TWI652747B - 可抑制含鉭材料之損壞的半導體元件之清洗液及利用該清洗液的半導體元件之清洗方法 - Google Patents
可抑制含鉭材料之損壞的半導體元件之清洗液及利用該清洗液的半導體元件之清洗方法 Download PDFInfo
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- TWI652747B TWI652747B TW104132920A TW104132920A TWI652747B TW I652747 B TWI652747 B TW I652747B TW 104132920 A TW104132920 A TW 104132920A TW 104132920 A TW104132920 A TW 104132920A TW I652747 B TWI652747 B TW I652747B
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- Prior art keywords
- tantalum
- cleaning
- mass
- film
- cleaning liquid
- Prior art date
Links
- 238000004140 cleaning Methods 0.000 title claims abstract description 112
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910052715 tantalum Inorganic materials 0.000 title claims abstract description 62
- 239000000463 material Substances 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000004065 semiconductor Substances 0.000 title claims abstract description 33
- 239000007788 liquid Substances 0.000 title claims description 30
- 229920002120 photoresistant polymer Polymers 0.000 claims abstract description 39
- 238000001312 dry etching Methods 0.000 claims abstract description 38
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003513 alkali Substances 0.000 claims abstract description 18
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 42
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 26
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 14
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 10
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 10
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 5
- 229940043430 calcium compound Drugs 0.000 claims description 5
- 150000001674 calcium compounds Chemical class 0.000 claims description 5
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 5
- 235000011056 potassium acetate Nutrition 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 235000011181 potassium carbonates Nutrition 0.000 claims description 5
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 5
- 235000011009 potassium phosphates Nutrition 0.000 claims description 5
