CN109972145A - A kind of chemical mechanical polishing liquid - Google Patents
A kind of chemical mechanical polishing liquid Download PDFInfo
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- CN109972145A CN109972145A CN201711439526.XA CN201711439526A CN109972145A CN 109972145 A CN109972145 A CN 109972145A CN 201711439526 A CN201711439526 A CN 201711439526A CN 109972145 A CN109972145 A CN 109972145A
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- China
- Prior art keywords
- chemical mechanical
- mechanical polishing
- polishing liquid
- copper
- polishing
- Prior art date
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- 238000005498 polishing Methods 0.000 title claims abstract description 98
- 239000000126 substance Substances 0.000 title claims abstract description 45
- 239000007788 liquid Substances 0.000 title claims abstract description 43
- 230000007797 corrosion Effects 0.000 claims abstract description 15
- 238000005260 corrosion Methods 0.000 claims abstract description 15
- 239000003112 inhibitor Substances 0.000 claims abstract description 15
- 239000007800 oxidant agent Substances 0.000 claims abstract description 14
- -1 hydrocarbyl sulfonate analog anion Chemical class 0.000 claims abstract description 13
- 239000008139 complexing agent Substances 0.000 claims abstract description 12
- 230000001590 oxidative effect Effects 0.000 claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 8
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 7
- 239000004094 surface-active agent Substances 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 239000006061 abrasive grain Substances 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 3
- MOFINMJRLYEONQ-UHFFFAOYSA-N [N].C=1C=CNC=1 Chemical group [N].C=1C=CNC=1 MOFINMJRLYEONQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 claims description 2
- VKZRWSNIWNFCIQ-WDSKDSINSA-N (2s)-2-[2-[[(1s)-1,2-dicarboxyethyl]amino]ethylamino]butanedioic acid Chemical compound OC(=O)C[C@@H](C(O)=O)NCCN[C@H](C(O)=O)CC(O)=O VKZRWSNIWNFCIQ-WDSKDSINSA-N 0.000 claims description 2
- FMCUPJKTGNBGEC-UHFFFAOYSA-N 1,2,4-triazol-4-amine Chemical compound NN1C=NN=C1 FMCUPJKTGNBGEC-UHFFFAOYSA-N 0.000 claims description 2
- MVRGLMCHDCMPKD-UHFFFAOYSA-N 3-amino-1h-1,2,4-triazole-5-carboxylic acid Chemical compound NC1=NNC(C(O)=O)=N1 MVRGLMCHDCMPKD-UHFFFAOYSA-N 0.000 claims description 2
- XZGLNCKSNVGDNX-UHFFFAOYSA-N 5-methyl-2h-tetrazole Chemical compound CC=1N=NNN=1 XZGLNCKSNVGDNX-UHFFFAOYSA-N 0.000 claims description 2
- 239000004475 Arginine Substances 0.000 claims description 2
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- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004471 Glycine Substances 0.000 claims description 2
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 claims description 2
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- DCXYFEDJOCDNAF-REOHCLBHSA-N L-asparagine Chemical compound OC(=O)[C@@H](N)CC(N)=O DCXYFEDJOCDNAF-REOHCLBHSA-N 0.000 claims description 2
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims description 2
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 2
- ZDXPYRJPNDTMRX-VKHMYHEASA-N L-glutamine Chemical compound OC(=O)[C@@H](N)CCC(N)=O ZDXPYRJPNDTMRX-VKHMYHEASA-N 0.000 claims description 2
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 claims description 2
- ROHFNLRQFUQHCH-YFKPBYRVSA-N L-leucine Chemical compound CC(C)C[C@H](N)C(O)=O ROHFNLRQFUQHCH-YFKPBYRVSA-N 0.000 claims description 2
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims description 2
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 claims description 2
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 claims description 2
- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 claims description 2
- ROHFNLRQFUQHCH-UHFFFAOYSA-N Leucine Natural products CC(C)CC(N)C(O)=O ROHFNLRQFUQHCH-UHFFFAOYSA-N 0.000 claims description 2
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004472 Lysine Substances 0.000 claims description 2
- BVWCKYAYMBDPIP-UHFFFAOYSA-N NC=1C=C(C=C(C1)N)C=CC1=CC=CC=C1 Chemical compound NC=1C=C(C=C(C1)N)C=CC1=CC=CC=C1 BVWCKYAYMBDPIP-UHFFFAOYSA-N 0.000 claims description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical group [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 2
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 claims description 2
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 claims description 2
- QIVBCDIJIAJPQS-UHFFFAOYSA-N Tryptophan Natural products C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 claims description 2
- KZSNJWFQEVHDMF-UHFFFAOYSA-N Valine Natural products CC(C)C(N)C(O)=O KZSNJWFQEVHDMF-UHFFFAOYSA-N 0.000 claims description 2
