TW201641670A - 選擇性移除鈦氮化物硬遮罩及蝕刻殘留物的移除 - Google Patents
選擇性移除鈦氮化物硬遮罩及蝕刻殘留物的移除 Download PDFInfo
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- TW201641670A TW201641670A TW105110101A TW105110101A TW201641670A TW 201641670 A TW201641670 A TW 201641670A TW 105110101 A TW105110101 A TW 105110101A TW 105110101 A TW105110101 A TW 105110101A TW 201641670 A TW201641670 A TW 201641670A
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- Prior art keywords
- group
- ammonium
- composition
- combinations
- liquid carrier
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- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 135
- -1 amine salt Chemical class 0.000 claims abstract description 53
- 239000007800 oxidant agent Substances 0.000 claims abstract description 35
- 239000007788 liquid Substances 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 230000002378 acidificating effect Effects 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 16
- 239000003880 polar aprotic solvent Substances 0.000 claims abstract description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003989 dielectric material Substances 0.000 claims abstract description 14
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000001450 anions Chemical class 0.000 claims abstract description 9
- 150000002825 nitriles Chemical class 0.000 claims abstract description 9
- 230000007797 corrosion Effects 0.000 claims abstract description 7
- 238000005260 corrosion Methods 0.000 claims abstract description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003112 inhibitor Substances 0.000 claims abstract description 7
- 239000004310 lactic acid Substances 0.000 claims abstract description 7
- 235000014655 lactic acid Nutrition 0.000 claims abstract description 7
- 150000003948 formamides Chemical class 0.000 claims abstract description 6
- 150000004040 pyrrolidinones Chemical class 0.000 claims abstract description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 49
- 239000000463 material Substances 0.000 claims description 29
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 26
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 24
- 230000007613 environmental effect Effects 0.000 claims description 23
- 230000001590 oxidative effect Effects 0.000 claims description 23
- 229910052721 tungsten Inorganic materials 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 18
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 18
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 14
- 235000019270 ammonium chloride Nutrition 0.000 claims description 12
- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 11