- 150000003438 strontium compounds Chemical class 0.000 claims description 5
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 5
- 150000001553 barium compounds Chemical class 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims 1
- 150000003482 tantalum compounds Chemical class 0.000 claims 1
- 239000010408 film Substances 0.000 description 57
- 239000000243 solution Substances 0.000 description 41
- 238000005530 etching Methods 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 13
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 239000011229 interlayer Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- -1 hexafluorosilicic acid Chemical compound 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- FCKYPQBAHLOOJQ-UHFFFAOYSA-N Cyclohexane-1,2-diaminetetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)C1CCCCC1N(CC(O)=O)CC(O)=O FCKYPQBAHLOOJQ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 2
- NKQIMNKPSDEDMO-UHFFFAOYSA-L barium bromide Chemical compound [Br-].[Br-].[Ba+2] NKQIMNKPSDEDMO-UHFFFAOYSA-L 0.000 description 2
- 229910001620 barium bromide Inorganic materials 0.000 description 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 2
- 229910001626 barium chloride Inorganic materials 0.000 description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 2
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 2
- 229910001632 barium fluoride Inorganic materials 0.000 description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 description 2
- SGUXGJPBTNFBAD-UHFFFAOYSA-L barium iodide Chemical compound [I-].[I-].[Ba+2] SGUXGJPBTNFBAD-UHFFFAOYSA-L 0.000 description 2
- 229910001638 barium iodide Inorganic materials 0.000 description 2
- 229940075444 barium iodide Drugs 0.000 description 2
- WAKZZMMCDILMEF-UHFFFAOYSA-H barium(2+);diphosphate Chemical compound [Ba+2].[Ba+2].[Ba+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O WAKZZMMCDILMEF-UHFFFAOYSA-H 0.000 description 2