- 235000004279 alanine Nutrition 0.000 claims description 2
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 claims description 2
- 235000009582 asparagine Nutrition 0.000 claims description 2
- 229960001230 asparagine Drugs 0.000 claims description 2
- 235000003704 aspartic acid Nutrition 0.000 claims description 2
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229960001484 edetic acid Drugs 0.000 claims description 2
- NLVXSWCKKBEXTG-UHFFFAOYSA-M ethenesulfonate Chemical compound [O-]S(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-M 0.000 claims description 2
- 235000013922 glutamic acid Nutrition 0.000 claims description 2
- 239000004220 glutamic acid Substances 0.000 claims description 2
- ZDXPYRJPNDTMRX-UHFFFAOYSA-N glutamine Natural products OC(=O)C(N)CCC(N)=O ZDXPYRJPNDTMRX-UHFFFAOYSA-N 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 claims description 2
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- OCNPXKLQSGAGKT-UHFFFAOYSA-N propyl benzenesulfonate Chemical compound CCCOS(=O)(=O)C1=CC=CC=C1 OCNPXKLQSGAGKT-UHFFFAOYSA-N 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 239000004474 valine Substances 0.000 claims description 2
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims 1
- WZUUZPAYWFIBDF-UHFFFAOYSA-N 5-amino-1,2-dihydro-1,2,4-triazole-3-thione Chemical compound NC1=NNC(S)=N1 WZUUZPAYWFIBDF-UHFFFAOYSA-N 0.000 claims 1
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 claims 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical class CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims 1
- RUSUZAGBORAKPY-UHFFFAOYSA-N acetic acid;n'-[2-(2-aminoethylamino)ethyl]ethane-1,2-diamine Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCNCCNCCN RUSUZAGBORAKPY-UHFFFAOYSA-N 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims 1
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 claims 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 63
- 239000010949 copper Substances 0.000 abstract description 56
- 229910052802 copper Inorganic materials 0.000 abstract description 50
- 239000012530 fluid Substances 0.000 abstract description 22
- 230000007547 defect Effects 0.000 abstract description 10
- 229910052715 tantalum Inorganic materials 0.000 abstract description 8
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 abstract description 8
- 230000004888 barrier function Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 230000003628 erosive effect Effects 0.000 description 9
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- 239000003082 abrasive agent Substances 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000036961 partial effect Effects 0.000 description 3
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- 150000003871 sulfonates Chemical class 0.000 description 3
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- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 150000000178 1,2,4-triazoles Chemical class 0.000 description 1
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Chemical compound C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-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
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-M Methanesulfonate Chemical compound CS([O-])(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
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- 230000003213 activating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 125000003630 glycyl group Chemical group [H]N([H])C([H])([H])C(*)=O 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
- B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
- B24B37/042—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor
- B24B37/044—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor characterised by the composition of the lapping agent
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F3/00—Brightening metals by chemical means
- C23F3/04—Heavy metals
- C23F3/06—Heavy metals with acidic solutions
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
The present invention provides a kind of chemical mechanical polishing liquid, which includes Silica abrasive particle, corrosion inhibitor, complexing agent, oxidant and hydrocarbyl sulfonate analog anion surfactants.The polishing fluid can be applied to the polishing of metal copper-connection, can significantly improve copper removal rate, and reduce the removal rate of tantalum simultaneously.Further, it is also possible to improve polishing after copper wire saucerization, while polish after without copper remain and corrode the defects of.