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 10
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 9
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 9
- 239000004065 semiconductor Substances 0.000 claims description 9
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 9
- 125000005210 alkyl ammonium group Chemical group 0.000 claims description 8
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 150000002222 fluorine compounds Chemical class 0.000 claims description 8
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 8
- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical compound CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 claims description 7
- 229910017107 AlOx Inorganic materials 0.000 claims description 7
- 150000007513 acids Chemical class 0.000 claims description 7
- 150000003863 ammonium salts Chemical group 0.000 claims description 7
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 7
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 7
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 5
- 239000005695 Ammonium acetate Substances 0.000 claims description 5
- 239000004251 Ammonium lactate Substances 0.000 claims description 5
- 239000004254 Ammonium phosphate Substances 0.000 claims description 5
- 235000019257 ammonium acetate Nutrition 0.000 claims description 5
- 229940043376 ammonium acetate Drugs 0.000 claims description 5
- 229940059265 ammonium lactate Drugs 0.000 claims description 5
- 235000019286 ammonium lactate Nutrition 0.000 claims description 5
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 5
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 5
- RZOBLYBZQXQGFY-HSHFZTNMSA-N azanium;(2r)-2-hydroxypropanoate Chemical compound [NH4+].C[C@@H](O)C([O-])=O RZOBLYBZQXQGFY-HSHFZTNMSA-N 0.000 claims description 5
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 5
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 claims description 5
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 claims description 5
- 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 claims description 5
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 5
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 claims description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 4
- 239000012964 benzotriazole Substances 0.000 claims description 4
- 150000002429 hydrazines Chemical class 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- UQSQSQZYBQSBJZ-UHFFFAOYSA-M fluorosulfonate Chemical compound [O-]S(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-M 0.000 claims description 3
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-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
