeta potential)의 절대값이 40mV 이상일 수 있다.The degree of repulsive force can be known by measuring the zeta potential. The cleaning liquid composition of the present invention may have an absolute value of zeta potential of 40 mV or more.
전해질 용액 중 콜로이드 입자가 대전하면, 입자가 접촉하는 계면에 대전과 반대 이온을 갖는 미립자가 일부는 흡착되어 고정층을 만들고, 그 외는 용액 중에 확산되어 고정층의 외측에 2중층을 만든다. 이 전기 2중층간에 생긴 전위차가 제타전위로서, 이 제타 전위의 절대값이 증가하면 입자간의 반발력이 강해진다.When the colloidal particles in the electrolyte solution are charged, some of the fine particles having charge and counter ions are adsorbed to the interface where the particles come into contact with each other to form a fixed layer, and others diffuse into the solution to form a double layer outside the fixed layer. The potential difference generated between the electric double layers is a zeta potential, and when the absolute value of the zeta potential increases, the repulsive force between particles becomes stronger.
본 발명의 세정액 조성물은 상기 범위의 제타전위 값을 가짐으로써, 오염물질간의 반발력이 크게 작용하여, 오염물질이 웨이퍼로부터 쉽게 이탈할 수 있으므로 세정력이 현저히 개선된다.Since the cleaning liquid composition of the present invention has a zeta potential value in the above range, the repulsive force between contaminants acts greatly, and thus the cleaning power is remarkably improved since the contaminants can be easily released from the wafer.
또한, 상기 구조를 갖는 본 발명에 따른 음이온 계면활성제는 세정용 조성물 내의 다른 조성과의 반응에 의한 고체염을 생성 및 악취 유발의 염려도 적은 장점이 있다.In addition, the anionic surfactant according to the present invention having the above structure has the advantage of generating a solid salt by reaction with other compositions in the cleaning composition and fear of causing odor.
본 발명에 따른 음이온 계면활성제는 그 기능을 다 할 수 있는 범위 내에서는 그 함량이 특별히 한정되지 않으며, 예를 들면 세정용 조성물 총 중량 중 0.001 내지 10중량%로 포함될 수 있다. 음이온 계면활성제의 함량이 0.001중량% 미만인 경우에는 오염물질 제거력 개선 효과가 미미할 수 있으며, 10중량% 초과인 경우에는 임계미셀농도(Critical Micelle Concentration)가 되거나 이를 초과하여 물에 용해되지 않을 수 있어 오염물질 제거력 개선 효과가 미미할 수 있고, 다량의 수소이온 발생으로 인해 적정 pH 범위를 벗어나게 될 수 있다. 그러한 측면에서 바람직하게는 0.01 내지 5중량%로 포함될 수 있다.The content of the anionic surfactant according to the present invention is not particularly limited within the range capable of performing its function, for example, may be included in 0.001 to 10% by weight of the total weight of the cleaning composition. If the content of the anionic surfactant is less than 0.001% by weight, the effect of removing pollutants may be insignificant, and if it is more than 10% by weight, the critical micelle concentration may be greater than or not dissolved in water. The effect of improving the material removal power may be insignificant, and due to the generation of a large amount of hydrogen ions, it may be out of the proper pH range. In such aspect, it may be preferably included in 0.01 to 5% by weight.
본 발명의 반도체 웨이퍼 세정용 조성물은 유기산, 무기산 또는 이들의 염을 포함한다.The semiconductor wafer cleaning composition of the present invention contains an organic acid, an inorganic acid or a salt thereof.
유기산, 무기산 또는 이들의 염은 오염물질들 사이에 배열되어 전기적 반발력을 일으켜 오염물질의 분산성을 향상시킨다. 이에 따라 세정력을 개선한다. 또한, 적정 pH를 유지하는 pH 조절제로 작용한다.Organic acids, inorganic acids or salts thereof are arranged between contaminants to cause electrical repulsion to improve the dispersibility of the contaminants. This improves the cleaning power. It also acts as a pH adjuster to maintain the proper pH.