Description
Technical field
The present invention relates to chemical mechanical polishing liquid field more particularly to a kind of chemical mechanical polishing of metals liquid.
Background technique
With the development of semiconductor technology, the microminiaturization of electronic component is contained in one integrated circuit millions of
Transistor.The transistor that can largely switch rapidly is incorporated based on traditional aluminium or aluminium alloy interconnection line, reduces signal
Transmission speed, and mass energy is consumed in electric current transmittance process, therefore, semiconductor technology is hindered to a certain extent
Development.
For this purpose, people begin look for the material with higher electrical properties to replace aluminium.It is well known that the resistance of copper is small,
Possess good electric conductivity, the transmission speed of signal between transistor in circuit can be accelerated, smaller parasitic capacitance can also be provided
Ability, to reduce circuit for the sensibility of electromigration.Therefore, above-mentioned electrical advantages make copper in semiconductor technology development
With good development prospect.
But in the ic manufacturing process of copper, it has been found that copper can migrate or diffuse into the crystalline substance of integrated circuit
Body area under control domain, has an adverse effect hence for the transistor performance in semiconductor, thus the interconnection line of copper can only be by inlaying
Technique manufacture, it may be assumed that form groove in first layer, fill copper barrier layer and copper, in the trench to form plain conductor and cover
On the dielectric layer.Thereafter, copper extra on dielectric layer/copper barrier layer is removed by chemically mechanical polishing, finally in groove
Leave single interconnection line.
The CMP process of copper is generally divided into 3 steps, and step 1 uses higher lower pressure, with fast and efficient
Removal rate removal substrate surface on a large amount of copper and leave certain thickness copper, step 2 is removed with lower removal rate and is remained
Remaining metallic copper is simultaneously parked in barrier layer, and step 3 removes barrier layer and part of dielectric layer and metallic copper with barrier polishing solution again, from
And realize planarization.
However, metal layer has portion concave above copper wire before copper polishing.When polishing, the copper on dielectric material is in master
(higher) is easy to be removed under body pressure, and polish pressure suffered by the copper of recess is lower than prevailing pressure, and copper removal rate is small.
With the progress of polishing, the difference in height of copper can be gradually reduced, to reach planarization.But during the polishing process, if copper is thrown
The chemical action of light liquid is too strong, and static etch rate is too high, even if then the passivating film of copper is at low pressures, (such as copper wire is recessed
Place) it is also easy to be removed, cause planarization efficiency to reduce, the saucerization after polishing increases.Therefore, for the chemical machinery of copper
It for polishing, on the one hand needs to remove copper extra on barrier layer as early as possible, on the other hand needs to minimize copper wire after polishing
Saucerization.
With the development of integrated circuit, on the one hand, in traditional IC industry, in order to improve integrated level, reduce energy consumption, contracting
Short delaing time, line width is more and more narrow, and dielectric layer uses lower low dielectric (low-k) material of mechanical strength, the number of plies of wiring
Also more and more, in order to guarantee the performance and stability of integrated circuit, the requirement to copper CMP is also higher and higher.It wants
Asking reduces polish pressure in the case where guaranteeing the removal rate of copper, improves the planarization of copper line surface, controls surface defect.Separately
On the one hand, since physical limitation, line width cannot infinitely reduce, semicon industry no longer merely relies on to be collected on a single chip
Performance is improved at more devices, and turns on multi-chip package.