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 2
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 2
- LEVWYRKDKASIDU-IMJSIDKUSA-N L-cystine Chemical class [O-]C(=O)[C@@H]([NH3+])CSSC[C@H]([NH3+])C([O-])=O LEVWYRKDKASIDU-IMJSIDKUSA-N 0.000 claims description 2
- 229920002873 Polyethylenimine Chemical class 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 2
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 claims description 2
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 2
- 235000018417 cysteine Nutrition 0.000 claims description 2
- 229960002449 glycine Drugs 0.000 claims description 2
- 235000013905 glycine and its sodium salt Nutrition 0.000 claims description 2
- 238000004377 microelectronic Methods 0.000 claims description 2
- 150000003852 triazoles Chemical class 0.000 claims description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims 6
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims 3
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims 2
- ICIWUVCWSCSTAQ-UHFFFAOYSA-N iodic acid Chemical class OI(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-N 0.000 claims 2
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 claims 1
- QISSVLCQDNIJCS-UHFFFAOYSA-N 2-fluoro-1h-indole Chemical compound C1=CC=C2NC(F)=CC2=C1 QISSVLCQDNIJCS-UHFFFAOYSA-N 0.000 claims 1
- XHKUTQNVGAHLPK-UHFFFAOYSA-N 2-fluorocyclohexa-2,5-diene-1,4-dione Chemical compound FC1=CC(=O)C=CC1=O XHKUTQNVGAHLPK-UHFFFAOYSA-N 0.000 claims 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 1
- QIMURSUDTKEODG-UHFFFAOYSA-N NNNC(=S)N=N Chemical compound NNNC(=S)N=N QIMURSUDTKEODG-UHFFFAOYSA-N 0.000 claims 1
- 229940037003 alum Drugs 0.000 claims 1
- 150000004056 anthraquinones Chemical class 0.000 claims 1
- AJGPQPPJQDDCDA-UHFFFAOYSA-N azanium;hydron;oxalate Chemical compound N.OC(=O)C(O)=O AJGPQPPJQDDCDA-UHFFFAOYSA-N 0.000 claims 1
- 150000004305 cyclobutadienes Chemical class 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 238000009472 formulation Methods 0.000 abstract description 53
- 239000013011 aqueous formulation Substances 0.000 abstract description 14
- 239000004094 surface-active agent Substances 0.000 abstract description 5
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 abstract 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical class O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 abstract 1
- 150000003462 sulfoxides Chemical class 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 25
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 17
- 239000010937 tungsten Substances 0.000 description 17
