CN102373012B - Chemical-mechanical polishing solution - Google Patents
Chemical-mechanical polishing solution Download PDFInfo
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- CN102373012B CN102373012B CN201010250450.8A CN201010250450A CN102373012B CN 102373012 B CN102373012 B CN 102373012B CN 201010250450 A CN201010250450 A CN 201010250450A CN 102373012 B CN102373012 B CN 102373012B
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- mechanical polishing
- chemical mechanical
- tungsten
- polishing liquid
- silver
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- 238000005498 polishing Methods 0.000 title claims abstract description 91
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 48
- 239000010937 tungsten Substances 0.000 claims abstract description 48
- 238000000227 grinding Methods 0.000 claims abstract description 15
- 239000003112 inhibitor Substances 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 238000005530 etching Methods 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 8
- 230000003750 conditioning effect Effects 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 44
- 239000000126 substance Substances 0.000 claims description 37
- 239000007788 liquid Substances 0.000 claims description 32
- -1 transition metal salt Chemical class 0.000 claims description 17
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 15
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 10
- 239000007800 oxidant agent Substances 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 7
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims description 4
- 229910000367 silver sulfate Inorganic materials 0.000 claims description 4
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- RBWNDBNSJFCLBZ-UHFFFAOYSA-N 7-methyl-5,6,7,8-tetrahydro-3h-[1]benzothiolo[2,3-d]pyrimidine-4-thione Chemical compound N1=CNC(=S)C2=C1SC1=C2CCC(C)C1 RBWNDBNSJFCLBZ-UHFFFAOYSA-N 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical group N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052755 nonmetal Inorganic materials 0.000 claims description 2
- 229940096017 silver fluoride Drugs 0.000 claims description 2
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 claims description 2
- 150000002978 peroxides Chemical group 0.000 claims 2
- 230000003068 static effect Effects 0.000 abstract description 9
- 150000001408 amides Chemical group 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 25
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 15
- 229910052710 silicon Inorganic materials 0.000 description 15
- 239000010703 silicon Substances 0.000 description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 239000012530 fluid Substances 0.000 description 9
- 229910052742 iron Inorganic materials 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 150000001413 amino acids Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229940085991 phosphate ion Drugs 0.000 description 3
- JZBCTZLGKSYRSF-UHFFFAOYSA-N 2-Ethyl-3,5-dimethylpyrazine Chemical compound CCC1=NC=C(C)N=C1C JZBCTZLGKSYRSF-UHFFFAOYSA-N 0.000 description 2
- IGJQUJNPMOYEJY-UHFFFAOYSA-N 2-acetylpyrrole Chemical compound CC(=O)C1=CC=CN1 IGJQUJNPMOYEJY-UHFFFAOYSA-N 0.000 description 2
- JVRHDWRSHRSHHS-UHFFFAOYSA-N 3-hydroxysilylpropan-1-amine Chemical compound NCCC[SiH2]O JVRHDWRSHRSHHS-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- IAEGWXHKWJGQAZ-UHFFFAOYSA-N trimethylpyrazine Chemical compound CC1=CN=C(C)C(C)=N1 IAEGWXHKWJGQAZ-UHFFFAOYSA-N 0.000 description 2
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- 239000001363 2-ethyl-3,5-dimethylpyrazine Substances 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 108010024636 Glutathione Proteins 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 241000271897 Viperidae Species 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 229960005191 ferric oxide Drugs 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229960003180 glutathione Drugs 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- WJLUBOLDZCQZEV-UHFFFAOYSA-M hexadecyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CCCCCCCCCCCCCCCC[N+](C)(C)C WJLUBOLDZCQZEV-UHFFFAOYSA-M 0.000 description 1
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N methyl alcohol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 125000002081 peroxide group Chemical group 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- DPJRMOMPQZCRJU-UHFFFAOYSA-M thiamine hydrochloride Chemical compound Cl.[Cl-].CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N DPJRMOMPQZCRJU-UHFFFAOYSA-M 0.000 description 1
- 229960000344 thiamine hydrochloride Drugs 0.000 description 1
- 235000019190 thiamine hydrochloride Nutrition 0.000 description 1
- 239000011747 thiamine hydrochloride Substances 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 150000003624 transition metals Chemical class 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
-
- 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]
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
The invention discloses a chemical-mechanical polishing solution. The chemical-mechanical polishing solution comprises water, a grinding agent, a compound etching tungsten, a tungsten etch inhibitor, and a base material profile conditioning agent, wherein the tungsten etch inhibitor is an amide containing a double bond. The tungsten polishing speed of the polishing solution is very high, and simultaneously the tungsten static etch rate of the polishing solution is very low.