유기산은 특별히 한정되지 않으며, 예를 들면 포름산, 아세트산, 프로피온산, 부티르산, 팔미트산, 스테아르산, 올레산, 옥살산, 말론산, 숙신산, 타타르산, 말레산, 글리콜산, 글루타르산, 아디프산, 술포숙신산, 발레르산, 카프로산, 카프릴산, 카프릭산, 로르산, 미리스트산, 젖산, 사과산, 시트르산, 주석산 등의 지방족 유기산; 벤조산, 살리실산, 파라톨루엔술폰산, 나프토산, 니코틴산, 톨루엔산, 아니스산, 쿠민산, 프탈산 등의 방향족 유기산을 들 수 있다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.The organic acid is not particularly limited, and for example, formic acid, acetic acid, propionic acid, butyric acid, palmitic acid, stearic acid, oleic acid, oxalic acid, malonic acid, succinic acid, tartaric acid, maleic acid, glycolic acid, glutaric acid, adipic acid Aliphatic organic acids such as sulfosuccinic acid, valeric acid, caproic acid, caprylic acid, capric acid, loric acid, myristic acid, lactic acid, malic acid, citric acid and tartaric acid; And aromatic organic acids such as benzoic acid, salicylic acid, paratoluenesulfonic acid, naphthoic acid, nicotinic acid, toluic acid, aniseic acid, cuminic acid and phthalic acid. These can be used individually or in mixture of 2 or more types.
무기산은 특별히 한정되지 않으며, 예를 들면 염산, 황산, 질산, 인산, 탄산 등을 들 수 있다.The inorganic acid is not particularly limited, and examples thereof include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and carbonic acid.
염은 특별히 한정되지 않으며, 예를 들면 칼륨염, 나트륨염, 암모늄염, 칼슘염, 마그네슘염 등을 들 수 있다.A salt is not specifically limited, For example, potassium salt, sodium salt, ammonium salt, calcium salt, magnesium salt, etc. are mentioned.
유기산, 무기산 또는 이들의 염의 함량은 특별히 한정되지 않으며, 예를 들면 세정용 조성물 총 중량 중 0.01 내지 10중량%로 포함될 수 있다. 유기산, 무기산 또는 이들의 염의 함량이 0.01중량% 미만인 경우에는, 전기적 반발력 형성에 의한 분산성 개선 효과가 미미할 수 있다. 또한 10중량% 초과인 경우에는 적정 pH 범위를 초과할 수 있고 용해도도 떨어져서 마찬가지로 세정력 개선 효과가 미미할 수 있다.The content of the organic acid, the inorganic acid or salts thereof is not particularly limited, and may be included, for example, in an amount of 0.01 to 10% by weight of the total weight of the cleaning composition. When the content of the organic acid, inorganic acid or salts thereof is less than 0.01% by weight, the effect of improving dispersibility due to the formation of electrical repulsive force may be insignificant. In addition, in the case of more than 10% by weight, it may exceed the appropriate pH range and the solubility is also lowered, so the effect of improving the cleaning power may be insignificant.
본 발명의 세정용 조성물은 상기 성분들을 구체적인 필요에 따라 적절하게 채택한 후, 물을 첨가하여 전체 조성을 조절하게 되어 전체 조성물의 잔량은 물이 차지한다. 바람직하게는 상기 성분들이 전술한 함량 범위를 갖도록 조절한다.In the cleaning composition of the present invention, after appropriately adopting the above components according to specific needs, water is added to adjust the overall composition so that the remaining amount of the entire composition is occupied by water. Preferably the components are adjusted to have the aforementioned content ranges.
물의 종류는 특별히 한정되지 않으나, 탈이온 증류수인 것이 바람직하다.Although the kind of water is not specifically limited, It is preferable that it is deionized distilled water.
또한, 본 발명은 상기 세정용 조성물로 반도체 웨이퍼를 세정하는 세정 방법을 제공한다.The present invention also provides a cleaning method for cleaning a semiconductor wafer with the cleaning composition.