- 238000005530 etching Methods 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000010949 copper Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- HQFQTTNMBUPQAY-UHFFFAOYSA-N cyclobutylhydrazine Chemical class NNC1CCC1 HQFQTTNMBUPQAY-UHFFFAOYSA-N 0.000 description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 235000012431 wafers Nutrition 0.000 description 4
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910018286 SbF 6 Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- MBAKFIZHTUAVJN-UHFFFAOYSA-I hexafluoroantimony(1-);hydron Chemical compound F.F[Sb](F)(F)(F)F MBAKFIZHTUAVJN-UHFFFAOYSA-I 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 244000208734 Pisonia aculeata Species 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 125000002015 acyclic group Chemical group 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
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- BTBJBAZGXNKLQC-UHFFFAOYSA-N ammonium lauryl sulfate Chemical compound [NH4+].CCCCCCCCCCCCOS([O-])(=O)=O BTBJBAZGXNKLQC-UHFFFAOYSA-N 0.000 description 1
- 229940063953 ammonium lauryl sulfate Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- YCLDXRHGQVDVJR-UHFFFAOYSA-N carbamothioylurea Chemical class NC(=O)NC(N)=S YCLDXRHGQVDVJR-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- HWEQKSVYKBUIIK-UHFFFAOYSA-N cyclobuta-1,3-diene Chemical compound C1=CC=C1 HWEQKSVYKBUIIK-UHFFFAOYSA-N 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- ACSQSQMTEKFKDX-UHFFFAOYSA-N fluorane Chemical compound F.F.F ACSQSQMTEKFKDX-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 150000004028 organic sulfates Chemical class 0.000 description 1
- 150000002905 orthoesters Chemical class 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical class OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium 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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
- H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
-
- 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
-
- 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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
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Abstract
用於滌除鈦氮化物硬遮罩及移除鈦氮化物蝕刻殘留物的配方包含胺鹽緩衝劑、非環境氧化劑,而且剩下部分為液態載劑,該液態載劑包括水及選自由二甲基碸、乳酸、甘醇及極性非質子溶劑所組成的群組的非水液態載劑,該極性非質子溶劑包括但不限於環丁碸類、亞碸類、腈類、甲醯胺類及吡咯烷酮類。該等配方具有pH<4,較佳地<3,更佳地<2.5。用水充當液態載劑的水性配方及具有水和非極性非質子溶劑的半水性配方另外含有酸性氟化物。該等配方提供高鈦氮化物蝕刻速率同時提供對W、AlN、AlO及低-k介電材料的優良相容性。該等配方可包含弱配位陰離子、腐蝕抑制劑及表面活性劑。有多數系統及製程使用該等配方來滌除鈦氮化物硬遮罩並且移除鈦氮化物蝕刻殘留物。
Description
本案請求2015年3月31日申請的美國臨時申請案第62/140,846號之權益。此申請案之揭示內容在此以引用的方式併入本文。
本發明關於相對於存有的金屬導體層和低-k介電層選擇性地蝕刻硬遮罩層及/或蝕刻殘留物之組合物、系統及方法。更明確地說,本發明關於相對於鎢、銅和低-k介電層選擇性地蝕刻鈦氮化物硬遮罩及/或蝕刻殘留物之組合物、系統及方法。
