US20050097825A1 - Compositions and methods for a barrier removal - Google Patents
Compositions and methods for a barrier removal Download PDFInfo
- Publication number
- US20050097825A1 US20050097825A1 US10/704,058 US70405803A US2005097825A1 US 20050097825 A1 US20050097825 A1 US 20050097825A1 US 70405803 A US70405803 A US 70405803A US 2005097825 A1 US2005097825 A1 US 2005097825A1
- Authority
- US
- United States
- Prior art keywords
- triazole
- amino
- composition
- methyl
- polishing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 230000004888 barrier function Effects 0.000 title claims abstract description 83
- 239000000203 mixture Substances 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims description 17
- 238000005498 polishing Methods 0.000 claims abstract description 61
- 229910052751 metal Inorganic materials 0.000 claims abstract description 58
- 239000002184 metal Substances 0.000 claims abstract description 58
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 57
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000000463 material Substances 0.000 claims abstract description 52
- -1 azole compound Chemical class 0.000 claims abstract description 51
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000004065 semiconductor Substances 0.000 claims abstract description 20
- 239000003112 inhibitor Substances 0.000 claims description 14
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims description 11
- 239000007800 oxidant agent Substances 0.000 claims description 11
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims description 10
- 239000008139 complexing agent Substances 0.000 claims description 9
- 230000002401 inhibitory effect Effects 0.000 claims description 9
- 229920002635 polyurethane Polymers 0.000 claims description 6
- 239000004814 polyurethane Substances 0.000 claims description 6
- NHAZGSRLKBTDBF-UHFFFAOYSA-N 1,2,4-triazol-1-amine Chemical compound NN1C=NC=N1 NHAZGSRLKBTDBF-UHFFFAOYSA-N 0.000 claims description 5
- GTKOKCQMHAGFSM-UHFFFAOYSA-N 1-methyltetrazol-5-amine Chemical compound CN1N=NN=C1N GTKOKCQMHAGFSM-UHFFFAOYSA-N 0.000 claims description 5
- OMAFFHIGWTVZOH-UHFFFAOYSA-N 1-methyltetrazole Chemical compound CN1C=NN=N1 OMAFFHIGWTVZOH-UHFFFAOYSA-N 0.000 claims description 5
- JWAWEQBUZOGIBZ-UHFFFAOYSA-N 1-methyltriazole Chemical compound CN1C=CN=N1 JWAWEQBUZOGIBZ-UHFFFAOYSA-N 0.000 claims description 5
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 claims description 5
- ZGHVPBISEIPFJS-UHFFFAOYSA-N 2-(tetrazol-1-yl)ethanamine Chemical compound NCCN1C=NN=N1 ZGHVPBISEIPFJS-UHFFFAOYSA-N 0.000 claims description 5
- CHEYEJGXQSHSFE-UHFFFAOYSA-N 2-(triazol-1-yl)ethanamine Chemical compound NCCN1C=CN=N1 CHEYEJGXQSHSFE-UHFFFAOYSA-N 0.000 claims description 5
- VRESBNUEIKZECD-UHFFFAOYSA-N 2-methyltetrazole Chemical compound CN1N=CN=N1 VRESBNUEIKZECD-UHFFFAOYSA-N 0.000 claims description 5
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 5
- XYYXDARQOHWBPO-UHFFFAOYSA-N 3,5-dimethyl-1h-1,2,4-triazole Chemical compound CC1=NNC(C)=N1 XYYXDARQOHWBPO-UHFFFAOYSA-N 0.000 claims description 5
- VALUMXGSLBMNES-UHFFFAOYSA-N 4,5-dimethyl-2h-triazole Chemical compound CC=1N=NNC=1C VALUMXGSLBMNES-UHFFFAOYSA-N 0.000 claims description 5
- FJRZOOICEHBAED-UHFFFAOYSA-N 5-methyl-1h-1,2,4-triazol-3-amine Chemical compound CC1=NNC(N)=N1 FJRZOOICEHBAED-UHFFFAOYSA-N 0.000 claims description 5
- PZKFSRWSQOQYNR-UHFFFAOYSA-N 5-methyl-1h-1,2,4-triazole Chemical compound CC1=NC=NN1 PZKFSRWSQOQYNR-UHFFFAOYSA-N 0.000 claims description 5
- HCEKEODXLSQFDV-UHFFFAOYSA-N 5-methyltriazol-1-amine Chemical compound CC1=CN=NN1N HCEKEODXLSQFDV-UHFFFAOYSA-N 0.000 claims description 5
- AJNQPSCMOSUVKK-UHFFFAOYSA-N 5-propan-2-yl-1h-1,2,4-triazole Chemical compound CC(C)C=1N=CNN=1 AJNQPSCMOSUVKK-UHFFFAOYSA-N 0.000 claims description 5
- DBIANVDDNNLGOY-UHFFFAOYSA-N 5-propyltriazol-1-amine Chemical compound CCCC1=CN=NN1N DBIANVDDNNLGOY-UHFFFAOYSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- MPSUGQWRVNRJEE-UHFFFAOYSA-N triazol-1-amine Chemical compound NN1C=CN=N1 MPSUGQWRVNRJEE-UHFFFAOYSA-N 0.000 claims description 5
- 150000003852 triazoles Chemical class 0.000 claims description 5
- 150000003536 tetrazoles Chemical class 0.000 claims 2
- 235000012431 wafers Nutrition 0.000 description 24
- 150000003851 azoles Chemical class 0.000 description 17
- 239000010949 copper Substances 0.000 description 14
- 239000012530 fluid Substances 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 229910052802 copper Inorganic materials 0.000 description 11
- 239000002002 slurry Substances 0.000 description 11
- 239000002585 base Substances 0.000 description 10
- 230000003628 erosive effect Effects 0.000 description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 239000003082 abrasive agent Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000003989 dielectric material Substances 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 4
- 239000012964 benzotriazole Substances 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 229910052809 inorganic oxide Inorganic materials 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 150000004767 nitrides Chemical class 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 238000006748 scratching Methods 0.000 description 4
- 230000002393 scratching effect Effects 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 230000003115 biocidal effect Effects 0.000 description 3
- 239000003139 biocide Substances 0.000 description 3
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- 150000001875 compounds Chemical class 0.000 description 3
- 150000001923 cyclic compounds Chemical class 0.000 description 3
- 230000009977 dual effect Effects 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 150000001247 metal acetylides Chemical class 0.000 description 3
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- 230000008569 process Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- 229940100555 2-methyl-4-isothiazolin-3-one Drugs 0.000 description 2
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical compound CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
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- 239000000654 additive Substances 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
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- 238000004519 manufacturing process Methods 0.000 description 2
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- BEGLCMHJXHIJLR-UHFFFAOYSA-N methylisothiazolinone Chemical compound CN1SC=CC1=O BEGLCMHJXHIJLR-UHFFFAOYSA-N 0.000 description 2
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- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
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- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
- JOELYYRJYYLNRR-UHFFFAOYSA-N 2,3,5-trihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC(O)=C1O JOELYYRJYYLNRR-UHFFFAOYSA-N 0.000 description 1
- GLDQAMYCGOIJDV-UHFFFAOYSA-N 2,3-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC(O)=C1O GLDQAMYCGOIJDV-UHFFFAOYSA-N 0.000 description 1
- GLVYLTSKTCWWJR-UHFFFAOYSA-N 2-carbonoperoxoylbenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1C(O)=O GLVYLTSKTCWWJR-UHFFFAOYSA-N 0.000 description 1
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
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- 229910052593 corundum Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- LMBWSYZSUOEYSN-UHFFFAOYSA-N diethyldithiocarbamic acid Chemical compound CCN(CC)C(S)=S LMBWSYZSUOEYSN-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 229950004394 ditiocarb Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229940104869 fluorosilicate Drugs 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 229950006191 gluconic acid Drugs 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-N iodic acid Chemical class OI(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical class OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 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 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- 229910003468 tantalcarbide Inorganic materials 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
-
- 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
- H01L21/32115—Planarisation
- H01L21/3212—Planarisation by chemical mechanical polishing [CMP]
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
-
- 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
- C11D3/12—Water-insoluble compounds
- C11D3/14—Fillers; Abrasives ; Abrasive compositions; Suspending or absorbing agents not provided for in one single group of C11D3/12; Specific features concerning abrasives, e.g. granulometry or mixtures
-
- 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
- C11D7/20—Water-insoluble oxides
-
- 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
- C11D7/3281—Heterocyclic compounds
-
- C11D2111/22—
Definitions
- the invention relates to chemical mechanical planarization (CMP) of semiconductor wafer materials and, more particularly, to CMP compositions and methods for removing barrier materials of semiconductor wafers in the presence of dielectrics and interconnect metals.