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- VASZYFIKPKYGNC-DHTOPLTISA-N 2-[[(1r,2r)-2-[bis(carboxymethyl)amino]cyclohexyl]-(carboxymethyl)amino]acetic acid;hydrate Chemical compound O.OC(=O)CN(CC(O)=O)[C@@H]1CCCC[C@H]1N(CC(O)=O)CC(O)=O VASZYFIKPKYGNC-DHTOPLTISA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- UNMYWSMUMWPJLR-UHFFFAOYSA-L Calcium iodide Chemical compound [Ca+2].[I-].[I-] UNMYWSMUMWPJLR-UHFFFAOYSA-L 0.000 description 1
- 244000132059 Carica parviflora Species 0.000 description 1
- 235000014653 Carica parviflora Nutrition 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- JJJBUGDRBSGCTD-UHFFFAOYSA-N [Sr].[N+](=O)(O)[O-] Chemical compound [Sr].[N+](=O)(O)[O-] JJJBUGDRBSGCTD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 239000005441 aurora Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 229910001622 calcium bromide Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910001640 calcium iodide Inorganic materials 0.000 description 1
- 229940046413 calcium iodide Drugs 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000004820 halides Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000012487 rinsing solution Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- YJPVTCSBVRMESK-UHFFFAOYSA-L strontium bromide Chemical compound [Br-].[Br-].[Sr+2] YJPVTCSBVRMESK-UHFFFAOYSA-L 0.000 description 1
- 229910001625 strontium bromide Inorganic materials 0.000 description 1
- 229940074155 strontium bromide Drugs 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 description 1
- 229910001637 strontium fluoride Inorganic materials 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- KRIJWFBRWPCESA-UHFFFAOYSA-L strontium iodide Chemical compound [Sr+2].[I-].[I-] KRIJWFBRWPCESA-UHFFFAOYSA-L 0.000 description 1
- 229910001643 strontium iodide Inorganic materials 0.000 description 1
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- JOPDZQBPOWAEHC-UHFFFAOYSA-H tristrontium;diphosphate Chemical compound [Sr+2].[Sr+2].[Sr+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JOPDZQBPOWAEHC-UHFFFAOYSA-H 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/0206—Cleaning during device manufacture during, before or after processing of insulating layers
- H01L21/02063—Cleaning during device manufacture during, before or after processing of insulating layers the processing being the formation of vias or contact holes
