WO2012048517A1 - -种化学机械平坦化浆料 - Google Patents
-种化学机械平坦化浆料 Download PDFInfo
- Publication number
- WO2012048517A1 WO2012048517A1 PCT/CN2011/001452 CN2011001452W WO2012048517A1 WO 2012048517 A1 WO2012048517 A1 WO 2012048517A1 CN 2011001452 W CN2011001452 W CN 2011001452W WO 2012048517 A1 WO2012048517 A1 WO 2012048517A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- chemical mechanical
- mechanical planarizing
- slurry according
- planarizing slurry
- acid
- Prior art date
Links
- 239000002002 slurry Substances 0.000 title claims abstract description 33
- 238000005498 polishing Methods 0.000 claims abstract description 62
- -1 copper metals Chemical class 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 14
- 239000007800 oxidant agent Substances 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims description 44
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 39
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 10
- XWNSFEAWWGGSKJ-UHFFFAOYSA-N 4-acetyl-4-methylheptanedinitrile Chemical compound N#CCCC(C)(C(=O)C)CCC#N XWNSFEAWWGGSKJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000004153 Potassium bromate Substances 0.000 claims description 9
- 229940094037 potassium bromate Drugs 0.000 claims description 9
- 235000019396 potassium bromate Nutrition 0.000 claims description 9
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000003002 pH adjusting agent Substances 0.000 claims description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 239000003623 enhancer Substances 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 claims description 3
- 239000001230 potassium iodate Substances 0.000 claims description 3
- 235000006666 potassium iodate Nutrition 0.000 claims description 3
- 229940093930 potassium iodate Drugs 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001413 amino acids Chemical class 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 230000000844 anti-bacterial effect Effects 0.000 claims description 2
- 239000003899 bactericide agent Substances 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 239000003112 inhibitor Substances 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 150000007530 organic bases Chemical class 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229940046063 potassium chlorate Drugs 0.000 claims description 2
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 claims description 2
- ORQYPOUSZINNCB-UHFFFAOYSA-N potassium;hypobromite Chemical compound [K+].Br[O-] ORQYPOUSZINNCB-UHFFFAOYSA-N 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims 1
- 229910000420 cerium oxide Inorganic materials 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 229910052740 iodine Inorganic materials 0.000 claims 1
- 239000011630 iodine Substances 0.000 claims 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims 1
- LLYCMZGLHLKPPU-UHFFFAOYSA-N perbromic acid Chemical compound OBr(=O)(=O)=O LLYCMZGLHLKPPU-UHFFFAOYSA-N 0.000 claims 1
- 229910052814 silicon oxide Inorganic materials 0.000 claims 1
- 239000010949 copper Substances 0.000 abstract description 18
- 229910052802 copper Inorganic materials 0.000 abstract description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 16
- 229910021420 polycrystalline silicon Inorganic materials 0.000 abstract description 14
- 239000000758 substrate Substances 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 238000005260 corrosion Methods 0.000 abstract description 6
- 230000007797 corrosion Effects 0.000 abstract description 6
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 239000000356 contaminant Substances 0.000 abstract description 3
- 239000007769 metal material Substances 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 description 13
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 229920005591 polysilicon Polymers 0.000 description 9
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000004471 Glycine Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000007517 polishing process Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GYSCBCSGKXNZRH-UHFFFAOYSA-N 1-benzothiophene-2-carboxamide Chemical compound C1=CC=C2SC(C(=O)N)=CC2=C1 GYSCBCSGKXNZRH-UHFFFAOYSA-N 0.000 description 1
- GHVNFZFCNZKVNT-UHFFFAOYSA-N Decanoic acid Natural products CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-M Methanesulfonate Chemical compound CS([O-])(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-M 0.000 description 1
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000012536 packaging technology Methods 0.000 description 1
- 125000005499 phosphonyl group Chemical group 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 229960003975 potassium Drugs 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007858 starting material Substances 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
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 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
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
-
- 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
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
- C09K3/1463—Aqueous liquid suspensions
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/32115—Planarisation
- H01L21/3212—Planarisation by chemical mechanical polishing [CMP]
Definitions
- the present invention relates to a chemical mechanical planarization paste in a semiconductor process, and more particularly to a high speed polishing polysilicon and copper chemical mechanical planarization paste.
