CN104371551B - A kind of alkali barrier chemical mechanical polishing liquid - Google Patents
A kind of alkali barrier chemical mechanical polishing liquid Download PDFInfo
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- CN104371551B CN104371551B CN201310354652.0A CN201310354652A CN104371551B CN 104371551 B CN104371551 B CN 104371551B CN 201310354652 A CN201310354652 A CN 201310354652A CN 104371551 B CN104371551 B CN 104371551B
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- Prior art keywords
- mechanical polishing
- chemical mechanical
- polishing liquid
- organic compound
- siliceous organic
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- 238000005498 polishing Methods 0.000 title claims abstract description 65
- 239000000126 substance Substances 0.000 title claims abstract description 27
- 239000007788 liquid Substances 0.000 title claims abstract description 25
- 230000004888 barrier function Effects 0.000 title claims abstract description 13
- 239000003513 alkali Substances 0.000 title claims abstract description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910000077 silane Inorganic materials 0.000 claims abstract description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 40
- -1 amino, sulfydryl Chemical group 0.000 claims description 24
- 150000002894 organic compounds Chemical class 0.000 claims description 24
- 239000000377 silicon dioxide Substances 0.000 claims description 16
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 12
- 239000006061 abrasive grain Substances 0.000 claims description 12
- 150000002500 ions Chemical class 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 6
- 150000001721 carbon Chemical group 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- 229910001414 potassium ion Inorganic materials 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 5
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical group [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 5
- 239000002585 base Substances 0.000 claims description 5
- 239000008139 complexing agent Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N malonic acid group Chemical group C(CC(=O)O)(=O)O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 150000003536 tetrazoles Chemical class 0.000 claims description 4
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 239000008346 aqueous phase Substances 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 3
- 150000003852 triazoles Chemical group 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000004471 Glycine Substances 0.000 claims description 2
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- 150000003851 azoles Chemical class 0.000 claims 1
- 125000005605 benzo group Chemical group 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims 1
- 239000000084 colloidal system Substances 0.000 abstract description 7
- 239000012530 fluid Substances 0.000 description 17
- 229910052715 tantalum Inorganic materials 0.000 description 8
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 229910008051 Si-OH Inorganic materials 0.000 description 3
- 229910006358 Si—OH Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- BYQGDWOPYJNETQ-UHFFFAOYSA-N C=CC(OCCC[N](O)(O)O)=O Chemical compound C=CC(OCCC[N](O)(O)O)=O BYQGDWOPYJNETQ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010068052 Mosaicism Diseases 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 229910007157 Si(OH)3 Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000001891 dimethoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- DUIOPKIIICUYRZ-UHFFFAOYSA-N semicarbazide Chemical group NNC(N)=O DUIOPKIIICUYRZ-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 210000003765 sex chromosome Anatomy 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
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
Abstract
The invention provides a kind of alkali barrier chemical mechanical polishing liquid for including silane coupler, and it can realize the high power concentration of alkali barrier chemical mechanical polishing liquid and the stability of colloid.
Description
Technical field
The present invention relates to a kind of alkali barrier chemical mechanical polishing liquid containing silicon-containing organic compound.
Background technology
With the continuous development of semiconductor technology, and large scale integrated circuit interconnection layer is continuously increased, conductive layer and
The planarization of insulating medium layer becomes particularly critical.Twentieth century eighties, the chemically mechanical polishing initiated by IBM Corporation
（CMP）Technology is considered as the most efficient method of current global planarizartion.
Chemically mechanical polishing（CMP）It is combined into by chemical action, mechanism and both effects.It is generally by one
The individual grinding table with polishing pad, and a grinding head composition for being used to carry chip.Wherein grinding head fixes chip, then
The front of chip is pressed on polishing pad.When being chemically-mechanicapolish polished, grinding head linear movement or edge on polishing pad
The direction of motion rotation as grinding table.At the same time, the slurries containing abrasive grains are dripped on polishing pad, and because from
Heart effect is laid on polishing pad.Chip surface realizes global planarizartion under double action mechanically and chemically.
At present, chemical mechanical polishing liquid（CMP）Abrasive grains generally use silica used, including Ludox
（colloidal silica）And aerosil（fumed silica）.Themselves it is solid, but in aqueous
It can not settled with dispersed, it might even be possible to keep the long-time stability of 1 to 3 year.
Stability of the abrasive grains in aqueous phase（Do not settle）Can be explained with double electrode layer theory-due to each particle
Surface carries identical electric charge, and they are mutually exclusive, will not produce cohesion.