-
- 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
- C11D3/046—Salts
-
- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/08—Liquid soap, e.g. for dispensers; capsuled
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/06—Hydroxides
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/10—Salts
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/10—Salts
- C11D7/105—Nitrates; Nitrites
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
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Abstract
根據本發明可以提供一種清洗方法,其將具有Low-k膜與含10原子%以上之鉭之材料之半導體元件之表面之光阻及乾蝕刻殘渣予以除去,其特徵為:使用含有過氧化氫0.002~50質量%、鹼土類金屬化合物0.001~1質量%、鹼及水之清洗液。
Description
本發明係關於一種於半導體元件的製造步驟中,抑制低介電常數膜與含鉭材料的損壞,並將被處理物之表面之光阻及乾蝕刻殘渣予以除去之清洗液,以及使用該清洗液之清洗方法。
高度積體化的半導體元件的製造一般會採取如下之一系列的步驟:通常係於矽晶圓等的元件上形成作為導電用配線素材的金屬膜等的導電薄膜或以進行導電薄膜間的絕緣為目的之層間絕緣膜之後,於其表面均勻地塗佈光阻設置感光層,並對此實施選擇性的曝光・顯像處理,製作所希望的光阻圖案。接下來藉由將此光阻圖案作為光罩,對層間絕緣膜實施乾蝕刻處理,於該薄膜處形成所希望的圖案。然後,利用氧氣電漿灰化或使用清洗液清洗等,將光阻圖案及因乾蝕刻處理而產生的殘渣物(以下稱為「乾蝕刻殘渣」)等完全除去。
近年來,設計規則微型化在進步,信號傳輸的延遲已逐漸主導了高速運算處理的極限。因此,導電用配線素材由鋁過渡到電阻較低的銅,而層間絕緣膜由氧化矽膜向低介電常數膜(相對介電常數比3小的膜。以下稱為「Low-k膜」)的過渡正在進行。銅與層間絕緣膜的密合性並不充足,又銅與層間絕緣膜相接的話,銅會隨著時間擴散於層間絕緣膜。為了改善該等問題,一般會使用於銅與層間絕緣膜之間插入一種稱為障壁金屬(barrier metal)的含鉭材料的膜之方法。又,隨著設計規則的微型化,電晶體柵極的構成由氧化矽與多晶矽的組合已逐漸變更成為高介電常數材料與金屬的組合。有使用含鉭材料作為此金屬的情況。
以氧氣電漿除去光阻、乾蝕刻殘渣的情況,會發生Low-k膜會暴露於氧氣電漿等而受到損壞,且電性質顯著劣化的問題。又,含鉭材料暴露於氧氣電漿等而受到損壞,於其後的製造步驟會產生瑕疵。因此,使用Low-k膜與含鉭材料的半導體元件(圖1)的製造中,要求抑制Low-k膜與含鉭材料的損壞,同時與氧氣電漿步驟同等程度地除去光阻及乾蝕刻殘渣。
已知利用清洗液之處理係藉由使用含有過氧化氫且強鹼性的清洗液,可以除去光阻及乾蝕刻殘渣。含有過氧化氫且強鹼性的清洗液,對光阻及乾蝕刻殘渣的除去性優良,但與含鉭材料接液的話會造成含鉭材料強烈的損壞。因此,期望一種可以有效地除去光阻及乾蝕刻殘渣,而不會造成含鉭材料損壞的含有過氧化氫且強鹼性的清洗液,以及使用該清洗液之清洗方法。
專利文獻1中提出利用含有鹼、WzMXy(式中,M係選自於由Si、Ge、Sn、Pt、P、B、Au、Ir、Os、Cr、Ti、Zr、Rh、Ru以及Sb構成的群組中的金屬;X係選自於F、Cl、Br以及I所構成的群組中的鹵化物;W係選自於H、鹼金屬或鹼土類金屬及不含金屬離子之氫氧化物鹼基部分;y係相對應於鹵化金屬而為4或6;然後z係1、2或3)的清洗液的配線形成方法。專利文獻1記載的清洗方法因既無法除去光阻也無法抑制Low-k膜的損壞,故無法使用於本目的(參照比較例8)。又,於本發明的清洗方法使用的清洗液中,摻合專利文獻1記載的WzMXy,代替以抑制含鉭材料的損壞為目的而摻合的鹼土類金屬化合物之清洗液,會造成含鉭材料與Low-k膜損壞(參照比較例9)。 [先前技術文獻] [專利文獻]
[專利文獻1]日本特表2007-510307號公報
[發明所欲解決之問題]
本發明之目的係提供一種於半導體元件的製造步驟中,抑制低介電常數膜與含鉭材料的損壞、除去被處理物表面的光阻及乾蝕刻殘渣的清洗液,以及使用該清洗液之清洗方法。 [解決問題之方式]