Description
Technical field
The present invention relates to a kind of chemical mechanical polishing liquid, be specifically related to a kind of chemical mechanical polishing liquid for tungsten.
Background technology
Along with the development of semiconductor technology, and the continuous increase of large scale integrated circuit interconnection layer, it is particularly crucial that the planarization of conductive layer and insulating medium layer becomes.Twentieth century eighties, the chemico-mechanical polishing of being initiated by IBM Corporation (CMP) technology is considered to the effective method of current overall planarization.
Chemico-mechanical polishing (CMP) is combined into by chemical action, mechanism and this two kinds of effects.It is conventionally by a grinding table with polishing pad, and a grinding head for carries chips forms.Wherein grinding head is fixed chip, then the front of chip is pressed on polishing pad.When carrying out chemico-mechanical polishing, grinding head moves or rotates along the direction of motion the same with grinding table at polishing pad Linear.Meanwhile, the slurries that contain grinding agent are dripped on polishing pad, and are laid on polishing pad because of centrifugal action.Chip surface is realized overall planarization under mechanical and chemical double action.
Main mechanism to metal level chemico-mechanical polishing (CMP) is considered to: oxidant is first by oxidation on metal surface film forming, the grinding agent that silicon dioxide and aluminium oxide be representative of take is removed this layer of oxide-film machinery, produce new metal surface continuation oxidized, these two kinds collaborative the carrying out of effect.
As the tungsten of one of chemico-mechanical polishing (CMP) object, under high current density, anti-electron transfer ability is strong, and can form good ohmic contact with silicon, so can be used as filling metal and the diffusion impervious layer of contact hole and interlayer hole.
The chemico-mechanical polishing of tungsten (CMP), has several different methods:
1991, F.B.Kaufman etc. have reported the method (" Chemical Mechanical Polishing for Fabricating Patterned W Metal Features asChip Interconnects " of the potassium ferricyanide for tungsten CMP, Journal of the Electro chemical Society, Vol.138, No.11, in November, 1991).
United States Patent (USP) 5340370 discloses a kind of formula for tungsten CMP (CMP), wherein contains the 0.1M potassium ferricyanide, and 5% silica contains the acetate as pH buffer simultaneously.Because the potassium ferricyanide is under ultraviolet light or solar radiation, and in acid medium, can decomposite hypertoxic hydrogen cyanide, thereby limit it and be widely used.
United States Patent (USP) 5527423, United States Patent (USP) 6008119, United States Patent (USP) 6284151 grades disclose the (NO by Fe
3)
3, alumina system is for the method for tungsten mechanical polishing (CMP).This polishing body ties up to static etch rate (static etch rate) aspect and has advantage, but owing to adopting aluminium oxide as grinding agent, product defects (defect) aspect exists significantly not enough.The ferric nitrate of high concentration makes the pH value of polishing fluid be highly acid simultaneously, and severe corrosion equipment meanwhile, generates iron rust, pollutes polishing pad.In addition, the iron ion of high concentration, as metal ion movably, has seriously reduced the reliability of semiconductor components and devices.