Double electrode layer theory comes from 1879, when Helmholtz research colloids move, proposes double ionic-layer theory earliest.This
For example same plate condenser of model, it is believed that the surface of solids carries certain electric charge, and medium carries another electric charge, and both are parallel,
And close proximity, 1910 and 1913, Gouy and Chapman successively made improvements, it is proposed that a diffusion electric double layer model.This
Individual model thinks, the counter ion in medium not only the electrostatic attraction by surface of solids ion, be fitly arranged near surface,
But also to be influenceed by warm-up movement, away from surface, irregularly disperse in media as well.This just forms diffusion electric double layer knot
Structure.Nineteen twenty-four, Stern further improve diffusion electric double layer model, and Stern thinks that diffusion layer should be divided into two parts：First
Part includes leafing of the absorption on surface, forms the electric double layer of an inner tight, referred to as Stern layers；Part II is
It is Gouy-Chapman diffusion layers.Ion in two layers mutually balances.Stern double ionic-layer theories can be considered by
Helmholtz models and Gouy-Chapman models combine.According to Stern models, colloid ion is being cut in motion
Zeta electric potential can be produced on dynamic face.Zeta electric potential is an important indicator of colloidal stability, because the stabilization of colloid is and grain
Electrostatic repulsion forces between son are closely related.The reduction of Zeta electric potential can reduce electrostatic repulsion forces, cause interparticle van
Der Waals attractions are dominant, so as to cause the coagulation of colloid and destruction.
The stability of colloid is also influenceed except being influenceed by zeta potentials by other many factors.For example, by temperature
Influence, at relatively high temperatures, the random warm-up movement aggravation of particle, the probability increase mutually collided, can accelerate to condense；For example, by
PH value influences, and than indifferent equilibrium under strong basicity, strong acidic condition, its neutral and alkali is most stable, and pH value 4-7 sections are least stable；
For example, being influenceed by kinds of surfactants, some surface-actives can play a part of dispersant, improve stability, and have
A little surfactants can reduce nanoparticle surface charge, reduce Coulomb repulsion, Accelerated subsidence.In surfactant, generally
Anionic surfactant is advantageous to the stability of nano particle, and cationic surface active agent is easily reduced stability；
For another example relevant with the molecular weight of additive, too long of polymer long-chain winds nano particle sometimes, increases the viscous of dispersion liquid
Degree, accelerate particle aggregation.Therefore, the stability of Ludox is influenceed by more reverse side factors.
United States Patent (USP) 60142706 and United States Patent (USP) 09609882 disclose the polishing fluid containing silane coupler and polishing
Method.The polishing method of United States Patent (USP) 60142706 is to be used under the conditions of acid and partial neutral polish, such as embodiment 1,2,3
PH value be all 2.3, the polishing for tungsten；The pH value of embodiment 4 is all 7.7, the polishing for barrier layers such as copper tantalums.This
Under the conditions of pH value, the polishing velocity of silica is all very low, as described in embodiment 4：" copper can be polished with faster speed
Position, and to polish oxide portions compared with low rate." to illustrate silica polishing velocity be the major defect of this method slowly.It is beautiful
Silica quality percentage used in state's patent 60142706 is less than 15%, because the dioxide-containing silica of high concentration can cause
System is unstable, therefore can not make highly concentrated polishing fluid, it is impossible to puts for a long time.
Silane coupler is used to improve surface roughness in United States Patent (USP) 09609882.
Chinese patent application 200880108217.7 disclose silane-containing coupling agent polishing fluid be used for polish silica and
The method of silicon nitride.
Above patent is not all found：In high ionic strength（>0.1mol/Kg）When, silica and gold can be significantly improved
Belong to the polishing velocity of tantalum.Problem is, when containing very high ionic strength（Such as containing more than>0.2mol/Kg potassium ions）,
The electric double layer of silica sol granule can significantly be compressed, and electrostatic repulsion forces reduce, and quickly form gel, heavy damage stability.
In the compound combination of the present invention, silane coupler can play a part of resisting high ionic strength, stable nanoparticles, make throwing
Light liquid is stable.It is especially noted that silane coupler is not in whole concentration ranges, but in some certain concentration range
Stabilizer can just be played a part of in section, too high silane coupled agent concentration can accelerate the sedimentation of nano particle on the contrary.More than
This problem is not all found in contrast patent.Therefore the present invention needs solve 3 problems simultaneously：1）Silica polishes and gold
The polishing velocity for belonging to tantalum is slow.2）The barrier materials such as copper, tantalum, silica can be thrown with fast speed simultaneously.3）Polishing fluid is steady
It is fixed.