본 발명의 세정방법은, 세정용 조성물을 직접 웨이퍼에 접촉시키는 방법으로 실시된다. 세정용 조성물의 웨이퍼로의 접촉방법에는, 세정조에 세정용 조성물을 채워 웨이퍼를 침지시키는 딥식, 노즐로부터 웨이퍼 상에 세정용 조성물을 흘려 보내면서 웨이퍼를 고속회전시키는 스핀식, 웨이퍼에 세정용 조성물을 분무하여 세정하는 스프레이식 등을 들 수 있다. 이와 같은 세정을 실시하기 위한 장치로는, 카세트에 수용된 복수장의 웨이퍼를 동시에 세정하는 배치식 세정장치, 1장의 웨이퍼를 홀더에 장착하여 세정하는 매엽식 세정장치 등이 있다. 본 발명의 세정방법은 상기 어느 방법에도 적용할 수 있다. 본 발명의 세정방법은 그 중에서도 세정시간의 단축, 세정용 조성물 사용량의 삭감이 문제가 되고 있는 매엽식 세정장치에 적용하면, 이들 문제가 해소되므로 바람직하다. 또 배치식 세정장치에서도 높은 파티클의 제거효과를 얻을 수 있으므로 바람직하다.The cleaning method of the present invention is carried out by a method of directly bringing a cleaning composition into contact with a wafer. The method for contacting the cleaning composition to the wafer includes a dip type in which a cleaning composition is filled in a cleaning tank to immerse the wafer, a spin type in which the wafer is rotated at a high speed while flowing the cleaning composition onto the wafer, and a cleaning composition in the wafer. A spray type etc. which spray and wash are mentioned. As an apparatus for performing such a washing | cleaning, there exist a batch type | mold washing | cleaning apparatus which wash | cleans a plurality of wafers accommodated in a cassette simultaneously, the sheet type washing | cleaning apparatus which mounts and wash | cleans one wafer to a holder. The washing method of the present invention can be applied to any of the above methods. The cleaning method of the present invention is preferable because the problem is solved when applied to a single sheet type washing apparatus in which the cleaning time is shortened and the amount of the composition used for cleaning is a problem. In addition, even in a batch type washing apparatus, since high particle removal effect can be acquired, it is preferable.
세정은 실온에서 수행해도 되지만, 세정효과를 향상시키는 목적에서 가온하여 수행될 수 있다. 통상, 20∼90℃ 범위, 바람직하게는 40∼80℃ 범위에서 수행될 수 있다.The washing may be carried out at room temperature, but may be carried out by heating for the purpose of improving the washing effect. Usually, it may be carried out in the range of 20 to 90 ° C, preferably in the range of 40 to 80 ° C.
세정 시간은 배치식 세정의 경우, 통상 30초 내지 30분간, 바람직하게는 1∼15분간, 매엽식 세정에서는 통상, 1초 내지 5분간, 바람직하게는 15초 내지 1분간 수행될 수 있다. 세정 시간이 너무 짧으면 세정 효과가 충분하지 않고, 너무 길면 쓰루풋이 저하될 뿐만 아니라, 세정 시간의 연장에 알맞은 효과의 향상을 기대할 수 없다.In the case of batch cleaning, the cleaning time may be generally performed for 30 seconds to 30 minutes, preferably 1 to 15 minutes, and for single sheet cleaning, usually 1 second to 5 minutes, preferably 15 seconds to 1 minute. If the cleaning time is too short, the cleaning effect will not be sufficient. If the cleaning time is too long, throughput will not only decrease, but improvement of the effect suitable for extending the cleaning time cannot be expected.
또한, 세정시에는, 물리력에 의한 세정방법, 예컨대 세정 브러시를 사용한 스크랩 세정 등의 기계적 세정, 또는 초음파 세정과 병용시켜도 된다. 특히 초음파 조사 또는 브러시 스크랩을 병용하면, 파티클 오염의 제거성이 더욱 향상되고, 세정시간의 단축으로도 이어지므로 바람직하다. 특히 웨이퍼에 주파수 0.5 메가헬츠 이상의 초음파를 조사하면, 계면활성제와의 상승작용에 의해, 0.1㎛ 레벨의 파티클의 제거성이 현저하게 향상되므로 바람직하다.In addition, at the time of washing | cleaning, you may use together with the washing | cleaning method by a physical force, for example, mechanical cleaning, such as scrap cleaning using a cleaning brush, or ultrasonic cleaning. In particular, the use of ultrasonic irradiation or brush scrap is preferable because the removal of particle contamination is further improved, and the cleaning time can be shortened. In particular, when the wafer is irradiated with an ultrasonic wave of frequency 0.5 MegaHeltz or more, the removal property of particles having a 0.1 μm level is remarkably improved by synergy with the surfactant.