United States Patent (USP) 5225034, United States Patent (USP) 5354490 discloses hydrogen peroxide and silver nitrate has been used jointly, is used as the finishing method that oxidant carries out metal (copper).But in the type method, silver nitrate consumption very large (being greater than 2%), causes polishing fluid high cost, grinding agent is unstable, easy precipitation, the problems such as hydrogen peroxide fast decoupled.
United States Patent (USP) 5958288 discloses ferric nitrate has been used as to catalyst, and hydrogen peroxide is used as oxidant, carries out the method for tungsten CMP.It should be noted that: in this patent, mentioned multiple transition metal, tested and confirm significantly effectively to only have ferro element.Therefore actual implementation result and the scope of this invention are very limited.Although the method has significantly reduced the consumption of ferric nitrate, because iron ion still exists, and between hydrogen peroxide, there is Fenton reaction, hydrogen peroxide can be rapidly and decomposition failure tempestuously, so the poor problem of this polishing fluid existence and stability.
United States Patent (USP) 5980775 and United States Patent (USP) 6068787, on United States Patent (USP) 5958288 bases, add organic acid to make stabilizer, have improved the decomposition rate of hydrogen peroxide.But its decomposition rate is still higher, within common two weeks, interior hydrogen peroxide concentration can reduce more than 10%, causes polishing velocity to decline, and polishing fluid is decomposition failure gradually.
In the system of iron and hydrogen peroxide, the static corrosion speed of tungsten is very fast, directly has influence on the yield of production, needs further to add the static corrosion inhibitor of tungsten for this reason.
CN98809580.7 adds at hydrogen peroxide the inhibitor of tungsten etching of using in the system of iron:
2,3,5-trimethylpyrazine, viper quinoline, pyridazine, pyrazine; Glutathione, thiophene, sulfydryl N-oxy picolinate, thiamine hydrochloride, the tetraethyl tetraalkylthiuram disulfide of reduction; Isostearoyl base ethyl imino group, cetyltrimethylammonium hydroxide trimethyl ammonium, 2-heptadecyl-4-ethyl-2-oxazoline-4-methyl alcohol, tricaprylylmethylammchloride chloride, 4,4-bis-Jia oxazolin, tetrabutylammonium, lauryl amine, tetramethyl ammonium hydroxide and its combination; Glycine, aminopropyl silanol, aminopropyl siloxanes, or the mixture of aminopropyl silanol and aminopropyl siloxanes.
CN200610077360.7 adds at hydrogen peroxide the inhibitor of tungsten etching of using in the system of iron:
Nitrogenous heterocycle, forms compound, aminoalkyl, amino acid or its combination of alkyl phosphate ion; The heterocycle of nitrogen-containing functional group, sulfide, alkyl phosphate ion; 2-ethyl-3,5-dimethyl pyrazine, 2-acetyl pyrrole, histidine and its combination; 2-mercaptobenzimidazole, cystinamine, and composition thereof; Form the compound of alkyl phosphate ion; Naturally occurring amino acid, synthetic amino acid and its mixture.
Contain silver ion, sulfate ion, oxidant, the chemical mechanical polishing liquid of inhibitor of tungsten etching has very high tungsten polishing velocity, but at whole silicon chip surface, silicon chip edge speed normally, the center of more past silicon chip, polishing velocity is slower, and the section of silicon chip (profile) figure is " ∨ " shape.On the contrary, the chemical mechanical polishing liquid that contains iron, hydrogen peroxide, the center of more past silicon chip, polishing velocity is faster, and the section of silicon chip (profile) figure is " ∧ " shape.So just caused the inhomogeneous situation of polishing velocity on silicon chip.Conventionally, wish that desirable section (profile) figure is "---" shape, like this, the polishing velocity of full wafer silicon chip is even, is conducive to improve the rate of finished products of producing.