As the development of semiconductor fabrication process needs a kind of gold to apply copper preferably in semiconductor technology
Belong to chemical mechanical polishing liquid, the removal rate of copper and the polishing selection ratio of copper and tantalum barrier layer is capable of providing, after improving polishing
The dish of copper wire, and polish after without copper remain and corrode the defects of.
Summary of the invention
To solve the above-mentioned problems, the present invention provides a kind of chemical mechanical polishing liquid that can be applied to copper-connection, pass through
Silica abrasive particle, corrosion inhibitor, complexing agent, oxidant, polyacrylic anionic surface are added in polishing fluid
The combination of activating agent and/or hydrocarbyl sulfonate improves the polishing selection ratio of copper and tantalum barrier layer, improves the dish of copper wire after polishing
Shape recess and dielectric layer corrode, and polish after without copper remain and corrode the defects of.
The present invention provides a kind of chemical mechanical polishing liquid, the chemical mechanical polishing liquid includes Silica abrasive
Grain, corrosion inhibitor, complexing agent, oxidant, polyacrylic acid analog anion surfactants and/or hydrocarbyl sulfonate.
Preferably, the average grain diameter of the abrasive grains is 60-140nm, more preferably 80-120nm.
Preferably, the particle diameter distribution index (PdI) of the abrasive grains is 0.1-0.6.
Preferably, the concentration of the abrasive grains is 0.05-2wt%, more preferably 0.1-1wt%.
Preferably, the complexing agent is ammonia carboxylic compound and its salt.
Preferably, the complexing agent is selected from glycine, alanine, valine, leucine, proline, phenylalanine, junket ammonia
Acid, tryptophan, lysine, arginine, histidine, serine, aspartic acid, glutamic acid, asparagine, glutamine, ammonia three
Acetic acid, ethylenediamine tetra-acetic acid, hexamethylene tetraacethyl, ethylenediamine disuccinic acid, diethylene triamine pentacetic acid (DTPA) and triethylene tetramine six
One of acetic acid is a variety of.
Preferably, the complexing agent content is mass percent 0.1-5wt%, it is highly preferred that the complexing agent content is
Mass percent 0.5-3wt%.
Preferably, the hydrocarbyl sulfonate is the hydrocarbyl sulfonate of C < 10；Wherein, the hydrocarbyl sulfonate be sylvite or
Sodium salt.
Preferably, the hydrocarbyl sulfonate includes methyl sulfonate, vinylsulfonate, allylsulfonate, p- methyl
Benzene sulfonate, p- ethyl phenenyl azochlorosulfonate acid salt, to one of propyl benzenesulfonate or a variety of.
Preferably, the concentration of the hydrocarbyl sulfonic salt surfactant is 0.001-0.5wt%, it is furthermore preferred that described
The concentration of hydrocarbyl sulfonic salt surfactant is 0.005-0.1wt%
Preferably, the corrosion inhibitor is nitrogen azole compounds.
Preferably, the corrosion inhibitor be selected from benzotriazole, 1,2,4- triazoles, 3- amino -1,2,4- triazole,
4- amino -1,2,4- triazole, 3,5- diaminostilbene, 2,4- triazoles, 5- carboxyl -3- amino -1,2,4- triazole, 3- ammonia
Base -5- sulfydryl -1,2,4- triazole, 5- acetic acid -1H- tetrazole, 5- methyl tetrazole, methylbenzotriazole and 5- amino -
One of 1H- tetrazole is a variety of.
Preferably, the corrosion inhibitor concentration is 0.001-2wt%, it is highly preferred that the corrosion inhibitor concentration is
0.005-1wt%.
Preferably, the oxidant is hydrogen peroxide.
Preferably, the concentration of the oxidant is 0.05-5wt%, more preferably 0.1-3wt%.
Preferably, the pH value of the chemical mechanical polishing liquid is 5-9.
Invention further provides a kind of application of chemical mechanical polishing liquid as described above in metal copper-connection.
It can also include other typical additives such as pH adjusting agent, viscosity modifier, defoaming agent in polishing fluid of the invention
Etc. reaching polishing effect.