- CMP chemical mechanical polishing
- the chemical mechanical polishing system is a chemical mechanical planarization technology that integrates cleaning, drying, on-line detection, and end point detection. It is a product of the development of integrated circuits (ICs) toward miniaturization, multi-layering, flattening, and thinning. Integrated circuits to increase production efficiency, reduce costs, and wafer planarization.
- CMP is widely used in the field of IC manufacturing, including polishing substrates, dielectrics, and interconnect materials.
- metal CMP is one of the key processes for device and interconnect fabrication in chip manufacturing below 90 nm, and it is a research hotspot in the sub-90 nm era.
- Metallic copper, aluminum, and tungsten are increasingly being used for interconnections on integrated circuit devices, and multilayer interconnections must be achieved by chemical mechanical polishing. Therefore, the development of a new generation of metal chemical mechanical polishing liquids has been attracting attention in the industry.
- a series of chemical mechanical polishing slurries suitable for polishing polycrystalline silicon have appeared, such as: US Pat. No. 2,011,152, 252 A1 discloses a composition and method for polysilicon CMP; and US 200610014390 A1 discloses a chemical mechanical machine for polysilicon and metal.
- Patent US Pat. No. 5,860,848 discloses a method of polysilicon CMP using a polymer electrolyte
- Patent CN 02114147.9 discloses a polishing solution for copper chemical-mechanical polishing process
- Patent CN 01818940.7 discloses a slurry for chemical mechanical polishing of copper
- Patent CN 98120987.4 discloses a CMP slurry manufacturing process for copper and a method of manufacturing an integrated circuit. But with 3D As packaging technology continues to mature, through-silicon via technology continues to gain more applications, while the application of high-speed polishing of polysilicon and copper has also attracted more and more attention.
- polishing liquids use hydrogen peroxide as the oxidant, but this oxidant inhibits the polishing of the polysilicon.
- the above-mentioned polishing liquid for high-speed copper polishing also has a case where the removal rate is insufficient, or there are defects, scratches, stains, and/or other residues on the surface of the substrate, or the polishing selectivity to copper is insufficient, or the polishing process is performed. There are problems such as local or overall corrosion. Therefore, it is necessary to develop a new chemical mechanical polishing slurry suitable for high speed processes.
- the technical problem to be solved by the present invention is that the polishing liquid for high-speed copper polishing in the prior art has insufficient removal rate, or defects, scratches, stains, and/or other residues on the surface of the substrate, or copper.
- the polishing selectivity is not sufficient, or there is a problem of local or overall corrosion during polishing, thereby providing a polishing paddle that can control local and overall corrosion of the material and reduce surface contamination of the substrate.
- the technical solution of the present invention is as follows:
- the metal chemical mechanical planarizing paddle of the present invention comprises abrasive particles, an oxidizing agent, a polishing rate increasing agent, and a carrier.
- the composition is composed of the following components in percentage by weight:
- the abrasive particles of the present invention may be referred to the prior art, preferably silica, alumina, yttria and/or polymer particles such as polyethylene or polytetrafluoroethylene, more preferably silica.
- the size of the abrasive particles is preferably 20 to 200 nm, more preferably 30 to 30 lOOnmo
- the oxidizing agent is preferably one or more selected from the group consisting of acids or soluble salts of halogen high-valent oxides (removing fluorine); including periodic acid, high bromic acid, high chlorine An acid, potassium iodate, potassium bromate, potassium chlorate, potassium hypoiodate, potassium hypobromite, potassium hypochlorite, etc., and one or more of the ammonium salts of the above acids.
- the polishing rate increasing agent may be one of an organic acid, an organic base, an amino acid, an ammonia compound, an organic decanoic acid or an organic sulfonic acid capable of reacting with polycrystalline silicon and a copper surface to form a soluble compound.