依據本發明可以解決上述問題。即,本發明係如下所述: <1>一種清洗方法,其將具有Low-k膜與含10原子%以上之鉭之材料之半導體元件之表面之光阻及乾蝕刻殘渣予以除去,其特徵為:使用含有過氧化氫0.002~50質量%、鹼土類金屬化合物0.001~1質量%、鹼及水之清洗液。 <2>如上述<1>中記載之清洗方法,其中,該清洗液之pH値為7~14。 <3>如上述<1>或<2>中記載之清洗方法,其中,該含10原子%以上之鉭之材料係選自於由氧化鉭、氮化鉭、及鉭構成之群組中之至少1種。 <4>如上述<1>至<3>中任一項記載之清洗方法,其中,該鹼土類金屬化合物係選自於由鈣化合物、鍶化合物、及鋇化合物構成之群組中之至少1種。 <5>如上述<1>至<4>中任一項記載之清洗方法,其中,該鹼之含量為0.1~20質量%。 <6>如上述<1>至<5>中任一項記載之清洗方法,其中,該鹼係選自於由氫氧化鉀、乙酸鉀、碳酸鉀、磷酸鉀、氨、氫氧化四甲銨、三乙胺、乙醇胺、及1-胺基-2-丙醇構成之群組中之至少1種。 <7>一種清洗液,其將具有Low-k膜與含10原子%以上之鉭之材料之半導體元件之表面之光阻及乾蝕刻殘渣予以除去,其特徵為:含有過氧化氫0.002~50質量%、鹼土類金屬化合物0.001~1質量%、鹼及水。 <8>如上述<7>中記載之清洗液,其中,該清洗液之pH値為7~14。 <9>如上述<7>或<8>中記載之清洗液,其中,該含10原子%以上之鉭之材料係選自於由氧化鉭、氮化鉭、及鉭構成之群組中之至少1種。 <10>如上述<7>至<9>中任一項記載之清洗液,其中,該鹼土類金屬化合物係選自於由鈣化合物、鍶化合物、及鋇化合物構成之群組中之至少1種。 <11>如上述<7>至<10>中任一項記載之清洗液,其中,該鹼之含量為0.1~20質量%。 <12>如上述<7>至<11>中任一項記載之清洗液,其中,該鹼係選自於由氫氧化鉀、乙酸鉀、碳酸鉀、磷酸鉀、氨、氫氧化四甲銨、三乙胺、乙醇胺、及1-胺基-2-丙醇構成之群組中之至少1種。 [發明之效果]
根據本發明的清洗液及使用該清洗液的清洗方法,可以於半導體元件的製造步驟中,抑制Low-k膜與含鉭材料的損壞、選擇性地除去被處理物的表面的光阻及乾蝕刻殘渣,並能以高成品率製造高精度、高品質的半導體元件。
本發明的清洗液及使用該清洗液之清洗方法係於製造半導體元件的清洗步驟使用,此時,能以充分滿足之程度清洗・除去光阻與乾蝕刻殘渣,且可以抑制Low-k膜與含鉭材料的損壞。
本發明的清洗液所適用的半導體元件中含有的含鉭材料係含有10原子%以上的鉭的材料,該鉭的原子組成百分比係以15原子%以上為佳、20原子%以上更佳、25原子%以上再更佳,30原子%以上特佳。含鉭材料的具體例子有氧化鉭、氮化鉭、鉭等。但含鉭材料若為含10原子%以上的鉭的材料,則不以此為限。 本發明中,鉭的含量可利用X射線光電子光譜法(XPS)的離子濺射法,藉由測量成為目標的含鉭材料的鉭原子的構成比而檢測之。有時會有因含鉭材料的表面附近受到氧化,而使氧原子的構成比較材料內部為高的情況。因此,鉭與氧的原子的構成比成為定值前,可以利用離子濺射對含鉭材料的表面進行蝕刻,測量因離子濺射而露出的含鉭材料內部的鉭原子的構成比。作為測量裝置,可以使用全自動XPS分析裝置K-Alpha(Thermo Fisher Scientific有限公司製)。
本發明的清洗液所含的鹼土類金屬化合物的濃度範圍係0.001~1質量%,以0.002~0.5質量%為佳,0.003~0.2質量%更佳,0.005~0.1質量%特佳。於上述範圍內的話,可以有效地防止含鉭材料的腐蝕。濃度範圍超過1質量%的話,會有乾蝕刻殘渣的除去性下降的情況。 本發明者們係初次發現:清洗液中所含的鹼土類金屬化合物會對含鉭材料表現出抗腐蝕效果。其機制尚未明瞭,但據認為係鹼土類金屬化合物會吸附於鉭的表面,防止清洗液中所含的過氧化氫或鹼侵蝕鉭。
鹼土類金屬化合物的具體例子係鈣化合物、鍶化合物以及鋇化合物。更具體可以舉例硝酸鋇、氫氧化鋇、氯化鋇、乙酸鋇、氧化鋇、溴化鋇、碳酸鋇、氟化鋇、碘化鋇、硫酸鋇、磷酸鋇、硝酸鈣、氫氧化鈣、氯化鈣、乙酸鈣、氧化鈣、溴化鈣、碳酸鈣、氟化鈣、碘化鈣、硫酸鈣、磷酸鈣、硝酸鍶、氫氧化鍶、碳酸鍶、氯化鍶、乙酸鍶、氧化鍶、溴化鍶、氟化鍶、碘化鍶、硫酸鍶、磷酸鍶等,但並不限於該等化合物。 於該等化合物之中,以硝酸鋇、氫氧化鋇、氯化鋇、乙酸鋇、氧化鋇、溴化鋇、碳酸鋇、氟化鋇、碘化鋇、硫酸鋇、磷酸鋇、硝酸鈣以及硝酸鍶為佳。 該等鹼土類金屬化合物可以單獨或組合2種以上進行摻合。
本發明的清洗液中所含的過氧化氫的濃度範圍係0.002~50質量%,以0.01~40質量%為佳,0.01~30質量%更佳,0.1~30質量%再更佳,0.5~25質量%特佳。於上述範圍內的話可以有效地除去乾蝕刻殘渣。
本發明的清洗液中含的鹼係以調整pH值為目的而加入。因此,鹼的種類沒有並沒有限制,也可以加入任意的濃度。鹼的濃度範圍以0.1~20質量%為佳,0.3~15質量%更佳,0.5~12質量%再更佳,0.6~10.4質量%特佳。於上述範圍內的話,可以有效地防止含鉭材料的腐蝕。濃度範圍超過20質量%的話,會有造成Low-k膜損壞的情況。 於本發明使用的鹼可使用氫氧化鉀、乙酸鉀、碳酸鉀、磷酸鉀、氨、氫氧化四甲銨、三乙胺、乙醇胺、1-胺基-2-丙醇等,但並不限於該等化合物。 該等之中,以氫氧化鉀、氨以及氫氧化四甲銨為佳。 該等鹼可以單獨或組合2種以上進行摻合。