본 발명의 세정 방법을 이용하여 세정할 수 있는 반도체 웨이퍼는 특별히 한정되지 않고 당 분야에서 통상적으로 사용되는 반도체 웨이퍼에 사용될 수 있으며, 예를 들면 실리콘, 게르마늄 등의 일원소계 반도체의 웨이퍼, 또는 갈륨-인, 갈륨비소, 인듐-인 등의 화합물 반도체의 웨이퍼 등을 들 수 있다.The semiconductor wafer which can be cleaned using the cleaning method of the present invention is not particularly limited and may be used for a semiconductor wafer commonly used in the art, for example, a wafer of a one-element semiconductor such as silicon, germanium, or gallium- Wafers of compound semiconductors, such as phosphorus, gallium arsenide, and indium phosphorus, etc. are mentioned.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 이들 실시예는 본 발명을 예시하는 것일 뿐 첨부된 특허청구범위를 제한하는 것이 아니며, 본 발명의 범주 및 기술사상 범위 내에서 실시예에 대한 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다.
Hereinafter, preferred examples are provided to help understanding of the present invention. However, these examples are only for exemplifying the present invention, and do not limit the appended claims, but are within the scope and spirit of the present invention. It will be apparent to those skilled in the art that various changes and modifications can be made to the present invention, and such modifications and changes belong to the appended claims.
실시예Example 및 And 비교예Comparative example
하기 표 1의 조성 및 함량을 갖는 반도체 웨이퍼 세정용 조성물을 제조하였다.To prepare a semiconductor wafer cleaning composition having the composition and content of Table 1.
(D)Deionized water
(D)
A-2: 테트라부틸암모늄 히드록시드
B-1: CnH2n +1-(Phenyl)-O-(EO)x-(Phosphate)(2H) (n=6, x=10, EO=옥시에틸렌기)
B-2: CnH2n +1-(Phenyl)-O-(EO)x-(Phosphate)(2H) (n=9, x=10, EO=옥시에틸렌기)
B-3: CnH2n +1-(Phenyl)-O-(EO)x-(Phosphate)(2H) (n=10, x=10, EO=옥시에틸렌기)
B-4: CnH2n +1-(Phenyl)-O-(EO)x-(Phosphate)(2H) (n=12, x=10, EO=옥시에틸렌기)
B-5: CnH2n +1-(Phenyl)-O-(EO)x-(Phosphate)(2H) (n=1, x=10, EO=옥시에틸렌기)
B-6: CnH2n +1-(Phenyl)-O-(EO)x-(Phosphate)(2H) (n=3, x=10, EO=옥시에틸렌기)
B-7: CnH2n +1-(Phenyl)-O-(EO)x-(Phosphate)(2H) (n=15, x=10, EO=옥시에틸렌기)
B-8: EO/PO block copolymer
(50% ethylene oxide, 중량평균분자량 2,500, PO=옥시프로필렌기)
B-9: CnH2n +1-O-(EO)x(PO)y-H (n=9, x=10, y=10)
B-10: CnH2n +1-O-(EO)x-H (n=9, x=10)
B-11: CnH2n +1-O-(EO)x-(Phosphate)(2H) (n=9, x=10)
C-1: 시트르산
C-2: 글루타르산
C-3: 옥살산
C-4: 인산,
C-5: 시트르산 암모늄염A-1: Tetramethylammonium Hydroxide
A-2: tetrabutylammonium hydroxide
B-1: C n H 2n + 1-(Phenyl) -O- (EO) x- (Phosphate) (2H) (n = 6, x = 10, EO = oxyethylene group)
B-2: C n H 2n + 1-(Phenyl) -O- (EO) x- (Phosphate) (2H) (n = 9, x = 10, EO = oxyethylene group)
B-3: C n H 2n + 1-(Phenyl) -O- (EO) x- (Phosphate) (2H) (n = 10, x = 10, EO = oxyethylene group)