由於比例持續朝著又更小的特徵尺寸,積體電路(IC)可靠度成了IC裝配技術越來越關心的議題。跡線互連件(trace interconnect)失效機構對裝置效能和可靠度的衝擊使得來自於整合方案、互連件材料及製程的要求多出許多。構成
雙鑲嵌互連件圖案需要最佳的低-k介電材料及其相關沉積、圖案微影蝕刻術、蝕刻及清潔。晶圓裝配的互連件圖案化的硬遮罩規劃方法能以最嚴格的最佳尺寸控制將圖案轉移至底層中。
由於技術節點(technology node)推進到奈米技術,於是在該圖案蝕刻製程的期間使用金屬硬遮罩材料例如TiN以獲得較佳的蝕刻/移除選擇性、較佳的圖案保持力及對於低-k材料的外廓控制。
配方已經發展至從基材後接(pull-back)或移除這些類型的金屬硬遮罩。
下述專利係代表例。
US2013/0157472描述包含Cl-或Br-、氧化劑及可能地Cu腐蝕抑制劑的配方,其係用以清潔含低-k介電質和Cu並且蝕刻TiN或TiNxOy硬遮罩和鎢。該配方經常含有6%過氧化氫當成氧化劑及二甘醇胺以將pH調整至>7。
US 2009/0131295 A1描述在電漿蝕刻之後於1至8的pH下使用酸性或鹼性氟化物或二氟化物從TiN移除硬遮罩殘留物(通常含有TiF)之方法。
US7479474 B2描述包含H2SiF6或HBF4以減少包含低-k介電質的基材中之氧化物蝕刻的清潔配方。
WO 2013/101907 A1描述包含包括六氟矽酸和六氟鈦酸鹽在內的蝕刻劑、至少一包括高價金屬、過氧化物或高氧化態物種在內的氧化劑及至少一溶劑之配方。
本發明關於相對於存有的金屬導體層和低-k介電層選擇性地蝕刻硬遮罩層及/或蝕刻殘留物之組合物、系統及方法。更明確地說,本發明關於相對於鎢、銅和低-k介電層選擇性地蝕刻鈦氮化物硬遮罩及/或蝕刻殘留物之組合物、系統及方法。
在一態樣中,本發明關於一種從包含TiN或TiNxOy及第二材料的半導體裝置選擇性地移除鈦氮化物(TiN或TiNxOy;其中x=0至1.3且y=0至2)的組合物,該組合物包含:一胺鹽緩衝劑;一非環境氧化劑;及液態載劑;其中該組合物不包含過氧化氫;該組合物的pH<4,較佳為<3,更佳為<2.5;該第二材料係選自由Cu、W、鋁氮化物(AlNx,而且x=0.5至1)、鋁氧化物(AlOx,而且x=1至1.5)、低-k介電材料和其組合所組成的群組,而且該組合物提供TiN或TiNxOy對比於該第二材料>1:1的移除選擇性,較佳地>5:1,而且更佳地>10:1。
在另一態樣中,本發明關於一種從微電子裝置表面選擇性移除鈦氮化物(TiN或TiNxOy,其中x=0至1.3而
且y=0至2)之系統,其包含:包含TiN或TiNxOy及第二材料的半導體裝置,從該半導體裝置選擇性移除該TiN或TiNxOy的組合物,其包含:胺鹽緩衝劑;非環境氧化劑;及液態載劑;其中該組合物不包含過氧化氫;該組合物的pH<4,較佳地<3,更佳地<2.5;該第二材料係選自由Cu、W、鋁氮化物(AlNx,而且x=0.5至1)、鋁氧化物(AlOx,而且x=1至1.5)、低-k介電材料及其組合所組成的群組;而且該組合物提供TiN或TiNxOy對比於該第二材料>1:1,較佳地>5:1,而且更佳地>10:1的移除選擇性。
在又另一態樣中,本發明關於一種選擇性移除鈦氮化物(TiN或TiNxOy,其中x=0至1.3而且y=0至2)之方法,其包含:提供包含TiN或TiNxOy及第二材料的半導體裝置;使該半導體裝置與包含以下的組合物接觸:胺鹽緩衝劑;非環境氧化劑;及液態載劑;其中
該組合物不包含過氧化氫;該組合物的pH<4,較佳地<3,更佳地<2.5;該第二材料係選自由Cu、W、鋁氮化物(AlNx,而且x=0.5至1)、鋁氧化物(AlOx,而且x=1至1.5)、低-k介電材料及其組合所組成的群組;而且選擇性移除TiN或TiNxOy;而且TiN或TiNxOy對比於該第二材料的移除選擇性係>1:1,較佳地>5:1,而且更佳地>10:1。
該胺鹽緩衝劑包括,但不限於,氯化銨;硫酸氫銨;磷酸銨類;草酸銨;全氟磺酸銨類;四氟硼酸銨;六氟鈦酸銨;六氟矽酸銨;選自檸檬酸銨、醋酸銨、乳酸銨的有機酸銨鹽類;及其組合;其中該銨鹽基具有N(R1R2R3R4)+的形式;其中R1、R2、R3、R4係獨立地選自由H、CH3、C2H5及C3H7所組成的群組。
該非環境氧化劑包括,但不限於,過硫酸鹽類,其包括但不限於過硫酸鈉、過硫酸銨;碘酸鹽;過碘酸鹽;Cl(I、III或V)化合物、Br(I、III或V)化合物;及其組合所組成的群組。
該液態載劑包括,但不限於,水及選自由二甲基碸、乳酸、甘醇及極性非質子溶劑所組成的群組中的至少一非水液態載劑,該極性非質子溶劑包括但不限於環丁碸類、亞碸類、腈類、甲醯胺類及吡咯烷酮類。極性非質子溶劑的具體實例包括,但不限於,環丁碸、乙腈、二甲基甲醯胺及
N-甲基吡咯烷酮。
當該液態載劑係水時,該組合物可為水性。該水性組合物另外包含酸性氟化物。
當該液態載劑含有水及至少一非水液態載劑時,該組合物可為半水性。當該非水液態載劑不是極性非質子溶劑時,該半水性組合物可另外包含酸性氟化物。
該酸性氟化物包括,但不限於,二氟化銨、二氟化烷基銨或氟化氫水溶液本身、氟矽酸、氟硼酸、水合氟鋁酸鹽的酸及其組合。該等組合物可另外包含負電荷高分散於整個結構中的弱配位陰離子、腐蝕抑制劑及表面活性劑。
該弱配位陰離子包括,但不限於,對-甲苯磺酸根(C7H8SO3 -)、硫酸根(SO4 2-)、硝酸根(NO3 -)、三氟甲磺酸根(CF3SO3 -)、氟硫酸根、全氟磺酸根(RfSO3 -;其中Rf係C1至C4全氟烷基)、全氟磺醯亞胺((Rf)2NSO2 -;其中Rf係C1至C4全氟烷基)、六氟矽酸根(SiF6 2-)、六氟鈦酸根(TiF6 2-)、四氟硼酸根(BF4 -)、六氟磷酸根(PF6 -)、六氟銻酸根(SbF6 -)、全氟烷基鋁酸根((RfO)4Al-,Rf係全氟烷基)及其組合。
隨後的揭示內容及附加的申請專利範圍將使本發明的其他態樣、特徵及具體實施例更清楚顯而易見一些。
一般而言,本發明關於相對於存有的金屬導體層及低-k介電層選擇性地蝕刻硬遮罩層及/或光阻劑蝕刻殘留物的組合物、系統及方法。明確地說,本發明描述能提供對於