- the polishing rate enhancer may further comprise an ammonia compound having a -fluorene structure, such as an azole, an anthracene or the like.
- the chemical mechanical planarizing paste of the present invention has a pH of 8.0 to 12.0, preferably 9.0 to 11.0.
- the ⁇ adjusting agent may be various bases to adjust ⁇ to a desired value, preferably tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, ammonia water, potassium hydroxide, Ethylamine, ethylenediamine, ethanolamine and/or triethanolamine and the like.
- the chemical mechanical planarizing paste of the present invention may further comprise a surfactant, a stabilizer, an inhibitor and a bactericide to further improve the polishing performance of the surface.
- the reagents and starting materials used in the present invention are commercially available. The positive effects of the present invention are:
- Table 1 shows the polishing liquids 1 to 30 of the present invention.
- the formulations in the table are used to uniformly mix the components, and the deionized water is used to make up 100% of the polishing liquid.
- a pH adjuster (20 wt% KOH or dilute HNO 3 , which is selected according to the pH value) is adjusted to the desired pH value, stirring is continued to a uniform fluid, and each chemical mechanical planarization slurry is obtained by standing for 30 minutes.
- Polishing solution of the invention 1 ⁇ 30 formula
- Table 2 shows the polishing liquids 31 to 36 of the present invention and the comparative polishing liquid.
- the formulation in the table is used to uniformly mix the components, and the deionized water is made up to 100% by mass, and finally the pH adjusting agent (20% KOH) is used. Or dilute HN0 3 , select according to the pH value) adjust to the desired pH value, continue to stir to a uniform fluid, and let stand for 30 minutes to obtain each chemical mechanical planarization slurry.