本發明的清洗液之pH值可於7~14的任意的範圍內使用。pH值以7.5~14為佳,為8~13.8更佳,為8.5~13.5再更佳。為此範圍的pH值的話,可以抑制Low-k膜與含鉭材料的損壞,且可以選擇性地除去被處理物表面的光阻及乾蝕刻殘渣。
本發明的清洗液中含的水係藉由蒸餾、離子交換處理、過濾器處理、各種吸附處理等將金屬離子、有機不純物或微粒粒子等除去的水為佳,純水、超純水特佳。於此情況,水的濃度係除去各種藥劑的剩餘部分。
本發明的清洗液中,依需要於不損及本發明的目的的範圍內,亦可摻合習知半導體用清洗液中使用的添加劑。例如,可以加入酸、金屬抗腐蝕劑、水溶性有機溶劑、氟化合物、氧化劑、還原劑、螯合劑、界面活性劑、消泡劑等作為添加劑。
使用本發明的清洗液的溫度係20~80℃,以50~70℃的範圍為佳,依據蝕刻的條件、或所使用的半導體元件適當地選擇即可。 本發明的清洗方法亦可因應需要而併用超音波。 使用本發明的清洗液的時間係0.3~120分鐘,以0.5~60分鐘的範圍為佳,依據蝕刻的條件、或所使用的半導體元件適當地選擇即可。. 作為使用本發明的清洗液後之沖洗液,可以使用如酒精的有機溶劑,但僅以水沖洗也已足夠。
作為本發明的清洗液適用的半導體元件中所含的一般的Low-k膜,會使用羥基矽倍半氧烷(HSQ)系或甲基矽倍半氧烷(MSQ)系的OCD(商品名,東京應化工業公司製)、摻碳氧化矽(SiOC)系的Black Diamond(商品名,Applied Materials公司製)、Aurora(商品名,ASM International公司製)、Coral(商品名,Novellus Systems公司製)以及無機系的Orion(商品名,TrikonTencnlogies公司製),但Low-k膜並不限定於該等產品。 本發明的清洗液適用的半導體元件亦可含有障壁絕緣膜及/或硬式光罩。
[實施例] 接下來藉由實施例以及比較例更具體地說明本發明。但是,本發明並不受該等實施例而有所限制。
<測量鉭膜厚度> 設有膜的晶圓的膜厚度係使用SII NanoTechnology股份有限公司製的螢光X射線裝置SEA1200VX進行測量。
<鉭的蝕刻速率之測量與判定> 含鉭材料的蝕刻速率的評估係使用設有含30原子%的鉭的氮化鉭膜的晶圓(ADVANTEC公司製)。將此設有膜的晶圓的清洗液處理前後的膜厚度除以處理時間的值定義為蝕刻速率並算出之。 蝕刻速率4Å/min以下為合格。
<SEM觀察> 觀察半導體元件的清洗・除去處理前後的狀況係使用以下的SEM(掃描式電子顯微鏡)裝置以10萬倍之倍率進行觀察。 測量設備:日立High Technologies股份有限公司製,超高解析場發射型掃描式電子顯微鏡SU9000 判定: Ⅰ.光阻的除去狀態 E:完全地除去光阻。. G:概略地除去光阻。 P:光阻的除去並不充分。 E與G的判定為合格。 Ⅱ. 乾蝕刻殘渣的除去狀態 E:完全地除去乾蝕刻殘渣。. G:概略地除去乾蝕刻殘渣。 P:乾蝕刻殘渣的除去並不充分。 E與G的判定為合格。 Ⅲ. Low-k膜的損壞 E:與清洗前相比看不出Low-k膜的變化。. G:與清洗前相比僅稍微看出Low-k膜的變化。 P:看得出Low-k膜形狀的變化。 E與G的判定為合格。
實施例1~11 使用具有如圖2所表示的具有光阻2與Low-k膜4的剖面的配線構造的半導體元件,檢測除去乾蝕刻殘渣3的清洗效果。使用表1中所載的清洗液,以表2所表示的溫度、時間進行浸漬,其後,實施利用超純水之沖洗、利用乾燥氮氣噴射之乾燥。藉由將清洗後的半導體元件以SEM進行觀察,判斷光阻2及乾蝕刻殘渣3(圖2)的除去狀態與Low-k膜4(圖2)的損壞。 使用設有上述含鉭材料的膜的晶圓(ADVANTEC公司製)檢測含鉭材料的損壞。以表2所表示的溫度、時間浸漬於表1所載的清洗液,其後實施利用超純水之沖洗、利用乾燥氮氣噴射之乾燥。以上述螢光X射線裝置SEA1200VX求出浸漬前後的膜厚度,並算出蝕刻速率。
於使用表2所表示的本發明的清洗液以及使用該清洗液之清洗方法的實施例1~11中可得知:防止Low-k膜4的損壞,同時完全地除去光阻2及乾蝕刻殘渣3。亦可得知:氮化鉭的蝕刻速率在4Å/min以下,且對含鉭材料的損壞小。
比較例1~7(無鹼土類金屬化合物) 以於實施例1、3~7所使用的清洗液(表1,清洗液1A、1C~1G)中不添加硝酸鋇的清洗液(表3,清洗液2A、2C~2G)清洗如圖2所示的半導體元件。又,測量氮化鉭的蝕刻速率。於表5表示清洗條件與清洗結果。與於比較例1~7中所表示的清洗液2A、2C~2G中加入硝酸鋇的清洗液(表1、清洗液1A、1C~1G)相比,於Low-k膜4的損壞與光阻2及乾蝕刻殘渣3的除去性上沒有差異,但氮化鉭的蝕刻速率變高。因此,使用2A、2C~2G的清洗液的清洗方法,於本發明之標的即半導體元件的製造步驟中,可以抑制Low-k膜的損壞、除去被處理物表面的光阻及乾蝕刻殘渣,但因對含鉭材料的損壞大,故不能使用於本發明之目的(表5)。又,由該等結果與實施例8~11可得知:鹼土類金屬化合物在不使光阻及乾蝕刻殘渣的除去性劣化,而抑制含鉭材料的損壞是有用的。