鈦氮化物硬遮罩材料(TiN或TiNxOy,其中x=0至1.3而且y=0至2),為求簡便在後文中叫做TiN硬遮罩材料,具有良好移除速率而不會損及金屬1層(M1)(例如鎢)及包括低k介電材料和在某些案例中鋁氮化物(AlNx,而且x=0.5至1)、鋁氧化物(AlOx,而且x=1至1.5)介電層在內的其他M1層組件之組合物、系統及方法。
預定於晶圓圖案化之後用於移除鈦氮化物硬遮罩材料(TiN或TiNxOy,其中x=0至1.3且y=0至2)的組合物或配方(組合物、配方在本發明中能相互交換使用)經常使用過氧化氫當成氧化劑。本文使用的措辭“配方”及“組合物”能相互交換使用。
涉及以過氧化氫當成用於移除鈦氮化物硬遮罩的氧化劑之化學物質經證明是有效的,但是似乎與該晶圓的M1層中之鎢材料不相容。該等配方經常蝕刻鎢比蝕刻該期望的TiN硬遮罩又更容易。當過氧化氫在稍微鹼性條件之下當成氧化劑使用以將該鈦氮化物溶解成過氧化鈦物種時,很不幸地該M1層金屬,例如鎢,也容易形成可溶性過氧化物而且受到這些化學物質的攻擊。
本發明的化學性質避免使用過氧化氫。也就是說,本發明,更明確地說,描述用於移除在28nm晶圓及更小節點上的鈦氮化物硬遮罩的滌除劑(配方)之新的無過氧化氫平台。本發明的這個態樣使該化學物質與鎢相容性更高許多。
於大氣條件下的空氣係溫和的環境氧化劑之實例。該措辭非環境氧化劑包括不是空氣或空氣中的氧之任何
氧化劑。
除非有指明,否則於大氣條件下的空氣正常存在於設備運轉的期間,所以咸認為該等配方存有溫和的環境氧化劑。
本發明於<4的低pH下操作,較佳地<3,而且更佳地<2.5。該配方可能是水性(其僅含有水)及半水性(其含有水及至少一非水液態載劑)配方二者。該等配方包含胺鹽緩衝劑、非環境氧化劑、酸性氟化物來源及液態載劑以移除該鈦氮化物硬遮罩而不會蝕刻鎢。此化學藥品也不會蝕刻介於該鎢和低-k介電層之間的TiN襯墊。該胺鹽緩衝劑係用以使該配方的pH維持於低於4,較佳地<3,而且更佳地<2.5。該非環境氧化劑及酸性氟化物係用以有效率地移除TiN。
該等配方含有胺鹽緩衝劑。該胺鹽緩衝劑可包括,但不限於,氯化銨、硫酸氫銨、磷酸銨類、草酸銨、全氟磺酸銨、四氟硼酸銨、六氟鈦酸銨或六氟矽酸銨(其可能由氫氧化銨及六氟矽酸構成)或有機酸的銨鹽類所組成的群組,該有機酸的銨鹽類包括但不限於檸檬酸銨、醋酸銨、乳酸銨及其組合。
而銨鹽基(ammonium)表示具有N(R1R2R3R4)+形式的任何胺鹽,其中R1、R2、R3、R4可能全都相同或不同,而且可能構成H、CH3、C2H5及C3H7。
該胺鹽緩衝劑的量係於0.5至10重量%的範圍,較佳地1至10重量%,而且更佳地2至8重量%。
該等配方含有包括但不限於過硫酸鹽類的非環
境氧化劑,該過硫酸鹽類包括,但不限於,過硫酸鈉、過硫酸銨、碘酸鹽、過碘酸鹽、Cl(I、III或V)化合物、Br(I、III或V)化合物及其組合。
該等非環境的非金屬氧化劑係以介於0.2至3重量%的量運用,較佳地0.5至2重量%而且更佳地0.5至1%。
該等配方含有能將<4000ppm的量溶化分解的酸性氟化物,或<2000ppm,或<500ppm,其取決於該氧化物的安定性,例如,O3-四乙基原矽酸酯(TEOS)層或其他低-k介電層。
該加溶化分解的酸性氟化物二氟化物可包括,但不限於二氟化銨、二氟化烷基銨或氟化氫水溶液本身、氟矽酸及水合氟鋁酸鹽的酸類。
該等配方也包括液態載劑,該液態載劑可包括,但不限於水及選自由二甲基碸、乳酸、甘醇及極性非質子溶劑所組成的群組的非水液態載劑,該極性非質子溶劑包括但不限於環丁碸類、亞碸類、腈類、甲醯胺類、吡咯烷酮類。極性非質子溶劑的具體實例包括,但不限於,環丁碸、乙腈、二甲基甲醯胺及N-甲基吡咯烷酮,或選自由環丁碸、二甲基亞碸、乳酸、甘醇類(例如丙二醇)和其混合物所組成的群組。
該等配方可另外含有呈酸性形式或經胺取代形式之弱配位陰離子。該弱配位陰離子也能用以使該配方的pH維持於低於4而且較佳為低於3;而且更佳為低於2.5。
弱配位陰離子使負電荷高分散於整個結構中而且因此預定能使極具反應性的陽離子,例如被溶解的鈦氮化
物的陽離子,安定化而且保持於水性配方中。
該弱配位陰離子可包括,但不限於,對-甲苯磺酸根(C7H8SO3 -)、硫酸根(SO4 2-)、硝酸根(NO3 -)、三氟甲磺酸根(CF3SO3 -)、氟硫酸根、全氟磺酸根類(RfSO3 -、其中Rf係C1至C4全氟烷基)、全氟磺醯亞胺類((Rf)2NSO2 -,其中Rf係C1至C4的全氟烷基)、六氟矽酸根(SiF6 2-)、六氟鈦酸根(TiF6 2-)、四氟硼酸根(BF4 -)、六氟磷酸根(PF6 -)、六氟銻酸根(SbF6 -)和全氟烷基鋁酸根類((RfO)4Al-),其中Rf係全氟烷基)及其組合。
該弱配位陰離子的量係於1至10重量%的範圍,較佳地2至8重量%,而且更佳地4至8重量%。
該等配方可含有腐蝕抑制劑以改善與其他金屬的相容性。
該腐蝕抑制劑可能包括,但不限於苯并三唑及經取代的苯并三唑、聚乙烯亞胺、苯磷二酚、半胱胺酸和胱胺酸衍生物、胺基乙酸、硫脲和胺基硫代甲醯脲(thiobiuret)、矽氧烷、氯化鋁、氟化鋁、咪唑、三唑及硼酸。
該腐蝕抑制劑係依照<10000ppm的量使用,較佳地<5000ppm,而且更佳地<1000ppm。
該等配方也可能含有表面活性劑以改善晶圓表面的可濕潤性。表面活性劑的實例包括但不限於月桂基硫酸銨及廣大範圍的有機硫酸鹽類,包括對-甲苯硫酸鹽類。該表面活性劑通常依<1000ppm的量使用,較佳地<500ppm而且更佳地<100ppm。
本發明的配方提供下述優點。
1.於70℃及更低下觀察到鈦氮化物的高蝕刻速率。
2.該等配方的水性溶液及半水性溶液係安定的。
3.含有低活性氟化物的配方顯示低TEOS蝕刻及圖案化PDEMs® 2.2 ILD膜。
4.觀察到的是低或基本上沒有鎢(W)的蝕刻,所以此平台的組合物能與該M1層相容而且可用於清潔該M1層。
5.該等配方不會損害介於該鎢與該低-k介電層之間的TiN襯墊。
6.半水性配方與其他配方相比顯示低鋁氮化物蝕刻量。
工作實施例顯現了本發明的關鍵特徵及益處。
水性配方係藉由摻混表1A所述的組分製備而成。半水性配方係按照摻混表1B的方式製備而成。
將不同類型的TiN、W、TEOS及典型層間介電質(ILD)材料,舉例來說,圖案化PDEMs 2.2,的晶圓浸於該等配方,同時於500rpm攪拌並且加熱至介於40與70℃之間。浸漬時間隨蝕刻速率而變。