- polishing liquids 31 to 36 and the comparative polishing liquid of the present invention in Table 2 were respectively polished on different materials (including a polycrystalline silicon substrate and a Cu substrate).
- the chemical mechanical polishing liquid of the present invention does not substantially cause local and overall corrosion during metal polishing, and has substantially no substrate surface defects, scratches, stains and other residual contaminants;
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Description
一种化学机械平坦化浆料
技术领域 本发明涉及半导体工艺中一种化学机械平坦化浆料, 更具体地说, 本发 明涉及一种用于高速抛光多晶硅和铜化学机械平坦化浆料。
技术背景
IC 制造工艺中平坦化技术已成为与光刻和刻蚀同等重要且相互依赖的 不可缺少的关键技术之一。 而化学机械抛光 (CMP) 工艺便是目前最有效、 最成熟的平坦化技术。 化学机械抛光系统是集清洗、 干燥、 在线检测、 终点 检测等技术与一体的化学机械平坦化技术, 是集成电路(IC) 向微细化、 多 层化、 平坦化、 薄型化发展的产物, 是集成电路提高生产效率、 降低成本、 晶圆全局平坦化必备技术。 CMP在 IC制造领域应用广泛, 抛光对象包括衬 底、介质及互连材料等。其中金属 CMP是 90纳米以下芯片制造中器件和互 连制造的关键工艺之一, 是亚 90纳米时代的研究热点。 金属铜, 铝, 钨正 在越来越多地应用于集成电路器件上的互连, 必须通过化学机械抛光实现多 层互连, 因而开发出新一代的金属化学机械抛光液一直让业界关注。 目前, 出现了一系列适合于抛光多晶硅的化学机械抛光浆料, 如: 专利 US2002151252A1 公开了一种用于多晶硅 CMP 的组合物和方法; 专利 US 200610014390A1 公开了一种用于多晶硅和金属的化学机械抛光浆料; 专利 US5860848公开了一种使用聚合体电解质的多晶硅 CMP的方法; 专利 CN 02114147.9 公开了一种铜化学一机械抛光工艺用抛光液; 专利 CN 01818940.7公开了铜的化学机械抛光所用的浆料; 专利 CN 98120987.4公开 了一种用于铜的 CMP浆液制造以及用于集成电路的制造方法。但是随着 3D
封装技术不断成熟, 硅通孔技术不断得到更多应用, 同时高速抛光多晶硅和 铜的应用也越来越引起人们的重视。 传统的铜抛光液使用过氧化氢为氧化 剂, 但是这种氧化剂会抑制多晶硅的抛光。 上述用于高速铜抛光的抛光液还 存在去除速率不足的情况, 或者衬底表面存在着缺陷、划伤、粘污和 /或其它 残留, 或者是对铜的抛光选择性不够, 或者是抛光过程中存在着局部或整体 腐蚀等问题。 因此有必要开发出新的适用于高速制程的化学机械抛光浆料。
发明概要 本发明所要解决的技术问题是现有技术中用于高速铜抛光的抛光液存 在去除速率不足, 或者衬底表面存在着缺陷、划伤、粘污和 /或其它残留, 或 者是对铜的抛光选择性不够, 或者是抛光过程中存在着局部或整体腐蚀等问 题, 从而提供一种能控制材料的局部和整体腐蚀, 减少衬底表面污染物的抛 光桨料。 本发明的技术方案如下:本发明的金属化学机械平坦化桨料包括研磨颗 粒, 氧化剂, 抛光速率提升剂, 和载体。
在本发明的抛光浆料实施例中, 按重量百分比该组合物由以下组分组 成:
研磨颗粒 0.05〜 10%
氧化剂 0.05〜 15%
抛光速率提升剂 0.1〜20%
载体 余量
本发明的研磨颗粒可以参照现有技术, 优选氧化硅、 氧化铝、 氧化铈和 /或聚合物颗粒, 如聚乙烯或聚四氟乙烯, 更优选氧化硅。
在本发明中, 该研磨颗粒的尺寸较佳地为 20〜200nm, 更佳地为 30〜