- CMP chemical mechanical planarization
- a semiconductor wafer has a wafer of silicon and a dielectric layer containing multiple trenches arranged to form a pattern for circuit interconnects within the dielectric layer.
- the pattern arrangements usually have a damascene structure or dual damascene structure.
- a barrier layer covers the patterned dielectric layer and a metal layer covers the barrier layer.
- the metal layer has at least sufficient thickness to fill the patterned trenches with metal to form circuit interconnects.
- CMP processes often include multiple planarization steps. For example, a first step removes a metal layer from underlying barrier dielectric layers. The first step polishing removes the metal layer, while leaving a smooth planar surface on the wafer with metal-filled trenches that provide circuit interconnects planar to the polished surface. First step polishing removes excess interconnect metals, such as copper at an initial high rate. After the first step removal, the second step polishing can remove a barrier that remains on the semiconductor wafer. This second step polishing removes the barrier from an underlying dielectric layer of a semiconductor wafer to provide a planar polished surface on the dielectric layer.
- a barrier typically is a metal, metal alloy or intermetallic compound, such as tantalum or tantalum nitride.
- the barrier forms a layer that prevents migration or diffusion between layers within a wafer.
- barriers prevent the diffusion of interconnect metal such as copper or silver into an adjacent dielectric.
- Barrier materials must be resistant to corrosion by most acids, and thereby, resist dissolution in a fluid polishing composition for CMP. Furthermore, these barrier materials may exhibit a toughness that resists removal by abrasive particles in a CMP slurry and from fixed abrasive pads.
- Erosion refers to unwanted recesses in the surface of dielectric layers that result from removing some of the dielectric layer by the CMP process. Erosion that occurs adjacent to the metal in trenches causes dimensional defects in the circuit interconnects. These defects contribute to attenuation of electrical signals transmitted by the circuit interconnects and impair subsequent fabrication of a dual damascene structures in a manner similar to dishing.
- the removal rate of the barrier, versus, a removal rate of the metal interconnect or the dielectric layer is known as the selectivity ratio.
- barrier removal slurries require a high abrasive concentration in a fluid polishing composition to remove a barrier material.
- abrasive concentration in U.S. Pat. No. 6,001,730, disclose slurries for polishing copper interconnects having barrier layers with up to 12 weight percent of an abrasive. But slurries having these high abrasive concentrations tend to provide detrimental erosion to the dielectric layer and result in dishing and scratching of the copper interconnect. In addition to this, high abrasive concentrations can result in peeling or delaminating of low-k dielectric layers from semiconductor wafers.
- the present invention provides an aqueous composition useful for polishing tantalum barrier material from a semiconductor wafer.
- the composition comprises an azole compound having a concentration sufficient to accelerate removal of the tantalum barrier material.
- the azole compound does not inhibit removal of the interconnect metal.
- the composition further comprises an abrasive.
- the composition has a greater selectivity for the tantalum barrier material relative to the dielectric.
- the present invention provides an aqueous composition useful for polishing a semiconductor wafer, the wafer comprising a tantalum barrier material in the presence of a dielectric and an interconnect metal, the composition comprising: an azole compound having a concentration sufficient to accelerate removal of the tantalum barrier material, the azole compound not inhibiting removal of the interconnect metal; an abrasive; and wherein the composition has a greater selectivity of the tantalum barrier material relative to the dielectric.
- the present invention provides an aqueous composition useful for polishing tantalum barrier material from a semiconductor wafer, comprising by weight percent 0 to 25 oxidizer, 0 to 6 inhibitor for a nonferrous metal, 0 to 15 complexing agent for the nonferrous metal, 0.05 to 25 azole compound, 0.05 to 10 abrasive, wherein the composition has a selectivity of the tantalum barrier material relative to a dielectric of at least 10 to 1 as measured with a microporous polyurethane polishing pad pressure measured normal to a wafer of 20.7 kPa and the azole compound is selected from the group comprising, 1,2,4-triazole, 3-methyl-1,2,4-triazole, 3,5-dimethyl-1,2,4-triazole, 1-amino-1,2,4-triazole, 3-amino-1,2,4-triazole, 5-amino-3-methyl-1,2,4-triazole, 3-isopropyl-1,2,4-triazole, 1,
- the present invention provides a chemical mechanical planarization method for polishing a semiconductor wafer, the wafer comprising a tantalum barrier material in the presence of a dielectric and an interconnect metal, the method comprising: contacting the wafer with a polishing composition, the polishing composition containing an azole compound and an abrasive, the azole compound having a concentration sufficient to accelerate removal of the tantalum barrier material, the azole compound not inhibiting removal of the interconnect metal; and polishing the wafer with a polishing pad to remove the tantalum barrier material at a removal rate greater than a removal rate for the dielectric as expressed in angstroms per minute.
- the solution and method provide unexpected selectivity for removing tantalum barrier materials.
- the solution relies upon an azole compound an abrasive to selectively remove tantalum barrier materials.
- the solution selectively removes barrier materials with reduced dielectric erosion and reduced dishing and scratching of the metal interconnects, such as copper. Furthermore, the solution removes tantalum barrier materials without peeling or delaminating low-k dielectric layers from semiconductor wafers.
- tantalum barrier refers to tantalum, tantalum-containing alloy, tantalum-base alloys and tantalum intermetallics.
- the solution has particular effectiveness for tantalum, tantalum-base alloys and tantalum intemetallics, such as tantalum carbides, nitrides and oxides.
- the slurry is most effective for accelerating the removal of tantalum barriers from patterned semiconductor wafers without inhibiting the removal rate of metal interconnects.
- the azole compound is defined herein as a compound containing two or more nitrogen atoms in a conjugated cyclic compound.
- the conjugated cyclic compound further comprises at least one double bond between the at least two nitrogen atoms.
- the nitrogen atoms in the conjugated cyclic compound may be adjacent to each other or may be separated by other atoms.
- the azole compound may be substituted by other groups along the cyclic ring members.
- the preferred substituting groups are electron donating groups.
- the term “electron-donating” refers to a chemical group bonded to a substance that transfers electron density to that substance.
- Electron-donating substituents include, for example, amino, hydroxyl (—OH), alkyl, substituted alkyl, hydrocabon radical, substituted hydrocarbon radical, amido, and aryl. These electron-donating substituents accelerate removal of tantalum-containing barrier materials.
- the azole compound when adsorbed onto the barrier surface, such as TaN or Ta, the electrons flow between the at least two nitrogen atoms through the conjugate bonds. Consequently, the azole compounds have a strong affinity to the barrier surface. This affinity for the barrier surface is theorized to accelerate the barrier removal rate with limited use of abrasives.
- Preferred azole compounds include, triazole compounds, for example, 1,2,4-triazole, 3-methyl-1,2,4-triazole, 3,5-dimethyl-1,2,4-triazole, 1-amino-1,2,4-triazole, 3-amino-1,2,4-triazole, 5-amino-3-methyl-1,2,4-triazole, 3 -isopropyl-1,2,4-triazole, 1,2,3-triazole, 1-methyl-1,2,3-triazole, 1-amino-1,2,3-triazole, 1-amino-5-methyl-1,2,3-triazole, 4,5-dimethyl-1,2,3-triazole, 1-amino-5-n-propyl-1,2,3-triazole, 1-( ⁇ -aminoethyl)-1,2,3-triazole, a substituted triazole compound having an electron-donating substituent, and mixtures thereof.