The present invention and above-mentioned 5 pieces of United States Patent (USP)s: 5225034,5354490,5980775,6068787 and 5958288 the main distinction is: 1) they all do not adopt acrylamide; 2) they all do not have to find, can not infer: the combination of hydrogen peroxide, silver ion and sulfate radical has effect beyond expectation to improving the polishing action of tungsten, and this combination is beyond thought to improving the effect of the polishing velocity of tungsten to those skilled in the art.
The present invention and above-mentioned patent CN98809580.7, the main distinction of CN200610077360.7 is: 1) the present invention adopts double bond containing acid amides (acrylamide) as inhibitor of tungsten etching, acrylamide is amide substance, and be the acid amides that contains two keys, in structure, be different from above-mentioned two pieces of patents.2) system of the present invention is the system that hydrogen peroxide adds silver ion, and above-mentioned two pieces of patents are to contain the system that hydrogen peroxide adds iron ion, is different from above-mentioned two pieces of patents in system.
Summary of the invention
The technical problem that the present invention solves is to provide new polishing fluid, improves the chemico-mechanical polishing speed of tungsten, improves the uniformity of polishing velocity on full wafer silicon chip, realizes the section (profile) of optimizing.
Chemical mechanical polishing liquid of the present invention, comprising: water, and grinding agent, can corrode the compound of tungsten, inhibitor of tungsten etching, and base material section (profile) conditioning agent, wherein said inhibitor of tungsten etching is the acid amides that contains two keys.Preferably, described base material is silicon chip.
In the present invention, inhibitor of tungsten etching is acrylamide, and content is mass percent 0.01%～0.5%.
In the present invention, the compound that can corrode tungsten comprises one or more oxidant.This oxidant is peroxide, preferably hydrogen peroxide.Content of hydrogen peroxide is mass percent 0.1～5%, is preferably 1～2%.
In the present invention, the compound that can corrode tungsten also further comprises one or more additives, and this additive can significantly improve tungsten polishing velocity, this additive package silver ion and sulfate ion.Described silver ion comes from silver salt, preferably, comes from one or more in silver fluoride, silver perchlorate, silver sulfate and/or silver nitrate.Described silver salt percentage by weight 0.05%～0.3%.
In the present invention, sulfate ion comes from sulfate, preferred nonmetallic sulfate, nonmetal sulfate preferably sulfuric acid ammonium.
In the present invention, himself both can provide silver ion silver sulfate, also can provide sulfate ion, but single use silver sulfate exists a technical limitations to be: the mol ratio of silver ion and sulfate ion is fixed, and in fact, this ratio is to need adjustablely, for example, need the amount of sulfate radical to be greater than the amount of silver ion, these excessive sulfate radicals can be provided by other sulfate, for example ammonium sulfate, potassium sulfate.
In the present invention, base material section (profile) conditioning agent is transition metal salt.Adding of the transition metal salt of trace, can significantly improve the uniformity of polishing velocity, improves the section (profile) of base material such as silicon chip.Described base material section (profile) conditioning agent is selected from molysite conventionally.The preferred ferric nitrate of molysite.In polishing fluid, iron nitrate concentration is calculated as with ferro element: 1～15ppm.
In chemical mechanical polishing liquid of the present invention, can also further contain organic acid stabilizer.Its purposes is mainly used in stablizing silver ion, prevents or slows down silver ion variable color under intense light irradiation condition.
In chemical mechanical polishing liquid of the present invention, can also further contain pH adjusting agent.The pH value of chemical mechanical polishing liquid of the present invention is 0.5～5.
Positive progressive effect of the present invention is: the invention provides a kind of new polishing fluid, for chemico-mechanical polishing, significantly improved the polishing velocity of tungsten, reduced the static corrosion speed (static etchrate) of tungsten, improved the polishing velocity uniformity on full wafer silicon chip, section (profile) figure that has improved silicon chip, is conducive to improve the rate of finished products of producing.
Accompanying drawing explanation
The tungsten of Fig. 1 comparative example 17 and embodiment 6 is removed speed section (profile) figure.