The content of the invention
The technical problems to be solved by the invention are how under high ionic strength, extend alkali barrier materials chemistry machine
The stability and decentralization of abrasive grains in tool polishing fluid, while it is higher to ensure that the barrier materials such as copper, tantalum, silica have
Polishing velocity.
The present invention discloses a kind of method, using siliceous organic compound, in polyelectrolyte ionic strength, can stablize
Abrasive grains, so as to produce the product of high power concentration.
The siliceous organic compound can be represented with following formulas：
Formula：
Herein, R is unhydrolyzable substituent, usually alkyl, containing 1-50 carbon atom, using 1-20 carbon atom as
Good, wherein 2-10 carbon atom is optimal；Carbon atom on the Long carbon chain can also continue to by oxygen, nitrogen, sulphur, phosphine, halogen, silicon etc. its
His atom continues to substitute.D is the organo-functional group being connected on R, can be amino, urea groups, sulfydryl, epoxy radicals, acrylic
Deng.A, B are same or different hydrolyzable substituent or hydroxyl；C can be hydrolyzable groups or hydroxyl or not
Hydrolyzable alkyl substituent；A, B and C are typically chloro, methoxyl group, ethyoxyl, methoxy ethoxy, acetoxyl group, hydroxyl
Deng generation silanol when these groups hydrolyze（Si(OH)3）, and combined with inorganic substances, form siloxanes.D is vinyl, ammonia
Base, epoxy radicals, acryloxy, sulfydryl or urea groups.These reactive groups can react and combine with organic substance.
Representational siliceous organic compound is silane coupler, such as following structure：
APTES（Trade name KH-550）
γ-(2,3- glycidoxies) propyl trimethoxy silicane（Trade name KH-560）
γ-(methacryloxypropyl) propyl trimethoxy silicane（Trade name KH-570）
Gamma-mercaptopropyltriethoxysilane（Trade name KH-580）
γ-mercaptopropyl trimethoxysilane（Trade name KH-590）
N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane（Trade name KH-602）
γ-aminoethylaminopropyl trimethoxy silane（Trade name KH-792）
The siliceous organic compound can be added in polishing fluid by number of ways, and 1：Abrasive grains are preparing polishing fluid
First it is bonded before with silicon-containing compound（The modification of abrasive grains surface, the surface treatment being commonly called as）, then grind surface is modified
Abrasive particle is added in polishing fluid.2：The siliceous organic compound is when producing polishing fluid and abrasive grains and other components
Mix simultaneously.3：The siliceous organic compound can first complete hydrolysis or partial hydrolysis, generate Si-OH groups, then again plus
Enter in polishing fluid, Si-OH groups and abrasive grains surface Si-OH bondings completely or part bonding in polishing fluid.Therefore this hair
The siliceous organic compound of bright use there may be a variety of shapes such as free, bonding, partial hydrolysis, complete hydrolysis in polishing
State.
Based on above-mentioned discovery, it is another aspect of the invention to provide a kind of alkali barrier chemical mechanical polishing liquid, contain
Have oxidant, complexing agent, Silica abrasive particle, azole, siliceous organic compound and containing more than or equal to
The electrolyte ion of 0.1mol/Kg ionic strength, wherein siliceous organic compound is freely to be dispersed in aqueous phase, or
It is connected between abrasive grains by chemical bond.
Wherein, siliceous organic compound has following molecular structure：
Wherein, R is unhydrolyzable substituent；D is the organo-functional group being connected on R；A, B are same or different
Hydrolyzable substituent or hydroxyl；C is hydrolyzable groups or hydroxyl, or the alkyl substituent of non-hydrolysable；D be amino, sulfydryl,
Epoxy radicals, acrylic, vinyl, acryloxy or urea groups.Preferably, R is alkyl in siliceous organic compound, and institute
Stating the carbon atom on alkyl carbon chain, other atoms continue to substitute by oxygen, nitrogen, sulphur, phosphine, halogen, silicon etc.；A, B and C be respectively chloro,
Methoxyl group, ethyoxyl, methoxy ethoxy, acetoxyl group or hydroxyl.
Wherein, siliceous organic compound is silane coupler, it is preferable that siliceous organic compound is 3- aminopropyls
Triethoxysilane（Trade name KH-550）, γ-(2,3- glycidoxy) propyl trimethoxy silicane（Trade name KH-560）,
γ-(methacryloxypropyl) propyl trimethoxy silicane（Trade name KH-570）, gamma-mercaptopropyltriethoxysilane（Trade name
KH-580）, γ-mercaptopropyl trimethoxysilane（Trade name KH-590）, N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxy
Base silane（Trade name KH-602）, γ-aminoethylaminopropyl trimethoxy silane（Trade name KH-792）In one or more.