- triazole compounds for example, 1,2,4-triazole, 3-methyl-1,
- azole compounds include, tetrazole compounds, for example, 1-methyltetrazole, 2-methyltetrazole, 5-amino-1H-tetrazole, 5-amino-1-methyltetrazole, 1-( ⁇ -aminoethyl)tetrazole, a substituted tetrazole compound having an electron-donating substituent, and mixtures thereof.
- Particularly effective azole compounds for accelerating the removal of tantalum barriers are 1,2,4-triazole and 3-amino-1,2,4-triazole.
- the azole compound may be present in the solution in a range of concentrations, for example from 0.05 to 25 weight percent. This specification expresses all concentrations in weight percent. A single type of azole compound may be present, or a mixture of azole compounds may be used. Most advantageously, the solution contains 0.1 to 10 weight percent azole compounds and for most applications, azole compound concentrations of 1 to 5 weight percent provide sufficient barrier removal rates. Most preferably, the concentration of the azole compound is 2 weight percent.
- the polishing composition contains 0.05 to 10 weight percent abrasive to facilitate barrier layer. Within this range, it is desirable to have the abrasive present in an amount of greater than or equal to 0.1 weight percent, and preferably greater than or equal to 0.5 weight percent. Also, desirable within this range is an amount of less than or equal to 5 weight percent, and preferably less than or equal to 3 weight percent. Most preferably, the abrasive concentration is from 1 to 2 weight percent.
- the abrasive has an average particle size of less than or equal to 50 nanometers (nm) for preventing excessive metal dishing and dielectric erosion.
- particle size refers to the average particle size of the abrasive. More preferably, it is desirable to use a colloidal abrasive having an average particle size of less than or equal to 40 nm. Further, minimal dielectric erosion and metal dishing advantageously occurs with colloidal silica having an average particle size of less than or equal to 30 nm. Decreasing the size of the colloidal abrasive to less than or equal to 30 nm, tends to improve the selectivity of the polishing composition, but, it also tends to decrease the barrier removal rate.
- the preferred colloidal abrasive may include additives, such as dispersants, surfactants and buffers to improve the stability of the colloidal abrasive.
- additives such as dispersants, surfactants and buffers to improve the stability of the colloidal abrasive.
- colloidal silica from Clariant S. A., of Puteaux, France.
- the polishing composition includes the abrasive for “mechanical” removal of barrier layers.
- Example abrasives include inorganic oxides, metal borides, metal carbides, metal nitrides, polymer particles and mixtures comprising at least one of the foregoing.
- Suitable inorganic oxides include, for example, silica (SiO 2 ), alumina (Al 2 O 3 ), zirconia (ZrO 2 ), ceria (CeO 2 ), manganese oxide (MnO 2 ), or combinations comprising at least one of the foregoing oxides. Modified forms of these inorganic oxides, such as, polymer-coated inorganic oxide particles and inorganic coated particles may also be utilized if desired.
- Suitable metal carbides, boride and nitrides include, for example, silicon carbide, silicon nitride, silicon carbonitride (SiCN), boron carbide, tungsten carbide, zirconium carbide, aluminum boride, tantalum carbide, titanium carbide, or combinations comprising at least one of the foregoing metal carbides, boride and nitrides.
- Diamond may also be utilized as an abrasive if desired.
- Alternative abrasives also include polymeric particles and coated polymeric particles. The preferred abrasive is silica.
- the use of the azole compound facilitates polishing with low abrasive concentrations.
- the polishing solutions containing azole compounds and low abrasive concentrations can readily remove the tantalum barrier material at a rate of at least 10 times greater than the dielectric removal rate as expressed in angstroms per minute. More preferably, the solution of the present invention can readily remove the tantalum barrier material at a rate of at least 100 times greater than the dielectric removal rate. Most preferably, the solution of the present invention can readily remove the tantalum barrier material at a rate of at least 1000 times greater than the dielectric removal rate.
- the polishing solutions containing azole compounds and low abrasive concentrations can readily remove the tantalum barrier material at a rate of at least 2 times greater than the metal removal rate as expressed in angstroms per minute. More preferably, the polishing solutions of the present invention can readily remove the tantalum barrier material at a rate of at least 5 times greater than the metal removal rate as expressed in angstroms per minute. Most preferably, the polishing solutions of the present invention can readily remove the tantalum barrier material at a rate of at least 10 times greater than the metal removal rate as expressed in angstroms per minute.
- the azole compounds of the present invention accelerate the removal of the tantalum barrier material.
- the azole compounds of the present invention are not inhibitors for the interconnect metal. In other words, the azole compounds of the present invention accelerate the removal rate of the tantalum barrier material without inhibiting removal of the interconnect metal.
- the azole compounds provide efficacy over a broad pH range in solutions containing a balance of water.
- This solution's useful pH range extends from at least 2 to 13.
- the solution advantageously relies upon a balance of deionized water to limit incidental impurities.
- the pH of the polishing fluid of this invention is preferably from 7 to 12, more preferably from pH 8-10. If the solution's pH is less than 7, an oxidizer may be added to enhance the azole efficacy for removing the barrier material.
- the bases used to adjust the pH of the slurry of this invention may be a base containing ammonium ion, such as ammonium hydroxide, bases containing alkyl-substituted ammonium ions, bases containing alkali metal ion, bases containing alkali-earth metal ion, bases containing group IIIB metal ion, bases containing group IVB metal ion, bases containing group VB metal ion and salts containing transition metal ion.
- the designed pH in the basic range is not only for removal of the barrier surface, but also helpful for the slurry of this invention to be stable.
- the pH may be adjusted by a known technique.
- an alkali may be directly added to a slurry in which a silica abrasive is dispersed and an organic acid is dissolved.
- a part or all of an alkali to be added may be added as an organic alkali salt.
- alkali which may be used, include alkali metal hydroxides such as potassium hydroxide, alkali metal carbonates such as potassium carbonate, ammonia and amines.
- the solution contains 0 to 25 weight percent oxidizer.
- the optional oxidizer is in the range of 0 to 15 weight percent.
- the oxidizer is particularly effective at assisting the solution in removing tantalum oxide films that can form at low pH ranges.
- the oxidizing agent can be at least one of a number of oxidizing compounds, such as hydrogen peroxide (H 2 O 2 ), monopersulfates, iodates, magnesium perphthalate, peracetic acid and other per-acids, persulfates, bromates, periodates, nitrates, iron salts, cerium salts, Mn (III), Mn (IV) and Mn (VI) salts, silver salts, copper salts, chromium salts, cobalt salts, halogens hypochlorites and a mixture thereof. Furthermore, it is often advantageous to use a mixture of oxidizer compounds. When the polishing slurry contains an unstable oxidizing agent such as, hydrogen peroxide, it is often most advantageous to mix the oxidizer into the slurry at the point of use.
- H 2 O 2 hydrogen peroxide
- monopersulfates iodates, magnesium perphthalate, peracetic acid and other per-acids, persulfates, bromates, period
- the solution contains 0 to 6 weight percent inhibitor to control interconnect removal rate by static etch or other removal mechanism. Adjusting the concentration of an inhibitor adjusts the interconnect metal removal rate by protecting the metal from static etch.
- the solution contains an optional 0.02 to 5 weight percent inhibitor for inhibiting static etch of copper or silver interconnects.
- the inhibitor may consist of a mixture of inhibitors.
- Azole inhibitors are particularly effective for copper and silver interconnects.