Embodiment
Preparation Example
Table 1 has provided the formula of chemical mechanical polishing liquid embodiment 1～11 of the present invention and comparative example 1～17, by listed component and content thereof in table 1, in deionized water, mixes, and by pH adjusting agent, is transferred to required pH value, can make chemical mechanical polishing liquid.
The formula of table 1 chemical mechanical polishing liquid embodiment 1～11 of the present invention and comparative example 1～17
Effect embodiment 1
Polishing condition: polishing machine platform is Logitech (Britain) 1PM52 type, polyte * polishing pad, 4cm * 4cm square wafer (Wafer), grinding pressure 4psi, 70 revs/min of grinding table rotating speeds, 150 revs/min of grinding head rotation rotating speeds, polishing fluid rate of addition 100ml/ minute.
Table 2 is for the comparative example 1～16 of tungsten polishing
| Tungsten polishing velocity (A/min) | Tungsten static corrosion speed (A/min) | |
| Comparative example 1 | 200 | |
| Comparative example 2 | 353 | |
| Comparative example 3 | 821 | 83 |
| Comparative example 4 | 1465 | 78 |
| Comparative example 5 | 2238 | 91 |
| Comparative example 6 | 2500 | 72 |
| Comparative example 7 | 2285 | 70 |
| Comparative example 8 | 2485 | 81 |
| Comparative example 9 | 2310 | 80 |
| Comparative example 10 | 810 | 2 |
| Comparative example 11 | 1450 | 10 |
| Comparative example 12 | 2100 | 0 |
| Comparative example 13 | 2430 | 1 |
| Comparative example 14 | 2170 | 1 |
| Comparative example 15 | 2301 | 2 |
| Comparative example 16 | 2010 | 0 |
Comparative example 1 shows: while only having hydrogen peroxide to exist, the polishing velocity of tungsten is very low.
Comparative example 2 shows: hydrogen peroxide and silver nitrate combination, the polishing velocity of tungsten is very low.
Comparative example 3～9 shows: under the existence that has sulfate radical, the combination of silver ion, sulfate radical and hydrogen peroxide, can significantly improve the polishing velocity of tungsten.
Comparative example 10～16 shows: add acrylamide, can significantly suppress the static corrosion speed of tungsten, still can keep the polishing velocity of very high tungsten simultaneously.
Effect embodiment 2
Polishing condition is: 8 inches of industrial boards, 200mm wafer, pressure 3.8psi.IC1000 polishing pad.
As shown in Figure 1, the polishing fluid that comparative example 17 contains silver ion, sulfate radical, hydrogen peroxide, erosion inhibitor has very high tungsten polishing velocity, but slower in the middle of the section of silicon chip (profile), and the polishing uniformity needs to improve.Embodiment 6, under same condition, adds micro-slaine, can significantly improve the polishing uniformity of tungsten, improves section (profile), improves the yield of product.
Claims (18)
1. a chemical mechanical polishing liquid, comprise: water, grinding agent, can corrode the compound of tungsten, inhibitor of tungsten etching, and base material section conditioning agent, it is characterized in that, described base material section conditioning agent is transition metal salt, and described transition metal salt is molysite, and described inhibitor of tungsten etching is acrylamide.
2. chemical mechanical polishing liquid according to claim 1, is characterized in that, described inhibitor of tungsten etching content is mass percent 0.01%～0.5%.
3. chemical mechanical polishing liquid according to claim 1, is characterized in that, the described compound that can corrode tungsten comprises one or more oxidants.
4. chemical mechanical polishing liquid according to claim 3, is characterized in that, described oxidant is peroxide.
5. described chemical mechanical polishing liquid according to claim 4, is characterized in that, described peroxide is hydrogen peroxide.
6. described chemical mechanical polishing liquid according to claim 5, is characterized in that, described content of hydrogen peroxide is mass percent 0.1～5%.