金屬的蝕刻速率係藉由靠著20565 Alves Drive Cupertino,CA 95014的Creative Design Engineering公司所製造的CDE RESMAP Model 273桌上型4點探針得到的表面電阻率求得蝕刻製程前後的膜厚度來測定。該ILD和TEOS的蝕刻速率係靠著SCI FilmTeK Ellipsometer得到的前後厚度來
測量。
將水性配方顯示於表1A。
將使用非水液態載劑的半水性配方顯示於表1B。
除了配方的pH>4的配方92I以外,所有配方皆具有<4的pH。
下列實施例及比較例使用該等配方來進行於40至70℃的TiN滌除研究。
將表1A和1B所示的配方於45和50℃下的蝕刻速率顯示於表2。
將配方92A拿來當作以過氧化氫用作氧化劑的比較例。該配方含有0.5%過氧化氫充當非環境氧化劑。此配方用3重量%氯化銨緩衝至Ph約4。由配方92A觀察到最小程度的TiN蝕刻,同時觀察到顯著的鎢蝕刻。
將配方92B拿來當作配方中含有非環境氧化劑(亦即過硫酸鹽),但是無酸性氟化物(亦即微量二氟化物)的另一比較例。92B的結果顯示出低TiN蝕刻速率。
將配方92I也拿來當作配方的pH>4的比較例。配方92I提供最小的TiN蝕刻速率,而非相對高的鎢蝕刻速率。
水性配方92D、E及F的數據顯示含有非環境氧化劑(亦即過硫酸鹽)及酸性氟化物(亦即微量二氟化物)的本發明的配方於pH<4下能提供高TiN蝕刻速率,同時提供對鎢及低-k介電材料的優良相容性。該等配方提供良好的TiN對W選擇性(達於17)及TiN對低-k介電材料選擇性(達於>100)。
關於添加非水液態載劑例如環丁碸(極性非質子
溶劑)或二甲基碸的半水性配方,表2的數據顯示有或無酸性氟化物(亦即微量二氟化物)之含有非環境氧化劑(亦即過硫酸鹽)的半水性配方於pH<4下也能提供高TiN蝕刻速率,同時提供對鎢及低-k介電材料的優良相容性。該等配方提供良好的TiN對W選擇性(達於10)及TiN對低-k介電材料選擇性(達於>100)。
再者,表2中的數據也顯示含有酸性氟化物的半水性配方使該鋁氮化物(AlN)蝕刻速率降低,同時於<500C的溫度下維持良好的TiN對W及/或TiN對低-k介電質蝕刻選擇性。該等配方顯示出對該AlN層的保護性。
含有極性非質子溶劑環丁碸充當唯一非水液態載劑的半水性配方在酸性氟化物不存在的情形(94D)下使該鋁氮化物(AlN)蝕刻速率大幅降低,同時維持良好的TiN對W及/或TiN對低-k介電質蝕刻選擇性。該等配方顯示出對該AlN層的保護性。
本發明的配方已經證實了其對移除該TiN硬遮罩的功效及其對鎢、鋁氮化物(AlN)及低-k介電材料的良好相容性。
本發明的半水性配方對期望對鋁氮化物或鋁氧化物的相容性之系統極為有用。
前述實施例及較佳具體實施例的描述理應視為舉例說明,而非限制如申請專利範圍所界定的發明。能輕易認清的是,上述特徵的許多變化例和組合均能被利用而不會悖離申請專利範圍所描述的發明。這樣的變化例不得視為悖
離本發明的精神和範疇,而且意圖將所有這樣的變化例均包括在下述申請專利範圍的範疇以內。
Claims (22)
- 一種從包含鈦氮化物及第二材料的半導體裝置選擇性地移除鈦氮化物(TiN或TiNxOy;其中x=0至1.3且y=0至2)之組合物,該組合物包含:一胺鹽緩衝劑;一非環境氧化劑;及液態載劑;其中該組合物不包含過氧化氫;該組合物的pH<4;該第二材料係選自由Cu、W、鋁氮化物(AlNx,而且x=0.5至1)、鋁氧化物(AlOx,而且x=1至1.5)、低-k介電材料和其組合所組成的群組,而且該組合物提供TiN或TiNxOy對比於該第二材料>1:1的移除選擇性,較佳地>5:1,而且更佳地>10:1。
- 如申請專利範圍第1項之組合物,其中該胺鹽緩衝劑存有0.5至10重量%的範圍而且係選自由以下所組成的群組:氯化銨;硫酸氫銨;磷酸銨類;草酸銨;全氟磺酸銨類;四氟硼酸銨;六氟鈦酸銨;六氟矽酸銨;選自檸檬酸銨、醋酸銨、乳酸銨的有機酸銨鹽類;及其組合;其中該銨鹽基具有N(R1R2R3R4)+的形式;其中R1、R2、R3、R4係獨立地選自由H、CH3、C2H5 及C3H7所組成的群組。
- 如申請專利範圍第1項之組合物,其中該非環境氧化劑存有0.2至3重量%的範圍而且係選自由過硫酸鹽,該過硫酸鹽係選自由過硫酸鈉、過硫酸銨及其組合所組成的群組;碘酸鹽;過碘酸鹽;Cl(I、III或V)化合物、Br(I、III或V)化合物;及其組合所組成的群組。
- 如申請專利範圍第1項之組合物,其中該液態載劑係水;而且該組合物另外包含<4000ppm之選自由二氟化銨、二氟化烷基銨、氟化氫水溶液、氟矽酸、氟硼酸、水合氟鋁酸鹽的酸及其組合所組成的群組的酸性氟化物。
- 如申請專利範圍第1項之組合物,其中該組合物係具有液態載劑的半水性組合物,該液態載劑包含水及選自由二甲基碸、乳酸、甘醇及極性非質子溶劑所組成的群組中的至少一非水液態載劑,該極性非質子溶劑係選自由環丁碸類、亞碸類、腈類、甲醯胺類、吡咯烷酮類及其組合所組成的群組;而且該組合物另外包含<4000ppm之選自由二氟化銨、二氟化烷基銨、氟化氫水溶液、氟矽酸、氟硼酸、水合氟鋁酸鹽的酸及其組合所組成的群組的酸性氟化物。
- 如申請專利範圍第4或5項之組合物,其中該胺鹽緩衝劑係選自由氯化銨、硫酸氫銨及其組合所組成的群組;該非 環境氧化劑係選自由過硫酸銨、過硫酸鈉及其組合所組成的群組;而且該酸性氟化物係選自由二氟化銨、氫氟酸及其組合所組成的群組。
- 如申請專利範圍第1項之組合物,其中該組合物係具有由水和極性非質子溶劑所組成的液態載劑之半水性組合物,該極性非質子溶劑係選自由環丁碸、亞碸、腈、甲醯胺及吡咯烷酮所組成的群組。
- 如申請專利範圍第7項之組合物,其中該胺鹽緩衝劑係選自由氯化銨、硫酸氫銨及其組合所組成的群組;而且該非環境氧化劑係選自由過硫酸銨、過硫酸鈉及其組合所組成的群組。