- Typical azole inhibitors include benzotriazole (BTA), mercaptobenzothiazole (MBT), tolytriazole and imidazole. BTA is a particularly effective inhibitor for copper and silver. Note, these inhibitors are specifically excluded from the definition of “azole” compounds for the purposes of this application. In other words, the azole compounds of the present invention are chosen for their selective ability to remove barrier materials and not for the purposes of inhibiting the removal rate of metal interconnects.
- the solution may contain 0 to 20 weight percent complexing agent for the nonferrous metal.
- the complexing agent when present, prevents precipitation of the metal ions formed by dissolving the nonferrous metal interconnects. Most advantageously, the solution contains 0 to 10 weight percent complexing agent for the nonferrous metal.
- Example complexing agents include acetic acid, citric acid, ethyl acetoacetate, glycolic acid, lactic acid, malic acid, oxalic acid, salicylic acid, sodium diethyl dithiocarbamate, succinic acid, tartaric acid, thioglycolic acid, glycine, alanine, aspartic acid, ethylene diamine, trimethyl diamine, malonic acid, gluteric acid, 3-hydroxybutyric acid, propionic acid, phthalic acid, isophthalic acid, 3-hydroxy salicylic acid, 3,5-dihydroxy salicylic acid, gallic acid, gluconic acid, pyrocatechol, pyrogallol, tannic acid, including, salts and mixtures thereof.
- the complexing agent is selected from the group consisting of acetic acid, citric acid, ethyl acetoacetate, glycolic acid, lactic acid, malic acid, oxalic acid and mixtures thereof.
- the complexing agent is citric acid.
- the polishing fluid of the present invention is applicable to any semiconductor substrate containing a conductive metal, such as copper, aluminum, tungsten, platinum, palladium, gold, or iridium; a barrier or liner film, such as tantalum, tantalum nitride, titanium, or titanium nitride; and an underlying dielectric layer.
- a conductive metal such as copper, aluminum, tungsten, platinum, palladium, gold, or iridium
- a barrier or liner film such as tantalum, tantalum nitride, titanium, or titanium nitride
- an underlying dielectric layer e.g., the term dielectric refers to a semi-conducting material of dielectric constant, k, which includes low-k and ultra-low k dielectric materials.
- the present methods removes tantalum barrier materials with little effect on conventional dielectrics and low-k dielectric materials.
- the solutions provide effective barrier removal rates with low concentrations of abrasives at low pressures (i.e., less than 20.7 kPa) and high tantalum selectivity, it facilitates polishing with low dielectric erosion rates.
- the solution and method are excellent for preventing erosion of multiple wafer constituents, for example, porous and nonporous low-k dielectrics, organic and inorganic low-k dielectrics, organic silicate glasses (OSG), fluorosilicate glass (FSG), carbon doped oxide (CDO), tetraethylorthosilicate (TEOS) and a silica derived from TEOS.
- the polishing solution may also include levelers such as, ammonium chloride, to control surface finish of the interconnect metal.
- the solution optionally may contain a biocide for limiting biological contamination.
- a biocide for example, Kordek® MLX microbicide 2-Methyl-4-isothiazolin-3-one in water (Rohm and Haas Company) provides an effective biocide for many applications.
- the biocide is typically used in the concentration prescribed by the supplier.
- the solution provides a tantalum nitride to dielectric and metal selectivity of at least 10 to 1 and at least 2 to 1, respectively, as measured with a microporous polyurethane polishing pad pressure measured normal to a wafer of 20.7 kPa.
- a particular polishing pad useful for determining selectivity is the Politex microporous polyurethane polishing pad.
- Adjusting the abrasive and azole compound concentrations adjusts the tantalum barrier removal rate. Adjusting the inhibitor, oxidizer, complexing agent and leveler concentrations adjusts the etch rate of the interconnect metals.
- This experiment measured removal rates of the TaN barrier, a dielectric layer of TEOS and copper from a semiconductor wafer.
- the test determined the effect of specific azole compounds and abrasives in a second step polishing operation.
- the polishing solutions had a pH of 9 adjusted with KOH and HNO 3. All solutions contained deionized water.
- polishing solutions included 1 weight percent silica abrasives having an average particle size of 50 nm.
- TABLE 1 Second Polishing Step Results Citric Abrasive BTA Acid TaN TEOS Cu Test Additive Wt. % (wt. %) (wt. %) (wt.
- second polishing step fluids containing an abrasive and 1,2,4-triazole or 3-amino-1,2,4-triazole provided excellent removal rates for the TaN, namely, at least 1995 angstroms per minute ( ⁇ /min).
- Polishing fluids containing an abrasive without an azole compound (Comparative Solutions, B and C) and polishing fluids containing an azole compound without an abrasive showed lower rates of TaN removal and poor removal selectivity relative to the dielectric (TEOS) and to the metal (Cu).
- the negative removal rates of the TaN and the dielectric are within the defined tolerances of the polishing machine and indicate no detectable TaN and/or TEOS loss.
- the removal selectivity of the TaN relative to the dielectric was 1995 to 1 and 2223 to 1, for Tests 1 and 2, respectively.
- the removal selectivity of the TaN to the metal was 15 to 1 and 13 to 1, for Tests 1 and 2, respectively.
- the selectivity discussed is at the test conditions for the Example as defined above. The selectivity may vary with changes made to the test parameters.
- Table 1 indicates that excellent removal of the barrier film (TaN) along with commensurate removal selectivity relative the metal film (Cu) and the dielectric layer (TEOS) is obtained when using polishing fluids containing azole compounds and an abrasive.
- An azole compound present at about 2 weight percent was useful for this removal, providing an excellent barrier removal rate and removal selectivity.
- All of the polishing fluids contained an abrasives content of 1 to 2 weight percent, an amount that is well below the abrasives concentration typically used in conventional second polishing step fluids.
- the solution and method provide excellent selectivity for removing tantalum barrier materials such as tantalum, tantalum nitride and tantalum oxide.
- the solution selectively removes tantalum barrier materials with reduced dielectric erosion.
- the solution can remove tantalum barriers without a detectable TEOS loss and without peeling or delaminating low-k dielectric layers.
- the solution reduces dishing and scratching of copper interconnects.
- the azole compounds of the present invention accelerate the removal of the tantalum barrier material without inhibiting removal of the interconnect metal.
Abstract
The present invention provides an aqueous composition useful for polishing a semiconductor wafer, the wafer comprising a tantalum barrier material in the presence of a dielectric and an interconnect metal. The composition comprises an azole compound having a concentration sufficient to accelerate removal of the tantalum barrier material. In addition, the azole compound does not inhibit removal of the interconnect metal. The composition further comprises an abrasive. Also, the composition has a greater selectivity of the tantalum barrier material relative to the dielectric.
Description
- The invention relates to chemical mechanical planarization (CMP) of semiconductor wafer materials and, more particularly, to CMP compositions and methods for removing barrier materials of semiconductor wafers in the presence of dielectrics and interconnect metals.
- Typically, a semiconductor wafer has a wafer of silicon and a dielectric layer containing multiple trenches arranged to form a pattern for circuit interconnects within the dielectric layer. The pattern arrangements usually have a damascene structure or dual damascene structure. A barrier layer covers the patterned dielectric layer and a metal layer covers the barrier layer. The metal layer has at least sufficient thickness to fill the patterned trenches with metal to form circuit interconnects.
- CMP processes often include multiple planarization steps. For example, a first step removes a metal layer from underlying barrier dielectric layers. The first step polishing removes the metal layer, while leaving a smooth planar surface on the wafer with metal-filled trenches that provide circuit interconnects planar to the polished surface. First step polishing removes excess interconnect metals, such as copper at an initial high rate. After the first step removal, the second step polishing can remove a barrier that remains on the semiconductor wafer. This second step polishing removes the barrier from an underlying dielectric layer of a semiconductor wafer to provide a planar polished surface on the dielectric layer.