Configuration can be concentrated in polishing fluid of the invention, be diluted when in use with deionized water and add oxidant to originally
The concentration range of invention uses.
Compared with prior art, the technical advantages of the present invention are that:
The removal rate of tantalum is reduced while 1. improving copper removal rate；
2. the saucerization of copper wire and dielectric layer after polishing can be improved to corrode；
Detailed description of the invention
Fig. 1 shows for the butterfly recess of copper wire in the copper graphic chips after the polishing of 3 polishing fluid of example by contrast and dielectric layer erosion
It is intended to；
Fig. 2 shows for the butterfly recess of copper wire in the copper graphic chips after the polishing of 37 polishing fluid of embodiment and dielectric layer erosion
It is intended to.
Specific embodiment
Below by specific embodiment, the advantages of the present invention are further explained, but protection scope of the present invention is not only limited to
In following embodiments.
Table 1 is each component content in the embodiment 1-36 of chemical mechanical polishing liquid of the invention.Polishing fluid system of the invention
Preparation Method is as follows: being uniformly mixed the other components in addition to oxidant according to the formula in following table, supplies quality percentage with water
Than to 100%.With KOH or HNO3Adjust required pH value.Using preceding oxidizer, it is uniformly mixed.
Table 1 is the formula of polishing fluid embodiment 1-36
Table 2 gives the embodiment 37-50 and comparative example 1-7 of chemical mechanical polishing liquid of the invention, by institute in table
To formula, the other components in addition to oxidant are uniformly mixed, supply mass percent to 100% with water.With KOH or HNO3
Adjust required pH value.Using preceding oxidizer, it is uniformly mixed.
Table 2 is the formula of polishing fluid comparative example 1-7 and embodiment 37-50
Such as table 1, shown in table 2, chemical mechanical polishing liquid provided by the invention is by choosing different-grain diameter size and partial size point
The SiO of cloth coefficient (PdI)2Grinding ingredient of the abrasive grains as chemical mechanical polishing liquid is prepared for different chemical machineries and throws
Light liquid embodiment 1-50.Further, 37-50 of the embodiment of the present invention and comparison polishing fluid 1-7 is respectively adopted to polish copper, institute
It is specifically as shown in table 3 to obtain polishing effect data.
Specific polishing condition: lower pressure 1.5psi, 2.0psi；Polishing disk and rubbing head revolving speed 73/67rpm, polishing pad
IC1010 polishes flow velocity 350ml/min, polishing machine platform 12 " ReflexionLK, polishing time 1min.
The polishing effect of table 3 comparative example 1-6 and embodiment 37-50
In conjunction with shown in table 2, table 3, polishing fluid embodiment 37-50 provided by the invention, no matter 2.0psi's or 1.5psi
Under polish pressure, after hydrocarbyl sulfonate is added, the removal rate of higher Cu is all had, while there is the polishing of lower Ta
Speed selects ratio so as to significantly improve the polishing of Cu/Ta, reaches as high as 2343.Meanwhile it can further control the dish of wafer
Shape recess value and dielectric layer erosion value.In particular, polishing fluid provided by the invention can significantly reduce dish in embodiment 43,44
The case where erosion of shape recess and dielectric layer.
In conjunction with shown in table 2, table 3, the SiO of different-grain diameter size and size distribution coefficient is added in embodiment 37-412Mill
After material, polishing fluid has marked difference to the removal rate of Cu, in conjunction with comparative example 3,4 as can be seen that working as SiO2The partial size of abrasive material
Smaller and broad particle distribution works as SiO2When the partial size of abrasive material is larger and narrower particle size distribution, the Cu of polishing fluid can be all caused
Removal rate is very low.And work as SiO2When the particle size and size distribution intensity (PdI) of abrasive material are in certain distribution, polishing
Liquid dramatically increases the removal rate of Cu, while significantly inhibiting to the removal rate of Ta, so that polishing fluid has
Higher Cu/Ta polishing selection ratio.In addition, embodiment 42 obtains higher Cu/Ta polishing selection ratio compared to comparative example 3,4
Meanwhile further improving the saucerization and erosion degree of copper wire.