Wherein, for the consideration of economical and practical consideration, and stability, preferably γ-(2,3- glycidoxy) propyl trimethoxy
Silane（Trade name KH-560）
Wherein, the concentration of siliceous organic compound is mass percent 0.01%~1%, it is therefore preferable to 0.05%~0.5%.
Wherein, the concentration of Silica abrasive particle is more than or equal to mass percent 15%, preferably greater than or equal to quality
Percentage 20%.
Wherein, the electrolyte ion of the ionic strength more than or equal to 0.1mol/Kg is metal ion and nonmetallic ion,
Preferably potassium ion.
Wherein, the pH value of chemical mechanical polishing liquid is 9 to 12.
Wherein, azole be one kind in the derivative of triazole, tetrazole, BTA and BTA or
It is a variety of, it is preferable that azole is the derivative of tetrazole and BTA, and the derivative is not hydroxyl, amido, imido
Base, carboxyl, sulfydryl, nitro, the derivative of alkyl.
Wherein, complexing agent is containing carboxyl, phosphoric acid group, amino acid and their derivative, it is preferable that complexing agent is
Malonic acid, citric acid, glycine, 1-hydroxy ethylidene-1,1-diphosphonic acid（HEDP）.
Wherein, oxidant is hydrogen peroxide.
The positive effect of the present invention is：
1：The present invention realizes under high ionic strength, alkali barrier polishing fluid, height by silane coupler
Concentration and colloid-stabilised sex chromosome mosaicism, while the polishing velocity of polishing fluid is unaffected.
2：The costs such as product raw material, packaging, transport, storage, management, manpower can be greatly reduced by highly concentrated.
3：The present invention is by adding ion concentration>0.1mol/Kg electrolyte, significantly improve silica and metal tantalum
Polishing velocity.
Embodiment
Advantages of the present invention is expanded on further below by specific embodiment, but protection scope of the present invention is not only limited to
In following embodiments.
Polishing fluid is prepared according to the composition of each embodiment and comparative example in table 1 and its ratio, is well mixed, uses water
Mass percent is supplied to 100%.With KOH or HNO3Adjust required pH value.Wherein polishing condition is：Throw polishing machine platform
For Mirra boards, Fujibo polishing pads, 200mm Wafer, lower pressure 1.5psi, polishing fluid rate of addition 150ml/ minutes.
By comparative example 1,2,3 as can be seen that in no silane coupler, and under high ionic strength (>0.1mol/
Kg), the electric double layer of electrolyte ion compression colloid, the stability of Ludox, average grain diameter are reduced) increase sharply, then precipitate
Layering.Embodiment 1,2,3 shows, under the same conditions, adds silane coupler, the stability of Ludox significantly increases, quiet
After only putting 7 days, abrasive grains average grain diameter does not increase, and polishing fluid is still stable.From embodiment 1,2,3 as can be seen that adding
Enter silane coupler, polishing velocity is had no significant effect.
Comparative example 4 shows, in the case of without potassium ion, the speed of copper and tantalum is all very low.
Comparative example 5 shows, in potassium ion 0.05mol/Kg（Less than 0.1mol/Kg）In the case of, the speed of copper and tantalum
It is not high.
Contrasted between the three of comparative example 3,4,5, it can be found that potassium ion>During 0.1mol/Kg, silica can be significantly improved
With the polishing velocity of metal tantalum.
Embodiment 1 to 15 all shows：Silane coupler is added, the stability of Ludox can be significantly improved.It is silane coupled
The dosage of agent is not the bigger the better, and is contrasted by embodiment 14,15 and embodiment 2, excessive silane coupler can also destroy throwing
The stability of light liquid.
Using silane coupler, the barrier polishing solution that stable high power concentrates, the polishing fluid that will be matched somebody with somebody can be produced
After the water for adding 2 times of volumes, it is polished, still can obtains faster polishing velocity, meets being actually needed for production.Pass through
It is highly concentrated that the costs such as product raw material, packaging, transport, storage, management, manpower can be greatly reduced.
It should be appreciated that % of the present invention refers to weight/mass percentage composition.