lOOnmo 在本发明中, 所述的氧化剂较佳地为选自卤素高价氧化物(除去氟)形 成的酸或可溶盐中的一种或几种; 包括高碘酸, 高溴酸, 高氯酸, 碘酸钾, 溴酸钾, 氯酸钾, 次碘酸钾, 次溴酸钾, 次氯酸钾等等, 以及上述酸的铵盐 中的一种或几种。 在本发明中,所述的抛光速率提升剂可为能够与多晶硅以及铜表面反应 形成易溶化合物的有机酸, 有机碱, 氨基酸, 氨类化合物, 有机瞵酸, 有机 磺酸中的一种或几种。 抛光速率提升剂还可以进一步包含含 -ΝΗ结构的氨类 化合物, 例如唑类, 胍类等等。
本发明的化学机械平坦化浆料 ρΗ值为 8.0〜12.0,较佳地 9.0〜 11.0。 ρΗ 调节剂可为各种碱, 以将 ρΗ调节至所需值即可, 较佳地四甲基氢氧化胺, 四乙基氢氧化胺, 四丙基氢氧化胺, 氨水, 氢氧化钾, 乙胺, 乙二胺, 乙醇 胺和 /或三乙醇胺等等。 本发明的化学机械平坦化浆料还可以包括表面活性剂、稳定剂, 抑制剂 和杀菌剂, 以进一步提高表面的抛光性能。 本发明所用试剂及原料均市售可得。 本发明的积极进步效果在于:
1 ) 通过抛光体系的作用提高金属抛光速率同时提高多晶硅和铜金属抛 光速率;
2)同时控制金属的材料的局部和整体腐蚀, 减少机台和衬底表面污染 物, 提高产品良率。
发明内容
下面通过实施例的方式进一步说明本发明,但并不因此将本发明限制在 所述的实施例范围之中。 实施例中各成分百分比均为质量百分比。
实施例 1〜30
表 1给出了本发明的抛光液 1〜30,将表中配方,将各成分混合均匀, 去离子水补足抛光液质量 100%。最后用 pH调节剂(20wt%KOH或稀 HN03, 根据 pH值的需要进行选择) 调节到所需 pH值, 继续搅拌至均匀流体, 静 置 30分钟即可得到各化学机械平坦化浆料。
本发明的抛光液 1~30配方
研磨顷粒 抛光速 ^提升剂 氧化剂
实施例 量 PH
具体物质 含 m w % A.体物 含
具体物质 含量 wt%
质 wt%
Si02 乙基磺
1 2 2 1 8
( 30nm ) 高碘酸
酸
氨基三
A1203
2 1 亚甲基 0.5
( lOOnm) 高碘酸 2 8
膦酸
2-羟基
Ce02
3 3 膦酰基 0.05 高碘酸 5 9
(200nm )
乙酸
聚乙烯 乙二胺
4 ( Mn: 5 四甲基 0.1 高溴酸 8 9
20000) 膦酸
聚四氟乙 乙二胺
5 烯 (Mn: 5 四甲基 0.5 高溴酸 0.05 10
40000) 膦酸
二亚乙
Si02 基二胺
6 3 1
( 50nm ) 高溴酸 0.08 10
五亚甲
基膦酸
甲基磺
7 Si02 1 1.5 高溴酸 0.1 10.4
酸
乙二胺
8 Si02 2 4 高溴酸 0.2 10.5
四乙酸
9 Si02 0.05 甘氨酸 2 高沒酸 0.5 10.6
10 Si02 2.5 甘氨酸 2.5 高溴酸 0.8 10.7
1 1 Si02 3.5 廿氨酸 3 高氯酸 1.2 】0.8
12 Si02 4.5 甘氨酸 15 高氯酸 1 10.9
13 Si02 4 甘氨酸 2 高氯酸 1.8 1 1
14 Si02 0.1 柠檬酸 0.1 高氯酸 2 1 1
15 Si02 0.2 柠檬酸 0.2 高氯酸 3 1 1
16 Si02 0.5 柠檬酸 0.5 高氯酸 4 1 1
17 Si02 0.8 柠檬酸 0.8 氯酸钾 5 12
柠檬酸
18 Si02 1.2 1 氯酸钾 6 12
二胺
柠檬酸
19 Si02 2.2 1 氯酸钾 7 12
二胺
柠檬酸
20 Si02 2 1.5 氯酸钾 8 12
二胺
柠檬酸
21 Si02 2 1.2 溴酸钾 9 12
三胺
柠檬酸
22 Si02 2 1.8 溴酸钾 15 12
三胺
柠檬酸
23 Si02 2 1 溴酸钾 8 10.5 三胺
羟基亚
24 Si02 2 1 溴酸钾 5 10.5 膦酸
羟基亚
25 Si02 2 1 溴酸胺 3 10.5 膦酸
羟基亚
26 Si02 2 1 溴酸胺 4 10.5 膦酸
羟基亚
27 Si02 2 5 溴酸钾 4 10.5 膦酸
羟基亚
1
28 Si02 10 膦酸 碘酸钾 4 10.5 甲基石黄
8
酸
29 柠檬酸
Si02 2 20 溴酸钾 4 1 1
二胺
柠檬酸
4
30 Si02 2 一胺 溴酸钾 2 10.5 甘氨酸 10
效果实施例
表 2给出了本发明的抛光液 31〜36和对比抛光液,将表中配方,将各成 分混合均匀,去离子水补足质量百分比 100%,最后用 pH调节剂(20%KOH