7. chemical mechanical polishing liquid according to claim 3, is characterized in that, the described compound that can corrode tungsten further comprises one or more additives.
8. chemical mechanical polishing liquid according to claim 7, is characterized in that, described additive package silver ion and sulfate ion.
9. chemical mechanical polishing liquid according to claim 8, is characterized in that, described silver ion comes from silver salt.
10. chemical mechanical polishing liquid according to claim 9, is characterized in that, described silver ion comes from one or more in silver fluoride, silver perchlorate, silver sulfate and/or silver nitrate.
11. chemical mechanical polishing liquid according to claim 9, is characterized in that, described silver salt percentage by weight is 0.05%～0.3%.
12. chemical mechanical polishing liquids according to claim 8, is characterized in that, described sulfate ion comes from sulfate.
13. chemical mechanical polishing liquids according to claim 12, is characterized in that, described sulfate ion comes from nonmetallic sulfate.
14. chemical mechanical polishing liquids according to claim 13, is characterized in that, described nonmetal sulfate is ammonium sulfate.
15. chemical mechanical polishing liquids according to claim 1, is characterized in that, described molysite is ferric nitrate.
16. chemical mechanical polishing liquids according to claim 15, is characterized in that, described iron nitrate concentration is calculated as with ferro element: 1～15ppm.
17. chemical mechanical polishing liquids according to claim 1, is characterized in that, described chemical mechanical polishing liquid further comprises organic acid.
18. chemical mechanical polishing liquids according to claim 1, is characterized in that, the pH value of described chemical mechanical polishing liquid is 0.5～5.
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| CN201010250450.8A CN102373012B (en) | 2010-08-11 | 2010-08-11 | Chemical-mechanical polishing solution |
| PCT/CN2011/001214 WO2012019425A1 (en) | 2010-08-11 | 2011-07-25 | Chemo-mechanical polishing liquid |
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| CN102533121B (en) * | 2010-12-27 | 2016-01-27 | 安集微电子（上海）有限公司 | A kind of chemical mechanical polishing liquid of polish tungsten |
| CN103360953A (en) * | 2012-04-05 | 2013-10-23 | 安集微电子科技(上海)有限公司 | Chemico-mechanical polishing liquid |
| KR20220046561A (en) * | 2019-08-08 | 2022-04-14 | 바스프 에스이 | Composition for inhibiting tungsten etching |
| EP4010442A1 (en) * | 2019-08-09 | 2022-06-15 | Basf Se | Compositions and methods for tungsten etching inhibition |
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| CN101684391A (en) * | 2008-09-26 | 2010-03-31 | 安集微电子（上海）有限公司 | Chemical mechanical polishing solution |
| CN102344760A (en) * | 2010-08-06 | 2012-02-08 | 安集微电子（上海）有限公司 | Chemically mechanical polishing agent |
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| US6083419A (en) * | 1997-07-28 | 2000-07-04 | Cabot Corporation | Polishing composition including an inhibitor of tungsten etching |
| KR100400030B1 (en) * | 2000-06-05 | 2003-09-29 | 삼성전자주식회사 | Slurry for chemical mechanical polishing metal layer, method of preparing the same, and method of metallization for semiconductor device using the same |
| KR20080088801A (en) * | 2007-03-30 | 2008-10-06 | 바스프 에스이 | Slurry composition for polishing color filter |
| JP2009070908A (en) * | 2007-09-11 | 2009-04-02 | Mitsui Chemicals Inc | Polishing slurry |
| CN101649162A (en) * | 2008-08-15 | 2010-02-17 | 安集微电子（上海）有限公司 | Polishing solution used for chemical mechanical grounding |
| CN102051129B (en) * | 2009-11-06 | 2014-09-24 | 安集微电子（上海）有限公司 | Chemical mechanical polishing solution |
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| CN102344760A (en) * | 2010-08-06 | 2012-02-08 | 安集微电子（上海）有限公司 | Chemically mechanical polishing agent |
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