- Unfortunately, CMP processes often result in the excess removal of unwanted metal from circuit interconnects, a condition known as “dishing”. This dishing can result from, both first step polishing, and second step polishing. Dishing in excess of acceptable levels causes dimensional losses in the circuit interconnects. These “thin” areas in the circuit interconnects attenuate electrical signals and impair continued fabrication of dual damascene structures.
- A barrier typically is a metal, metal alloy or intermetallic compound, such as tantalum or tantalum nitride. The barrier forms a layer that prevents migration or diffusion between layers within a wafer. For example, barriers prevent the diffusion of interconnect metal such as copper or silver into an adjacent dielectric. Barrier materials must be resistant to corrosion by most acids, and thereby, resist dissolution in a fluid polishing composition for CMP. Furthermore, these barrier materials may exhibit a toughness that resists removal by abrasive particles in a CMP slurry and from fixed abrasive pads.
- Erosion refers to unwanted recesses in the surface of dielectric layers that result from removing some of the dielectric layer by the CMP process. Erosion that occurs adjacent to the metal in trenches causes dimensional defects in the circuit interconnects. These defects contribute to attenuation of electrical signals transmitted by the circuit interconnects and impair subsequent fabrication of a dual damascene structures in a manner similar to dishing. The removal rate of the barrier, versus, a removal rate of the metal interconnect or the dielectric layer is known as the selectivity ratio.
- As discussed above, most barrier materials are difficult to remove by CMP, because the barrier materials resist removal by abrasion and by dissolution. Typical barrier removal slurries require a high abrasive concentration in a fluid polishing composition to remove a barrier material. For example, Farkas et al., in U.S. Pat. No. 6,001,730, disclose slurries for polishing copper interconnects having barrier layers with up to 12 weight percent of an abrasive. But slurries having these high abrasive concentrations tend to provide detrimental erosion to the dielectric layer and result in dishing and scratching of the copper interconnect. In addition to this, high abrasive concentrations can result in peeling or delaminating of low-k dielectric layers from semiconductor wafers.
- Hence, what is needed is an improved CMP composition and method for selectively removing tantalum barrier materials. In particular, there is a need for a CMP composition and method for selectively removing tantalum barrier materials with reduced dielectric erosion and reduced dishing and scratching of the metal interconnect. Furthermore, there is a desire to remove tantalum barrier materials without peeling low-k dielectric layers from semiconductor wafers.
- The present invention provides an aqueous composition useful for polishing tantalum barrier material from a semiconductor wafer. The composition comprises an azole compound having a concentration sufficient to accelerate removal of the tantalum barrier material. In addition, the azole compound does not inhibit removal of the interconnect metal. The composition further comprises an abrasive. Also, the composition has a greater selectivity for the tantalum barrier material relative to the dielectric.
- In a first aspect, the present invention provides an aqueous composition useful for polishing a semiconductor wafer, the wafer comprising a tantalum barrier material in the presence of a dielectric and an interconnect metal, the composition comprising: an azole compound having a concentration sufficient to accelerate removal of the tantalum barrier material, the azole compound not inhibiting removal of the interconnect metal; an abrasive; and wherein the composition has a greater selectivity of the tantalum barrier material relative to the dielectric.
- In a second aspect, the present invention provides an aqueous composition useful for polishing tantalum barrier material from a semiconductor wafer, comprising by weight percent 0 to 25 oxidizer, 0 to 6 inhibitor for a nonferrous metal, 0 to 15 complexing agent for the nonferrous metal, 0.05 to 25 azole compound, 0.05 to 10 abrasive, wherein the composition has a selectivity of the tantalum barrier material relative to a dielectric of at least 10 to 1 as measured with a microporous polyurethane polishing pad pressure measured normal to a wafer of 20.7 kPa and the azole compound is selected from the group comprising, 1,2,4-triazole, 3-methyl-1,2,4-triazole, 3,5-dimethyl-1,2,4-triazole, 1-amino-1,2,4-triazole, 3-amino-1,2,4-triazole, 5-amino-3-methyl-1,2,4-triazole, 3-isopropyl-1,2,4-triazole, 1,2,3-triazole, 1-methyl-1,2,3-triazole, 1-amino-1,2,3-triazole, 1-amino-5-methyl-1,2,3-triazole, 4,5-dimethyl-1,2,3-triazole, 1-amino-5-n-propyl-1,2,3-triazole, 1-(β-aminoethyl)-1,2,3-triazole, 1-methyltetrazole, 2-methyltetrazole, 5-amino-1H-tetrazole, 5-amino-1-methyltetrazole, 1-(β-aminoethyl)tetrazole, a substituted triazole or tetrazole compound having an electron-donating substituent, and a mixture thereof.
- In a third aspect, the present invention provides a chemical mechanical planarization method for polishing a semiconductor wafer, the wafer comprising a tantalum barrier material in the presence of a dielectric and an interconnect metal, the method comprising: contacting the wafer with a polishing composition, the polishing composition containing an azole compound and an abrasive, the azole compound having a concentration sufficient to accelerate removal of the tantalum barrier material, the azole compound not inhibiting removal of the interconnect metal; and polishing the wafer with a polishing pad to remove the tantalum barrier material at a removal rate greater than a removal rate for the dielectric as expressed in angstroms per minute.
- The solution and method provide unexpected selectivity for removing tantalum barrier materials. The solution relies upon an azole compound an abrasive to selectively remove tantalum barrier materials. The solution selectively removes barrier materials with reduced dielectric erosion and reduced dishing and scratching of the metal interconnects, such as copper. Furthermore, the solution removes tantalum barrier materials without peeling or delaminating low-k dielectric layers from semiconductor wafers.
- For purposes of this specification, tantalum barrier refers to tantalum, tantalum-containing alloy, tantalum-base alloys and tantalum intermetallics. The solution has particular effectiveness for tantalum, tantalum-base alloys and tantalum intemetallics, such as tantalum carbides, nitrides and oxides. The slurry is most effective for accelerating the removal of tantalum barriers from patterned semiconductor wafers without inhibiting the removal rate of metal interconnects.
- The azole compound is defined herein as a compound containing two or more nitrogen atoms in a conjugated cyclic compound. The conjugated cyclic compound further comprises at least one double bond between the at least two nitrogen atoms. The nitrogen atoms in the conjugated cyclic compound may be adjacent to each other or may be separated by other atoms. Also, the azole compound may be substituted by other groups along the cyclic ring members. The preferred substituting groups are electron donating groups. For purposes of the specification, the term “electron-donating” refers to a chemical group bonded to a substance that transfers electron density to that substance. F. A. Carey and R. J. Sundberg, in Advanced Organic Chemistry, Part A: Structure and Mechanisms, 3rd Edition New York: Plenum Press (1990), p. 208 and 546-561 provide a more detailed description of electron-donating substituents. Electron-donating substituents include, for example, amino, hydroxyl (—OH), alkyl, substituted alkyl, hydrocabon radical, substituted hydrocarbon radical, amido, and aryl. These electron-donating substituents accelerate removal of tantalum-containing barrier materials. In theory, when the azole compound is adsorbed onto the barrier surface, such as TaN or Ta, the electrons flow between the at least two nitrogen atoms through the conjugate bonds. Consequently, the azole compounds have a strong affinity to the barrier surface. This affinity for the barrier surface is theorized to accelerate the barrier removal rate with limited use of abrasives.
- Preferred azole compounds include, triazole compounds, for example, 1,2,4-triazole, 3-methyl-1,2,4-triazole, 3,5-dimethyl-1,2,4-triazole, 1-amino-1,2,4-triazole, 3-amino-1,2,4-triazole, 5-amino-3-methyl-1,2,4-triazole, 3 -isopropyl-1,2,4-triazole, 1,2,3-triazole, 1-methyl-1,2,3-triazole, 1-amino-1,2,3-triazole, 1-amino-5-methyl-1,2,3-triazole, 4,5-dimethyl-1,2,3-triazole, 1-amino-5-n-propyl-1,2,3-triazole, 1-(β-aminoethyl)-1,2,3-triazole, a substituted triazole compound having an electron-donating substituent, and mixtures thereof. Further, other azole compounds include, tetrazole compounds, for example, 1-methyltetrazole, 2-methyltetrazole, 5-amino-1H-tetrazole, 5-amino-1-methyltetrazole, 1-(β-aminoethyl)tetrazole, a substituted tetrazole compound having an electron-donating substituent, and mixtures thereof. Particularly effective azole compounds for accelerating the removal of tantalum barriers are 1,2,4-triazole and 3-amino-1,2,4-triazole.