B-4: C n H 2n + 1-(Phenyl) -O- (EO) x- (Phosphate) (2H) (n = 12, x = 10, EO = oxyethylene group)
B-5: C n H 2n + 1-(Phenyl) -O- (EO) x- (Phosphate) (2H) (n = 1, x = 10, EO = oxyethylene group)
B-6: C n H 2n + 1-(Phenyl) -O- (EO) x- (Phosphate) (2H) (n = 3, x = 10, EO = oxyethylene group)
B-7: C n H 2n + 1-(Phenyl) -O- (EO) x- (Phosphate) (2H) (n = 15, x = 10, EO = oxyethylene group)
B-8: EO / PO block copolymer
(50% ethylene oxide, weight average molecular weight 2,500, PO = oxypropylene group)
B-9: C n H 2n +1 -O- (EO) x (PO) y -H (n = 9, x = 10, y = 10)
B-10: C n H 2n +1 -O- (EO) x -H (n = 9, x = 10)
B-11: C n H 2n +1 -O- (EO) x- (Phosphate) (2H) (n = 9, x = 10)
C-1: citric acid
C-2: glutaric acid
C-3: oxalic acid
C-4: phosphoric acid,
C-5: ammonium citrate
실험예Experimental Example
(1) 제타 전위 측정(1) zeta potential measurement
실시예 및 비교예의 세정액 조성물 10mL를 각각 Quarz Cell에 담은 후 제타 전위 측정기(ELS-Z, 한국오츠카전자)로 제타 전위를 측정하였다. 상기 과정을 각각 10회 반복하여 그 평균값을 하기 표 2에 나타내었다.
10 mL of the cleaning solution compositions of Examples and Comparative Examples were placed in Quarz Cells, and zeta potentials were measured using a Zeta Potentiometer (ELS-Z, Otsuka Electronics Co., Ltd.). The above procedure was repeated 10 times, and the average value thereof is shown in Table 2 below.
(2) 세정력 평가(2) evaluation of cleaning power
6인치의 P-type 실리콘 웨이퍼의 초기 무게를 측정했다. 이후에 웨이퍼 상에 CMP 슬러리(Colloidal Silica Particles, 직경 0.03 내지 0.1㎛)를 코터기(제조사:DNS 모델명:SK-200W)를 이용하여 1,500rpm으로 10초간 코팅하고 80℃에서 10분간 베이킹한 후의 웨이퍼 무게를 측정했다.Initial weights of 6-inch P-type silicon wafers were measured. After the CMP slurry (Colloidal Silica Particles, diameter 0.03 ~ 0.1㎛) coated on the wafer for 10 seconds at 1,500rpm using a coater (manufacturer: DNS model name: SK-200W) and baked for 10 minutes at 80 ℃ The weight was measured.
이후에 상기 웨이퍼를 실시예 및 비교예의 세정용 조성물에 각각 5분간 침지시켜 세정한 후, 탈이온수에 5초간 세척하고 실온 건조시켰다. 건조된 웨이퍼의 무게를 측정한 후, 하기 수학식 1에 따라 세정용 조성물의 CMP 슬러리 제거율(세정력)을 구하였다.Thereafter, the wafers were immersed in the cleaning compositions of Examples and Comparative Examples for 5 minutes, and then washed, and then washed with deionized water for 5 seconds and dried at room temperature. After measuring the weight of the dried wafer, the removal rate (cleaning force) of the CMP slurry of the cleaning composition was determined according to Equation 1 below.
[수학식 1][Equation 1]
제거율(%) = (슬러리 코팅후 웨이퍼의 무게 - 세정된 웨이퍼의 무게) / (슬러리 코팅 후 웨이퍼의 무게 - 슬러리 코팅 전 웨이퍼의 무게)% Removal = (Weight of slurry after slurry coating-Weight of cleaned wafer) / (Weight of wafer after slurry coating-Weight of wafer before slurry coating)
결과는 하기 표 2에 나타내었다.The results are shown in Table 2 below.