Fig. 1 and Fig. 2 is further regarded to, is respectively in the copper graphic chips after using comparative example 3 and embodiment 37 to polish
Copper wire width is 5 microns, the close linear array area surface topography map that dielectric material width is 1 micron.It can be seen from the figure that using comparison
Example 3 is used as polishing fluid, and there are 125.7 nanometers of dish-like recess and the erosion of 43.9 nanometers of dielectric layer for the copper wire after polishing；And make
Use the present embodiment 37 as polishing fluid, the dish-like recess of the copper wire after polishing is reduced to 61.1 nanometers, and dielectric layer erosion is down to 9.2 and is received
Rice, the attenuating effect highly significant of polishing fluid of the invention to the erosion of the especially dielectric layer of the surface topography after polishing.
Meanwhile it 39 can be found compared with the component of comparative example 7 in conjunction with the embodiments, the azole corrosion inhibitor benzene with phenyl ring
And the combination of triazole and Sulfonates anionic surfactant greatly suppresses although the removal rate of tantalum can be reduced
The removal rate of copper can not be effectively removed copper.Compared with the embodiment of the present invention 39, comparative example 5 and 6, which is added to use, is free of benzene
The combination of the azole corrosion inhibitor and Sulfonates anionic surfactant of ring, but the pH value of comparative example 5 is too low, copper and tantalum
Removal rate it is also higher, cause it is dish-like recess and dielectric layer corrode it is larger.And the pH value of comparative example 6 is excessively high, leads to copper
Removal rate substantially reduces, and can not effectively remove copper.
Will with comparison polishing fluid 5 and embodiment 38,39 polish after blank copper wafer cleaning after with Defect Scanning instrument SP2 into
Row Defect Scanning, as a result, it has been found that the copper after the comparison polishing fluid 5 and embodiment 38 that are prepared with the abrasive grains of higher PdI polish is brilliant
The surface defect number of piece is higher than embodiment 39.Therefore, the PdI control of abrasive grains is just able to satisfy removal speed in a certain range
The requirement of rate and defect.
In conclusion by the present invention in that abrasive grains with PdI in a certain range, both ensure that high copper removal speed
Rate, and reduce surface defect.With the nitrogen azole corrosion inhibitor and Sulfonates for being free of phenyl ring by adding in polishing fluid
The combination of anionic surfactant maintains the high removal rate of copper, reduces the removal rate of tantalum barrier layer, realize and mention
The effect of high polishing fluid compares the polishing selection of copper and tantalum barrier layer；The polishing that the present invention is used for chip can improve copper wire after polishing
Dish-like recess (Dishing) and dielectric layer corrode (Erosion), and polish after without copper residue and it is corrosion-free the defects of.
It should be noted that the embodiment of the present invention has preferable implementation, and not the present invention is made any type of
Limitation, any one skilled in the art change or are modified to possibly also with the technology contents of the disclosure above equivalent effective
Embodiment, as long as without departing from the content of technical solution of the present invention, it is to the above embodiments according to the technical essence of the invention
Any modification or equivalent variations and modification, all of which are still within the scope of the technical scheme of the invention.
Claims (23)
1. a kind of chemical mechanical polishing liquid, which is characterized in that the chemical mechanical polishing liquid includes Silica abrasive particle, rotten
Corrosion inhibitor, complexing agent, oxidant and hydrocarbyl sulfonate analog anion surfactants.
2. chemical mechanical polishing liquid as described in claim 1, which is characterized in that the average grain diameter of the abrasive grains is 60-
140nm。
3. chemical mechanical polishing liquid as claimed in claim 2, which is characterized in that the average grain diameter of the abrasive grains is 80-
120nm。
4. chemical mechanical polishing liquid as described in claim 1, which is characterized in that the particle diameter distribution index of the abrasive grains
It (PdI) is 0.1-0.6.