比較例8(專利文獻1中記載的發明) 以含有TMAH 3.35質量%、CyDTA 0.11質量%、過氧化氫1.64質量%、六氟矽酸0.23質量%以及水94.67質量%的清洗液(表4,清洗液2H)清洗圖1所示的半導體元件。表5表示清洗條件與評估結果。此清洗液可除去乾蝕刻殘渣,且氮化鉭的蝕刻速率低,但不能除去光阻且會造成Low-k膜損壞。因此可得知:使用2H清洗液的清洗方法不能使用於本發明之標的即半導體元件的製造步驟中,抑制含鉭材料與Low-k膜的損壞且除去被處理物的表面的光阻及乾蝕刻殘渣之目的。
比較例9 以含有KOH4.5質量%、過氧化氫0.01質量%、六氟矽酸0.01質量%以及水95.48質量%的清洗液(表4,清洗液2I)清洗圖1所示的半導體元件。表5表示清洗條件與評估結果。使用此清洗液的清洗方法可以除去光阻與乾蝕刻殘渣,但氮化鉭的蝕刻速率高且會造成Low-k膜損壞。又,與使用於比較例3的清洗方法的含有KOH4.5質量%、過氧化氫0.01質量%以及水95.49質量%的清洗液(表3,清洗液2C)比較的話,因氮化鉭的蝕刻速率相當,可得知由於加入六氟矽酸而造成Low-k膜損壞。由上述可得知:使用2I的清洗液的清洗方法不能使用於本發明之標的即半導體元件的製造步驟中,抑制含鉭材料與Low-k膜的損壞及除去被處理物表面的光阻及乾蝕刻殘渣之目的。
【表1】
KOH:氫氧化鉀 TMAH:氫氧化四甲銨
【表2】
除去狀態Ⅰ:光阻2的除去狀態 除去狀態Ⅱ:乾蝕刻殘渣3的除去狀態 損壞Ⅰ:Low-k膜4的損壞 TaN ER:氮化鉭的蝕刻速率(含鉭材料的損壞)
【表3】
KOH:氫氧化鉀 TMAH:氫氧化四甲銨
【表4】
TMAH:氫氧化四甲銨 CyDTA:反式-1,2-二氨基環己烷-N,N,N‘,N’-四乙酸1水合物 KOH:氫氧化鉀
【表5】
除去狀態Ⅰ:光阻2的除去狀態 除去狀態Ⅱ:乾蝕刻殘渣3的除去狀態 損壞Ⅰ:Low-k膜4的損壞 TaN ER:氮化鉭的蝕刻速率(含鉭材料的損壞) [產業上利用性]
根據本發明的清洗液及清洗方法,能於半導體元件的製造步驟中抑制含鉭材料與Low-k膜的損壞、除去被處理物的表面的光阻及乾蝕刻殘渣,而能以高成品率製造高精度、高品質的半導體元件,於產業上是有用的。
1‧‧‧含鉭材料
2‧‧‧光阻
3‧‧‧乾蝕刻殘渣
4‧‧‧Low-k膜
5‧‧‧銅
[圖1]表示光阻及乾蝕刻殘渣除去前的半導體元件的含有銅與銅的障壁金屬鉭的構造之一例的概略剖視圖。 [圖2]表示光阻及乾蝕刻殘渣除去前的半導體元件的一例的概略剖視圖。
Claims (12)
- 一種清洗方法,其將具有Low-k膜與含10原子%以上之鉭之材料之半導體元件之表面之光阻及乾蝕刻殘渣予以除去,其特徵為:使用含有過氧化氫0.002~50質量%、鹼土類金屬化合物0.001~1質量%、鹼及水,且pH值為7.5~14之清洗液。
- 如申請專利範圍第1項之清洗方法,其中,該清洗液之pH值為8~13.8。
- 如申請專利範圍第1或2項之清洗方法,其中,該含10原子%以上之鉭之材料係選自於由氧化鉭、氮化鉭、及鉭構成之群組中之至少1種。
- 如申請專利範圍第1或2項之清洗方法,其中,該鹼土類金屬化合物係選自於由鈣化合物、鍶化合物、及鉭化合物構成之群組中之至少1種。
- 如申請專利範圍第1或2項之清洗方法,其中,該鹼之含量為0.1~20質量%。
- 如申請專利範圍第1或2項之清洗方法,其中,該鹼係選自於由氫氧化鉀、乙酸鉀、碳酸鉀、磷酸鉀、氨、氫氧化四甲銨、三乙胺、乙醇胺、及1-胺基-2-丙醇構成之群組中之至少1種。
- 一種清洗液,其將具有Low-k膜與含10原子%以上之鉭之材料之半導體元件之表面之光阻及乾蝕刻殘渣予以除去,其特徵為:含有過氧化氫0.002~50質量%、鹼土類金屬化合物0.001~1質量%、鹼及水,且pH值為7.5~14。
- 如申請專利範圍第7項之清洗液,其中,該清洗液之pH值為8~13.8。
- 如申請專利範圍第7或8項之清洗液,其中,該含10原子%以上之鉭之材料係選自於由氧化鉭、氮化鉭、及鉭構成之群組中之至少1種。
- 如申請專利範圍第7或8項之清洗液,其中,該鹼土類金屬化合物係選自於由鈣化合物、鍶化合物、及鋇化合物構成之群組中之至少1種。
- 如申請專利範圍第7或8項之清洗液,其中,該鹼之含量為0.1~20質量%。
- 如申請專利範圍第7或8項之清洗液,其中,該鹼係選自於由氫氧化鉀、乙酸鉀、碳酸鉀、磷酸鉀、氨、氫氧化四甲銨、三乙胺、乙醇胺、及1-胺基-2-丙醇構成之群組中之至少1種。
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