或稀 HN03, 根据 pH值的需要进行选择)调节到所需 pH值, 继续搅拌至均 匀流体, 静置 30分钟即可得到各化学机械平坦化浆料。
本发明的抛光液 31~36和对比抛光液配方
将表 2中本发明的抛光液 31〜36和对比抛光液分别对不同材料 (包括 多晶硅衬底、 Cu衬底, 进行抛光。 抛光条件相同, 抛光参数如下: Logitech. 抛光垫, 向下压力 3-5psi, 转盘转速 /抛光头转速 =60/80rpm, 抛光时间 120s, 化学机械平坦化浆料流速 100mL/min。 抛光结果见表 3。
表 3 本发明的抛光液 1~6和对比抛光液的抛光效果 不同压力下的去除速率 (A/min)
下压力
抛光液
(psi) 铜去除速 多晶硅去
率 表面缺陷 除速率
(A/min) (A/min)
31 3 4796 无 5000
32 3 6243 无 8000
33 3 6185 无 6000
34 6 6500 无 8200
35 5 8000 少 5600
36 5 6800 无 10380 对比 3 8500 多 1000
由以上数据和附图表明, 本发明的化学机械平坦化浆料具有以下优点:
1 ) 本发明的化学机械抛光液在金属抛光过程中基本不产生局部和整体 腐蚀, 基本无衬底表面缺陷、 划伤、 粘污和其它残留污染物;
2) 同时具有较高的多晶硅和铜的去除速率, 可满足 TSV 高速抛光要 求, 提高产量。
Claims
1.一种化学机械平坦化浆料, 其包含:
( a) 研磨颗粒,
(b) 氧化剂,
(c) 抛光速率提升剂,
(d) 载体。
2.如权利要求 1所述的化学机械平坦化浆料, 其特征在于: 所述研磨颗 粒的浓度为 0.05〜10wt%。
3.如权利要求 1所述的化学机械平坦化浆料, 其特征在于: 所述氧化剂 的浓度为 0.05〜15wt%。
4.如权利要求 1所述的化学机械平坦化浆料, 其特征在于: 所述抛光速 率提升剂的浓度为 0.1〜20wt%。
5.如权利要求 1所述的化学机械平坦化衆料, 其特征在于: 所述的载体 含量为余量。
6.如权利要求 1所述的化学机械平坦化浆料, 其特征在于: 所述研磨颗 粒为氧化物和 /或聚合物颗粒。
7.如权利要求 6所述的化学机械平坦化浆料, 其特征在于: 所述氧化物 颗粒为氧化硅, 氧化铝和 /或氧化铈。
8.如权利要求 6所述的化学机械平坦化浆料, 其特征在于: 所述聚合物 颗粒为聚乙烯和 /或聚四氟乙烯。
9.如权利要求 1, 6-8任一项所述的化学机械平坦化浆料, 其特征在于: 所述研磨颗粒的尺寸为 20〜200nm。
10. 如权利要求 9所述的化学机械平坦化浆料, 其特征在于: 所述研 磨颗粒的尺寸为 30~100nm。
11. 如权利要求 1 所述的化学机械平坦化浆料, 其特征在于: 所述氧 化剂选自氯、 溴和 /或碘的高价氧化物形成的酸或可溶盐的一种或几种。
12. 如权利要求 11所述的化学机械平坦化浆料, 其特征在于: 所述的 酸或可溶盐包括高碘酸, 高溴酸, 高氯酸, 碘酸钾, 溴酸钾, 氯酸钾, 次碘 酸钾, 次溴酸钾, 次氯酸钾及其铵盐中的一种或几种。
13. 如权利要求 1 所述的化学机械平坦化浆料, 其特征在于: 所述抛 光速率提升剂包括有机酸, 有机碱, 氨基酸, 氨类化合物, 有机瞵酸, 有机 磺酸, 含 -NH结构的胺类化合物中的一种或几种。
14. 如权利要求 13所述的化学机械平坦化浆料, 其特征在于: 所述胺 类化合物为唑类和 /或胍类。
15. 如权利要求 1所述的化学机械平坦化浆料, 还包含 pH调节剂。
16. 如权利要求 15所述的化学机械平坦化浆料,其特征在于:所述 pH 调节剂为各种碱。
17. 如权利要求 16所述的化学机械平坦化浆料, 其特征在于: 所述化 学机械平坦化浆料 pH值为 8.0~12.0。
18. 如权利要求 17所述的化学机械平坦化桨料, 其特征在于: 所述化 学机械平坦化浆料 pH值为 9.0〜11.0。
19. 如权利要求 16所述的化学机械平坦化浆料, 其特征在于: 所述碱 选自四甲基氢氧化胺, 四乙基氢氧化胺, 四丙基氢氧化胺, 氨水, 氢氧化钾, 乙胺, 乙二胺, 乙醇胺, 三乙醇胺的一种或几种。
20. 如权利要求 1 所述的化学机械平坦化浆料, 还包含表面活性剂、 稳定剂, 抑制剂, 杀菌剂中的一种或几种,
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