- Advantageously, the azole compound may be present in the solution in a range of concentrations, for example from 0.05 to 25 weight percent. This specification expresses all concentrations in weight percent. A single type of azole compound may be present, or a mixture of azole compounds may be used. Most advantageously, the solution contains 0.1 to 10 weight percent azole compounds and for most applications, azole compound concentrations of 1 to 5 weight percent provide sufficient barrier removal rates. Most preferably, the concentration of the azole compound is 2 weight percent.
- The polishing composition contains 0.05 to 10 weight percent abrasive to facilitate barrier layer. Within this range, it is desirable to have the abrasive present in an amount of greater than or equal to 0.1 weight percent, and preferably greater than or equal to 0.5 weight percent. Also, desirable within this range is an amount of less than or equal to 5 weight percent, and preferably less than or equal to 3 weight percent. Most preferably, the abrasive concentration is from 1 to 2 weight percent.
- The abrasive has an average particle size of less than or equal to 50 nanometers (nm) for preventing excessive metal dishing and dielectric erosion. For purposes of this specification, particle size refers to the average particle size of the abrasive. More preferably, it is desirable to use a colloidal abrasive having an average particle size of less than or equal to 40 nm. Further, minimal dielectric erosion and metal dishing advantageously occurs with colloidal silica having an average particle size of less than or equal to 30 nm. Decreasing the size of the colloidal abrasive to less than or equal to 30 nm, tends to improve the selectivity of the polishing composition, but, it also tends to decrease the barrier removal rate. In addition, the preferred colloidal abrasive may include additives, such as dispersants, surfactants and buffers to improve the stability of the colloidal abrasive. One such colloidal abrasive is colloidal silica from Clariant S. A., of Puteaux, France.
- The polishing composition includes the abrasive for “mechanical” removal of barrier layers. Example abrasives include inorganic oxides, metal borides, metal carbides, metal nitrides, polymer particles and mixtures comprising at least one of the foregoing. Suitable inorganic oxides include, for example, silica (SiO2), alumina (Al2O3), zirconia (ZrO2), ceria (CeO2), manganese oxide (MnO2), or combinations comprising at least one of the foregoing oxides. Modified forms of these inorganic oxides, such as, polymer-coated inorganic oxide particles and inorganic coated particles may also be utilized if desired. Suitable metal carbides, boride and nitrides include, for example, silicon carbide, silicon nitride, silicon carbonitride (SiCN), boron carbide, tungsten carbide, zirconium carbide, aluminum boride, tantalum carbide, titanium carbide, or combinations comprising at least one of the foregoing metal carbides, boride and nitrides. Diamond may also be utilized as an abrasive if desired. Alternative abrasives also include polymeric particles and coated polymeric particles. The preferred abrasive is silica.
- Advantageously, the use of the azole compound facilitates polishing with low abrasive concentrations. The polishing solutions containing azole compounds and low abrasive concentrations can readily remove the tantalum barrier material at a rate of at least 10 times greater than the dielectric removal rate as expressed in angstroms per minute. More preferably, the solution of the present invention can readily remove the tantalum barrier material at a rate of at least 100 times greater than the dielectric removal rate. Most preferably, the solution of the present invention can readily remove the tantalum barrier material at a rate of at least 1000 times greater than the dielectric removal rate. Further, the polishing solutions containing azole compounds and low abrasive concentrations can readily remove the tantalum barrier material at a rate of at least 2 times greater than the metal removal rate as expressed in angstroms per minute. More preferably, the polishing solutions of the present invention can readily remove the tantalum barrier material at a rate of at least 5 times greater than the metal removal rate as expressed in angstroms per minute. Most preferably, the polishing solutions of the present invention can readily remove the tantalum barrier material at a rate of at least 10 times greater than the metal removal rate as expressed in angstroms per minute. Note, the azole compounds of the present invention accelerate the removal of the tantalum barrier material. The azole compounds of the present invention are not inhibitors for the interconnect metal. In other words, the azole compounds of the present invention accelerate the removal rate of the tantalum barrier material without inhibiting removal of the interconnect metal.
- The azole compounds provide efficacy over a broad pH range in solutions containing a balance of water. This solution's useful pH range extends from at least 2 to 13. In addition, the solution advantageously relies upon a balance of deionized water to limit incidental impurities. The pH of the polishing fluid of this invention is preferably from 7 to 12, more preferably from pH 8-10. If the solution's pH is less than 7, an oxidizer may be added to enhance the azole efficacy for removing the barrier material. The bases used to adjust the pH of the slurry of this invention may be a base containing ammonium ion, such as ammonium hydroxide, bases containing alkyl-substituted ammonium ions, bases containing alkali metal ion, bases containing alkali-earth metal ion, bases containing group IIIB metal ion, bases containing group IVB metal ion, bases containing group VB metal ion and salts containing transition metal ion. The designed pH in the basic range is not only for removal of the barrier surface, but also helpful for the slurry of this invention to be stable. For the polishing slurry, the pH may be adjusted by a known technique. For example, an alkali may be directly added to a slurry in which a silica abrasive is dispersed and an organic acid is dissolved. Alternatively, a part or all of an alkali to be added may be added as an organic alkali salt. Examples of an alkali, which may be used, include alkali metal hydroxides such as potassium hydroxide, alkali metal carbonates such as potassium carbonate, ammonia and amines.
- Optionally, the solution contains 0 to 25 weight percent oxidizer. Advantageously, the optional oxidizer is in the range of 0 to 15 weight percent. The oxidizer is particularly effective at assisting the solution in removing tantalum oxide films that can form at low pH ranges. The oxidizing agent can be at least one of a number of oxidizing compounds, such as hydrogen peroxide (H2O2), monopersulfates, iodates, magnesium perphthalate, peracetic acid and other per-acids, persulfates, bromates, periodates, nitrates, iron salts, cerium salts, Mn (III), Mn (IV) and Mn (VI) salts, silver salts, copper salts, chromium salts, cobalt salts, halogens hypochlorites and a mixture thereof. Furthermore, it is often advantageous to use a mixture of oxidizer compounds. When the polishing slurry contains an unstable oxidizing agent such as, hydrogen peroxide, it is often most advantageous to mix the oxidizer into the slurry at the point of use.
- Optionally, the solution contains 0 to 6 weight percent inhibitor to control interconnect removal rate by static etch or other removal mechanism. Adjusting the concentration of an inhibitor adjusts the interconnect metal removal rate by protecting the metal from static etch. Advantageously, the solution contains an optional 0.02 to 5 weight percent inhibitor for inhibiting static etch of copper or silver interconnects. The inhibitor may consist of a mixture of inhibitors. Azole inhibitors are particularly effective for copper and silver interconnects. Typical azole inhibitors include benzotriazole (BTA), mercaptobenzothiazole (MBT), tolytriazole and imidazole. BTA is a particularly effective inhibitor for copper and silver. Note, these inhibitors are specifically excluded from the definition of “azole” compounds for the purposes of this application. In other words, the azole compounds of the present invention are chosen for their selective ability to remove barrier materials and not for the purposes of inhibiting the removal rate of metal interconnects.