The table specific embodiment of the invention and comparative example formula
Wherein, BTA is BTA, and Irgamet42 is methyl benzotriazazole derivative, and CAS is numbered：88477-
37-6。
The specific embodiment of the present invention is described in detail above, but it is intended only as example, it is of the invention and unlimited
It is formed on particular embodiments described above.To those skilled in the art, it is any to the equivalent modifications that carry out of the present invention and
Substitute also all among scope of the invention.Therefore, the impartial conversion made without departing from the spirit and scope of the invention and
Modification, all should be contained within the scope of the invention.
Claims (13)
1. a kind of alkali barrier chemical mechanical polishing liquid, it is characterised in that be more than by oxidant, complexing agent, mass percent
Or Silica abrasive particle equal to 15%, azole, siliceous organic compound and containing more than or equal to 0.1mol/
The electrolyte ion composition of Kg ionic strength, wherein, the siliceous organic compound is freely to be dispersed in aqueous phase, or
Through being connected between abrasive grains by chemical bond, the electrolyte ion of the ionic strength more than or equal to 0.1mol/Kg
It is potassium ion, complexing agent is malonic acid, citric acid, glycine, wherein,
The siliceous organic compound has following molecular structure：
Wherein, R is unhydrolyzable substituent；D is the organo-functional group being connected on R；A, B for it is same or different can water
The substituent or hydroxyl of solution；C is hydrolyzable groups or hydroxyl, or the alkyl substituent of non-hydrolysable；D is amino, sulfydryl, epoxy
Base, acrylic, vinyl, acryloxy or urea groups.
2. chemical mechanical polishing liquid as claimed in claim 1, it is characterised in that R is alkyl in the siliceous organic compound,
And the carbon atom on the alkyl carbon chain continues to substitute by one or more atoms in oxygen, nitrogen, sulphur, phosphine, silicon；A, B and C distinguish
For chloro, methoxyl group, ethyoxyl, methoxy ethoxy, acetoxyl group or hydroxyl.
3. chemical mechanical polishing liquid as claimed in claim 1, it is characterised in that the siliceous organic compound is silane coupled
Agent.
4. chemical mechanical polishing liquid as claimed in claim 3, it is characterised in that the siliceous organic compound is 3- aminopropans
Ethyl triethoxy silicane alkane, γ-(2,3- glycidoxy) propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl group front three
TMOS, gamma-mercaptopropyltriethoxysilane, γ-mercaptopropyl trimethoxysilane, N- (β-aminoethyl)-γ-aminopropyl first
Base dimethoxysilane, the one or more in γ-aminoethylaminopropyl trimethoxy silane.
5. chemical mechanical polishing liquid as claimed in claim 1, it is characterised in that the concentration of the siliceous organic compound is
Mass percent 0.01%~1%.
6. chemical mechanical polishing liquid as claimed in claim 1, it is characterised in that the concentration of the siliceous organic compound is
Mass percent 0.05%~0.5%.
7. chemical mechanical polishing liquid as claimed in claim 1, it is characterised in that the siliceous organic compound be γ-(2,
3- glycidoxies) propyl trimethoxy silicane.
8. chemical mechanical polishing liquid as claimed in claim 1, it is characterised in that the Silica abrasive granular mass percentage
Than for more than or equal to mass percent 20%.
9. chemical mechanical polishing liquid as claimed in claim 1, it is characterised in that the pH value of the chemical mechanical polishing liquid is 9
To 12.
10. chemical mechanical polishing liquid as claimed in claim 1, it is characterised in that the azole is triazole, tetrazole, benzene
And the one or more in the derivative of triazole and BTA.
11. chemical mechanical polishing liquid as claimed in claim 10, it is characterised in that the azole is tetrazole and the nitrogen of benzo three
The derivative of azoles.
12. chemical mechanical polishing liquid as claimed in claim 1, it is characterised in that the oxidant is hydrogen peroxide.
13. a kind of method of chemical mechanical polishing liquid polish stop material using as described in claim any one of 1-12.
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| EP3631045A4 (en) * | 2017-05-25 | 2021-01-27 | Fujifilm Electronic Materials U.S.A., Inc. | Chemical mechanical polishing slurry for cobalt applications |
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Effective date of registration: 20231130 Address after: 315800 No. 79, Qingshan Road, Chaiqiao street, Beilun District, Ningbo City, Zhejiang Province Patentee after: Ningbo Anji Microelectronics Technology Co.,Ltd. Address before: Room 602, Building 5, No. 3000 Longdong Avenue, Zhangjiang High tech Park, Pudong New Area, Shanghai, March 2012 Patentee before: ANJI MICROELECTRONICS (SHANGHAI) Co.,Ltd. |