(세정력,%)Removal rate
(Washing power,%)
(세정력,%)Removal rate
(Washing power,%)
상기 표 2를 참고하면, 실시예 1 내지 13의 세정용 조성물은 제타 전위의 절대값이 모두 40mV 이상으로 오염물질 간의 반발력이 매우 높아, 이에 따라 96% 이상의 매우 우수한 세정력을 나타내는 것을 확인할 수 있다.Referring to Table 2, the cleaning compositions of Examples 1 to 13, the absolute value of the zeta potential is all 40mV or more, the repulsion between the contaminants is very high, it can be seen that exhibits a very good cleaning power of 96% or more.
음이온 계면활성제를 바람직한 범위를 벗어나도록 과량으로 포함한 실시예 14의 경우 다른 실시예에 비해 효과가 다소 저하되었으나, 여전히 우수한 성능을 나타내었다.Example 14, which includes an anionic surfactant in an excess amount beyond the preferred range, had a slightly lower effect than other examples, but still showed excellent performance.
그러나 비교예 1 내지 4의 세정용 조성물은 제타 전위의 절대값이 35 미만으로 떨어지므로 오염물질 간의 반발력이 낮아, 세정력이 떨어져 CMP 슬러리가 다수 남아 있는 것을 확인하였다.However, in the cleaning compositions of Comparative Examples 1 to 4, the absolute value of the zeta potential dropped to less than 35, so that the repulsive force between contaminants was low, and the cleaning power was lowered to confirm that many CMP slurries remained.
Claims (9)
화학식 1로 표시되는 음이온 계면활성제; 및
유기산, 무기산 또는 이들의 염을 포함하며,
제타 전위의 절대값이 40mV 이상인, 반도체 웨이퍼 세정용 조성물:
[화학식 1]
(식 중, R은 탄소수 1 내지 15의 직쇄 또는 분지쇄인 알킬기 또는 알케닐기이고,
x는 1 내지 30의 정수임).
Quaternary ammonium hydroxides;
Anionic surfactant represented by the formula (1); And
Organic acids, inorganic acids or salts thereof;
A composition for cleaning a semiconductor wafer, wherein the absolute value of the zeta potential is 40 mV or more:
[Formula 1]
(Wherein R is a linear or branched alkyl or alkenyl group having 1 to 15 carbon atoms,
x is an integer from 1 to 30.
The method of claim 1, wherein the quaternary ammonium hydroxide is tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, cetyltrimethylammonium hydroxide and tetraethanolammonium At least one selected from the group consisting of hydroxide, a semiconductor wafer cleaning composition.
The semiconductor wafer cleaning composition according to claim 1, wherein the quaternary ammonium hydroxide is contained in an amount of 0.001 to 50% by weight based on the total weight of the cleaning composition.
The composition according to claim 1, wherein in Formula 1, R has 6 to 12 carbon atoms.
The semiconductor wafer cleaning composition of claim 1, wherein the anionic surfactant is present in an amount of 0.001 to 10% by weight based on the total weight of the cleaning composition.
The method of claim 1, wherein the organic acid is formic acid, acetic acid, propionic acid, butyric acid, palmitic acid, stearic acid, oleic acid, oxalic acid, malonic acid, succinic acid, tartaric acid, maleic acid, glycolic acid, glutaric acid, adipic acid, sulfo Succinic acid, valeric acid, caproic acid, caprylic acid, capric acid, loric acid, myristic acid, lactic acid, malic acid, citric acid, tartaric acid, benzoic acid, salicylic acid, paratoluenesulfonic acid, naphthoic acid, nicotinic acid, toluic acid, aniseic acid, At least one selected from the group consisting of cuminic acid and phthalic acid; The inorganic acid is at least one selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and carbonic acid, a semiconductor wafer cleaning composition.
The semiconductor wafer cleaning composition of claim 1, wherein the organic acid, the inorganic acid, or a salt thereof is included in an amount of 0.01 to 10 wt% based on the total weight of the cleaning composition.
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