- In addition to the inhibitor, the solution may contain 0 to 20 weight percent complexing agent for the nonferrous metal. The complexing agent, when present, prevents precipitation of the metal ions formed by dissolving the nonferrous metal interconnects. Most advantageously, the solution contains 0 to 10 weight percent complexing agent for the nonferrous metal. Example complexing agents include acetic acid, citric acid, ethyl acetoacetate, glycolic acid, lactic acid, malic acid, oxalic acid, salicylic acid, sodium diethyl dithiocarbamate, succinic acid, tartaric acid, thioglycolic acid, glycine, alanine, aspartic acid, ethylene diamine, trimethyl diamine, malonic acid, gluteric acid, 3-hydroxybutyric acid, propionic acid, phthalic acid, isophthalic acid, 3-hydroxy salicylic acid, 3,5-dihydroxy salicylic acid, gallic acid, gluconic acid, pyrocatechol, pyrogallol, tannic acid, including, salts and mixtures thereof. Advantageously, the complexing agent is selected from the group consisting of acetic acid, citric acid, ethyl acetoacetate, glycolic acid, lactic acid, malic acid, oxalic acid and mixtures thereof. Most advantageously, the complexing agent is citric acid.
- The polishing fluid of the present invention is applicable to any semiconductor substrate containing a conductive metal, such as copper, aluminum, tungsten, platinum, palladium, gold, or iridium; a barrier or liner film, such as tantalum, tantalum nitride, titanium, or titanium nitride; and an underlying dielectric layer. For purposes of the specification, the term dielectric refers to a semi-conducting material of dielectric constant, k, which includes low-k and ultra-low k dielectric materials. The present methods removes tantalum barrier materials with little effect on conventional dielectrics and low-k dielectric materials. Since the solutions provide effective barrier removal rates with low concentrations of abrasives at low pressures (i.e., less than 20.7 kPa) and high tantalum selectivity, it facilitates polishing with low dielectric erosion rates. The solution and method are excellent for preventing erosion of multiple wafer constituents, for example, porous and nonporous low-k dielectrics, organic and inorganic low-k dielectrics, organic silicate glasses (OSG), fluorosilicate glass (FSG), carbon doped oxide (CDO), tetraethylorthosilicate (TEOS) and a silica derived from TEOS.
- The polishing solution may also include levelers such as, ammonium chloride, to control surface finish of the interconnect metal. In addition to this, the solution optionally may contain a biocide for limiting biological contamination. For example, Kordek® MLX microbicide 2-Methyl-4-isothiazolin-3-one in water (Rohm and Haas Company) provides an effective biocide for many applications. The biocide is typically used in the concentration prescribed by the supplier.
- The solution provides a tantalum nitride to dielectric and metal selectivity of at least 10 to 1 and at least 2 to 1, respectively, as measured with a microporous polyurethane polishing pad pressure measured normal to a wafer of 20.7 kPa. A particular polishing pad useful for determining selectivity is the Politex microporous polyurethane polishing pad. Adjusting the abrasive and azole compound concentrations adjusts the tantalum barrier removal rate. Adjusting the inhibitor, oxidizer, complexing agent and leveler concentrations adjusts the etch rate of the interconnect metals.
- In the Examples, numerals represent examples of the invention and letters represent comparative examples. In addition, all example solutions contained 0.01 weight percent Kordek® MLX microbicide 2-Methyl-4-isothiazolin-3-one in water and 0.01 ammonium chloride brightener.
- This experiment measured removal rates of the TaN barrier, a dielectric layer of TEOS and copper from a semiconductor wafer. In particular, the test determined the effect of specific azole compounds and abrasives in a second step polishing operation. A Strausbaugh polishing machine using a Politex polyurethane polishing pad (Rodel, Inc.) under downforce conditions of about 3 psi (20.7 kPa) and a polishing solution flow rate of 200 cc/min, a platen speed of 120 RPM and a carrier speed of 114 RPM planarized the samples. The polishing solutions had a pH of 9 adjusted with KOH and HNO3. All solutions contained deionized water. In addition, polishing solutions included 1 weight percent silica abrasives having an average particle size of 50 nm.
TABLE 1 Second Polishing Step Results Citric Abrasive BTA Acid TaN TEOS Cu Test Additive Wt. % (wt. %) (wt. %) (wt. %) Å/min Å/min Å/min A None — 0 0.1 0 6 −3 38 B None — 1 0 0.15 26 32 116 C None — 1 0.2 0.15 163 39 91 D 1,2,4-triazole 2 0 0.1 0 −8 −1.4 33 E 3-amino- 2 0 0.1 0 −21 −5.1 49 1,2,4-triazole 1 1,2,4-triazole 2 1 0.1 0 1995 −0.2 135 2 3-amino- 2 2 0.1 0 2223 −0.4 174 1,2,4-triazole - As illustrated in Table 1, high removal rates of the TaN barrier film are obtained with a polishing fluid that includes an azole compound and an abrasive. In particular, second polishing step fluids containing an abrasive and 1,2,4-triazole or 3-amino-1,2,4-triazole (Tests 1 and 2, respectively) provided excellent removal rates for the TaN, namely, at least 1995 angstroms per minute (Å/min). Polishing fluids containing an abrasive without an azole compound (Comparative Solutions, B and C) and polishing fluids containing an azole compound without an abrasive (Comparative Solutions, D and E) showed lower rates of TaN removal and poor removal selectivity relative to the dielectric (TEOS) and to the metal (Cu). Note, the negative removal rates of the TaN and the dielectric are within the defined tolerances of the polishing machine and indicate no detectable TaN and/or TEOS loss. When an azole compound was present in the polishing fluid with an abrasive, the removal selectivity of the TaN relative to the dielectric was 1995 to 1 and 2223 to 1, for Tests 1 and 2, respectively. The removal selectivity of the TaN to the metal was 15 to 1 and 13 to 1, for Tests 1 and 2, respectively. Note, the selectivity discussed is at the test conditions for the Example as defined above. The selectivity may vary with changes made to the test parameters.
- The results shown in Table 1 indicates that excellent removal of the barrier film (TaN) along with commensurate removal selectivity relative the metal film (Cu) and the dielectric layer (TEOS) is obtained when using polishing fluids containing azole compounds and an abrasive. An azole compound present at about 2 weight percent was useful for this removal, providing an excellent barrier removal rate and removal selectivity. All of the polishing fluids contained an abrasives content of 1 to 2 weight percent, an amount that is well below the abrasives concentration typically used in conventional second polishing step fluids.
- The solution and method provide excellent selectivity for removing tantalum barrier materials such as tantalum, tantalum nitride and tantalum oxide. The solution selectively removes tantalum barrier materials with reduced dielectric erosion. For example, the solution can remove tantalum barriers without a detectable TEOS loss and without peeling or delaminating low-k dielectric layers. In addition, the solution reduces dishing and scratching of copper interconnects. Also, the azole compounds of the present invention accelerate the removal of the tantalum barrier material without inhibiting removal of the interconnect metal.
Claims (10)
1. An aqueous composition useful for polishing a semiconductor wafer, the wafer comprising a tantalum barrier material in the presence of a dielectric and an interconnect metal, the composition comprising:
an azole compound having a concentration sufficient to accelerate removal of the tantalum barrier material, the azole compound not inhibiting removal of the interconnect metal;
an abrasive; and
wherein the composition has a greater selectivity of the tantalum barrier material relative to the dielectric.
2. The composition of claim 1 wherein the concentration is 0.05 to 25 weight percent of the azole compound.
3. The composition of claim 1 wherein the composition comprises 0.05 to 10 weight percent of the abrasive.
4. The composition of claim 1 wherein the composition has a selectivity of the tantalum barrier material relative to a metal of at least 2 to 1 as measured with a microporous polyurethane polishing pad pressure measured normal to a wafer of 20.7 kPa.
5. The composition of claim 1 wherein the azole compound is selected from the group comprising: triazole, tetrazole, and a mixture thereof.