5. chemical mechanical polishing liquid as described in claim 1, which is characterized in that the concentration of the abrasive grains is 0.05-
2wt%.
6. chemical mechanical polishing liquid as claimed in claim 5, which is characterized in that the concentration of the abrasive grains is 0.1-
1wt%.
7. chemical mechanical polishing liquid as described in claim 1, which is characterized in that the complexing agent be ammonia carboxylic compound and its
Salt.
8. chemical mechanical polishing liquid as claimed in claim 7, which is characterized in that the complexing agent be selected from glycine,
Alanine, valine, leucine, proline, phenylalanine, tyrosine, tryptophan, lysine, arginine, histidine,
Serine, aspartic acid, glutamic acid, asparagine, glutamine, nitrilotriacetic acid, ethylenediamine tetra-acetic acid, hexamethylene tetraacethyl,
One of ethylenediamine disuccinic acid, diethylene triamine pentacetic acid (DTPA) and triethylenetetramine hexaacetic acid are a variety of.
9. chemical mechanical polishing liquid according to claim 7, which is characterized in that the complexing agent content is mass percent
0.1-5wt%.
10. chemical mechanical polishing liquid according to claim 7, which is characterized in that the complexing agent content is quality percentage
Compare 0.5-3wt%.
11. chemical mechanical polishing liquid as described in claim 1, which is characterized in that the hydrocarbyl sulfonate is the alkyl of C < 10
Sulfonate；Wherein, the hydrocarbyl sulfonate is sylvite or sodium salt.
12. chemical mechanical polishing liquid as claimed in claim 11, which is characterized in that the hydrocarbyl sulfonic salt surfactant
Concentration be 0.001-0.5wt%.
13. chemical mechanical polishing liquid as claimed in claim 12, which is characterized in that the hydrocarbyl sulfonic salt surfactant
Concentration be 0.005-0.1wt%.
14. chemical mechanical polishing liquid as claimed in claim 13, which is characterized in that the hydrocarbyl sulfonate includes methane sulfonic acid
Salt, vinylsulfonate, allylsulfonate, p- toluenesulfonate, p- ethyl phenenyl azochlorosulfonate acid salt, in propyl benzenesulfonate
It is one or more.
15. chemical mechanical polishing liquid as described in claim 1, which is characterized in that the corrosion inhibitor is nitrogen azole chemical combination
Object.
16. chemical mechanical polishing liquid as claimed in claim 15, which is characterized in that the corrosion inhibitor is selected from 1,2,4- tri-
Nitrogen azoles, 3- amino -1,2,4- triazole, 4- amino -1,2,4- triazole, 3,5- diaminostilbene, 2,4- triazoles, 5- carboxyl -
3- amino -1,2,4- triazole, 3- amino -5- sulfydryl -1,2,4- triazole, 5- acetic acid -1H- tetrazole, 5- methyl tetrazole
With one of 5- amino -1H- tetrazole or a variety of.
17. chemical mechanical polishing liquid as claimed in claim 16, which is characterized in that the corrosion inhibitor concentration is 0.001-
2wt%.
18. chemical mechanical polishing liquid as claimed in claim 16, which is characterized in that the corrosion inhibitor concentration is 0.005-
1wt%.
19. chemical mechanical polishing liquid as described in claim 1, which is characterized in that the oxidant is hydrogen peroxide.
20. chemical mechanical polishing liquid as claimed in claim 19, which is characterized in that the concentration of the oxidant is 0.05-
5wt%.
21. chemical mechanical polishing liquid as claimed in claim 20, which is characterized in that the concentration of the oxidant is 0.1-
3wt%.
22. chemical mechanical polishing liquid as described in claim 1, which is characterized in that the pH value of the chemical mechanical polishing liquid is
5‐9。
23. a kind of such as application of the described in any item chemical mechanical polishing liquids of claim 1-22 in metal copper-connection.
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