- 如申請專利範圍第1項之組合物,其另外包含選自由以下所組成的群組中之至少其一:弱配位陰離子,其存有1至10重量%的範圍而且係選自由以下所組成的群組:對-甲苯磺酸根(C7H8SO3 -)、硫酸根(SO4 2-)、硝酸根(NO3 -)、三氟甲磺酸根(CF3SO3 -)、全氟磺酸根(RfSO3 -;其中Rf係C1至C4全氟烷基)、全氟磺醯亞胺((Rf)2NSO2 -;其中Rf係C1至C4全氟烷基)、六氟矽酸根(SiF6 2-)、六氟鈦酸根(TiF6 2-)、四氟硼酸根(BF4 -)、六氟磷酸根(PF6 -)、六氟銻酸根(SbF6 -)、全氟烷基鋁酸根((RfO)4Al-,Rf係全氟烷基)及其 組合;及腐蝕抑制劑,其係於<2000ppm的範圍而且係選自由苯并三唑或經取代的苯并三唑、聚乙烯亞胺、苯磷二酚、半胱胺酸和胱胺酸衍生物、胺基乙酸、硫脲和胺基硫代甲醯脲、矽氧烷、氯化鋁、氟化鋁、咪唑、三唑、硼酸及其組合所組成的群組。
- 如申請專利範圍第1項之組合物,其中該組合物的Ph係<3;該組合物提供TiN或TiNxOy對比於該第二材料>5:1的移除選擇性。
- 一種從微電子裝置表面選擇性移除鈦氮化物(TiN或TiNxOy,其中x=0至1.3而且y=0至2)之系統,其包含:包含TiN或TiNxOy及第二材料的半導體裝置,從該半導體裝置選擇性移除該TiN或TiNxOy的組合物,其包含:0.5至10重量%的選自由以下所組成的群組之胺鹽緩衝劑:氯化銨;硫酸氫銨;磷酸銨類;草酸銨;全氟磺酸銨類;四氟硼酸銨;六氟鈦酸銨;六氟矽酸銨;選自檸檬酸銨、醋酸銨、乳酸銨的有機酸銨鹽類;及其組合;其中該銨鹽基具有N(R1R2R3R4)+的形式;而且R1、R2、R3、R4係獨立地選自由H、CH3、C2H5及C3H7所組成的群組;0.2至3重量%的選自由以下所組成的群組之非環境氧化 劑:過硫酸鹽類、碘酸鹽類、過碘酸鹽類、Cl(I、III或V)化合物、Br(I、III或V)化合物及其組合;及液態載劑;其中該組合物不包含過氧化氫;該組合物的pH<4;該第二材料係選自由Cu、W、鋁氮化物(AlNx,而且x=0.5至1)、鋁氧化物(AlOx,而且x=1至1.5)、低-k介電材料及其組合所組成的群組;而且該組合物提供TiN或TiNxOy對比於該第二材料>1:1的移除選擇性。
- 如申請專利範圍第11項之系統,其中該組合物中的液態載劑係水;而且該組合物另外包含<4000ppm之選自由二氟化銨、二氟化烷基銨、氟化氫水溶液、氟矽酸、氟硼酸、水合氟鋁酸鹽的酸及其組合所組成的群組的酸性氟化物。
- 如申請專利範圍第11項之系統,其中該組合物係具有液態載劑的半水性組合物,該液態載劑包含水及選自由二甲基碸、乳酸、甘醇及極性非質子溶劑所組成的群組中的至少一非水液態載劑,該極性非質子溶劑係選自由環丁碸類、亞碸類、腈類、甲醯胺類、吡咯烷酮類及其組合所組成的群組;而且該組合物另外包含<4000ppm之選自由二氟化銨、二氟化烷基銨、氟化氫水溶液、氟矽酸、氟硼酸、水 合氟鋁酸鹽的酸及其組合所組成的群組的酸性氟化物。
- 如申請專利範圍第12或13項之系統,其中該組合物中的胺鹽緩衝劑係選自由氯化銨、硫酸氫銨及其組合所組成的群組;該組合物中的非環境氧化劑係選自由過硫酸銨、過硫酸鈉及其組合所組成的群組;而且該組合物中的酸性氟化物係選自由二氟化銨、氫氟酸及其組合所組成的群組。
- 如申請專利範圍第11項之系統,其中該組合物係具有由水和極性非質子溶劑所組成的液態載劑之半水性組合物,該極性非質子溶劑係選自由環丁碸、亞碸、腈、甲醯胺及吡咯烷酮所組成的群組。
- 如申請專利範圍第15項之系統,其中該組合物中的胺鹽緩衝劑係選自由氯化銨、硫酸氫銨及其組合所組成的群組;而且該組合物中的非環境氧化劑係選自由過硫酸銨、過硫酸鈉及其組合所組成的群組。
- 一種選擇性移除鈦氮化物(TiN或TiNxOy,其中x=0至1.3而且y=0至2)之方法,其包含:提供包含TiN或TiNxOy及第二材料的半導體裝置;使該半導體裝置與包含以下的組合物接觸:0.5至10重量%的選自由以下所組成的群組之胺鹽緩衝劑:氯化銨;硫酸氫銨;磷酸銨類;草酸銨;全氟磺酸 銨類;四氟硼酸銨;六氟鈦酸銨;六氟矽酸銨;選自檸檬酸銨、醋酸銨、乳酸銨的有機酸銨鹽類;及其組合;其中該銨鹽基具有N(R1R2R3R4)+的形式;而且R1、R2、R3、R4係獨立地選自由H、CH3、C2H5及C3H7所組成的群組;0.2至3重量%的選自由以下所組成的群組之非環境氧化劑:過硫酸鹽類、碘酸鹽類、過碘酸鹽類、Cl(I、III或V)化合物、Br(I、III或V)化合物及其組合;及液態載劑;其中該組合物不包含過氧化氫;該組合物的pH<4;而且選擇性移除TiN或TiNxOy;其中該第二材料係選自由Cu、W、鋁氮化物(AlNx,而且x=0.5至1)、鋁氧化物(AlOx,而且x=1至1.5)、低-k介電材料及其組合所組成的群組;而且TiN或TiNxOy與該組合物直接接觸;而且TiN或TiNxOy對比於該第二材料的移除選擇性係>1:1。
- 如申請專利範圍第17項之方法,其中該組合物中的液態載劑係水;而且該組合物另外包含<4000ppm之選自由二氟化銨、二氟化烷基銨、氟化氫水溶液、氟矽酸、氟硼酸、水 合氟鋁酸鹽的酸及其組合所組成的群組的酸性氟化物。
- 如申請專利範圍第17項之方法,其中該組合物係具有液態載劑的半水性組合物,該液態載劑包含水及選自由二甲基碸、乳酸、甘醇及極性非質子溶劑所組成的群組中的至少一非水液態載劑,該極性非質子溶劑係選自由環丁碸類、亞碸類、腈類、甲醯胺類、吡咯烷酮類及其組合所組成的群組;而且該組合物另外包含<4000ppm之選自由二氟化銨、二氟化烷基銨、氟化氫水溶液、氟矽酸、氟硼酸、水合氟鋁酸鹽的酸及其組合所組成的群組的酸性氟化物。
- 如申請專利範圍第18或19項之方法,其中該組合物中的胺鹽緩衝劑係選自由氯化銨、硫酸氫銨及其組合所組成的群組;該組合物中的非環境氧化劑係選自由過硫酸銨、過硫酸鈉及其組合所組成的群組;而且該組合物中的酸性氟化物係選自由二氟化銨、氫氟酸及其組合所組成的群組。
- 如申請專利範圍第17項之方法,其中該組合物係具有由水和極性非質子溶劑所組成的液態載劑之半水性組合物,該極性非質子溶劑係選自由環丁碸、亞碸、腈、甲醯胺及吡咯烷酮所組成的群組。
- 如申請專利範圍第21項之方法,其中該組合物中的胺鹽緩衝劑係選自由氯化銨、硫酸氫銨及其組合所組成的群組; 而且該組合物中的非環境氧化劑係選自由過硫酸銨、過硫酸鈉及其組合所組成的群組。
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