6. The composition of claim 5 wherein the triazole is selected from the group comprising: 1,2,4-triazole, 3-methyl-1,2,4-triazole, 3,5-dimethyl-1,2,4-triazole, 1-amino-1,2,4-triazole, 3-amino-1,2,4-triazole, 5-amino-3-methyl-1,2,4-triazole, 3-isopropyl-1,2,4-triazole, 1,2,3-triazole, 1-methyl-1,2,3-triazole, 1-amino-1,2,3-triazole, 1-amino-5-methyl-1,2,3-triazole, 4,5-dimethyl-1,2,3-triazole, 1-amino-5-n-propyl-1,2,3-triazole, 1-(β-aminoethyl)-1,2,3-triazole, a substituted triazole compound having an electron-donating substituent, and a mixture thereof.
7. The composition of claim 5 wherein the tetrazole is selected from the group comprising: 1-methyltetrazole, 2-methyltetrazole, 5-amino-1H-tetrazole, 5-amino-1-methyltetrazole, 1-(β-aminoethyl)tetrazole, a substituted tetrazole compound having an electron-donating substituent, and a mixture thereof.
8. An aqueous composition useful for polishing tantalum barrier material from a semiconductor wafer, comprising by weight percent 0 to 25 oxidizer, 0 to 6 inhibitor for a nonferrous metal, 0 to 15 complexing agent for the nonferrous metal, 0.05 to 25 azole compound, 0.05 to 12 abrasive, wherein the composition has a selectivity of the tantalum barrier material relative to a dielectric of at least 10 to 1 as measured with a microporous polyurethane polishing pad pressure measured normal to a wafer of 20.7 kPa and the azole compound is selected from the group comprising, 1,2,4-triazole, 3-methyl-1,2,4-triazole, 3,5-dimethyl-1,2,4-triazole, 1-amino-1,2,4-triazole, 3-amino-1,2,4-triazole, 5-amino-3-methyl-1,2,4-triazole, 3-isopropyl-1,2,4-triazole, 1,2,3-triazole, 1-methyl-1,2,3-triazole, 1-amino-1,2,3-triazole, 1-amino-5-methyl-1,2,3-triazole, 4,5-dimethyl-1,2,3-triazole, 1-amino-5-n-propyl-1,2,3-triazole, 1-(β-aminoethyl)-1,2,3-triazole, 1-methyltetrazole, 2-methyltetrazole, 5-amino-1H-tetrazole, 5-amino-1-methyltetrazole, 1-(β-aminoethyl)tetrazole, a substituted triazole or tetrazole compound having an electron-donating substituent, and a mixture thereof.
9. A chemical mechanical planarization method for polishing a semiconductor wafer, the wafer comprising a tantalum barrier material in the presence of a dielectric and an interconnect metal, the method comprising:
contacting the wafer with a polishing composition, the polishing composition containing an azole compound and an abrasive, the azole compound having a concentration sufficient to accelerate removal of the tantalum barrier material, the azole compound not inhibiting removal of the interconnect metal; and
polishing the wafer with a polishing pad to remove the tantalum barrier material at a removal rate greater than a removal rate for the dielectric as expressed in angstroms per minute.
10. The method of claim 9 wherein the azole compound is selected from the group comprising: 1,2,4-triazole, 3-methyl-1,2,4-triazole, 3,5-dimethyl-1,2,4-triazole, 1-amino-1,2,4-triazole, 3-amino-1,2,4-triazole, 5-amino-3-methyl-1,2,4-triazole, 3-isopropyl-1,2,4-triazole, 1,2,3-triazole, 1-methyl-1,2,3-triazole, 1-amino-1,2,3-triazole, 1-amino-5-methyl-1,2,3-triazole, 4,5-dimethyl-1,2,3-triazole, 1-amino-5-n-propyl-1,2,3-triazole, 1-(β-aminoethyl)-1,2,3 -triazole, 1-methyltetrazole, 2-methyltetrazole, 5-amino-1H-tetrazole, 5-amino-1-methyltetrazole, 1-(β-aminoethyl)tetrazole, a substituted triazole or tetrazole compound having an electron-donating substituent, and a mixture thereof.
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/704,058 US20050097825A1 (en) | 2003-11-06 | 2003-11-06 | Compositions and methods for a barrier removal |
EP04256560A EP1548075A3 (en) | 2003-11-06 | 2004-10-25 | Compositons and methods for barrier removal |
TW093132825A TW200529979A (en) | 2003-11-06 | 2004-10-28 | Compositions and methods for barrier removal |
KR1020040089297A KR20050043666A (en) | 2003-11-06 | 2004-11-04 | Compositions and methods for barrier removal |
CNA2004100922439A CN1630045A (en) | 2003-11-06 | 2004-11-05 | Compositions and methods for barrier removal |
JP2004323087A JP2005167219A (en) | 2003-11-06 | 2004-11-08 | Composition and method for removing barrier |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/704,058 US20050097825A1 (en) | 2003-11-06 | 2003-11-06 | Compositions and methods for a barrier removal |
Publications (1)
Publication Number | Publication Date |
---|---|
US20050097825A1 true US20050097825A1 (en) | 2005-05-12 |
Family
ID=34552034
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/704,058 Abandoned US20050097825A1 (en) | 2003-11-06 | 2003-11-06 | Compositions and methods for a barrier removal |
Country Status (6)
Country | Link |
---|---|
US (1) | US20050097825A1 (en) |
EP (1) | EP1548075A3 (en) |
JP (1) | JP2005167219A (en) |
KR (1) | KR20050043666A (en) |
CN (1) | CN1630045A (en) |
TW (1) | TW200529979A (en) |
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US20060000808A1 (en) * | 2004-07-01 | 2006-01-05 | Fuji Photo Film Co., Ltd. | Polishing solution of metal and chemical mechanical polishing method |
US20060116313A1 (en) * | 2004-11-30 | 2006-06-01 | Denise Geitz | Compositions comprising tannic acid as corrosion inhibitor |
US20070224806A1 (en) * | 2006-03-23 | 2007-09-27 | Fujifilm Corporation | Metal polishing slurry |
US20070224822A1 (en) * | 2006-03-23 | 2007-09-27 | Cabot Microelectronics Corporation | Halide anions for metal removal rate control |
US20070293048A1 (en) * | 2006-06-19 | 2007-12-20 | Lee Jon-Won | Polishing slurry |
US20080026582A1 (en) * | 2005-06-16 | 2008-01-31 | United Microelectronics Corp. | Planarization process for pre-damascene structure including metal hard mask |
US20080041725A1 (en) * | 2006-08-21 | 2008-02-21 | Micron Technology, Inc. | Method of selectively removing conductive material |
US20080096390A1 (en) * | 2006-03-23 | 2008-04-24 | Cabot Microelectronics Corporation | Halide anions for metal removal rate control |
US20100176335A1 (en) * | 2007-06-08 | 2010-07-15 | Techno Semichem Co., Ltd. | CMP Slurry Composition for Copper Damascene Process |
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JP2006179845A (en) * | 2004-11-26 | 2006-07-06 | Fuji Photo Film Co Ltd | Polishing solution for metal, and polishing method |
JP2007012679A (en) * | 2005-06-28 | 2007-01-18 | Asahi Glass Co Ltd | Abrasive and manufacturing method of semiconductor integrated circuit device |
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CN101418189B (en) * | 2007-10-26 | 2013-10-02 | 安集微电子(上海)有限公司 | Polishing fluid of metal copper |
JP5403924B2 (en) * | 2008-02-29 | 2014-01-29 | 富士フイルム株式会社 | Polishing liquid for metal and chemical mechanical polishing method |
TWI454561B (en) * | 2008-12-30 | 2014-10-01 | Uwiz Technology Co Ltd | A polishing composition for planarizing the metal layer |
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Also Published As
Publication number | Publication date |
---|---|
EP1548075A2 (en) | 2005-06-29 |
KR20050043666A (en) | 2005-05-11 |
JP2005167219A (en) | 2005-06-23 |
EP1548075A3 (en) | 2005-09-07 |
CN1630045A (en) | 2005-06-22 |
TW200529979A (en) | 2005-09-16 |
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