CN101451046B - Polishing composition for silicon wafer polishing - Google Patents
Polishing composition for silicon wafer polishing Download PDFInfo
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- CN101451046B CN101451046B CN200810247567A CN200810247567A CN101451046B CN 101451046 B CN101451046 B CN 101451046B CN 200810247567 A CN200810247567 A CN 200810247567A CN 200810247567 A CN200810247567 A CN 200810247567A CN 101451046 B CN101451046 B CN 101451046B
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- 238000005498 polishing Methods 0.000 title claims abstract description 173
- 239000000203 mixture Substances 0.000 title claims abstract description 67
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 52
- 239000010703 silicon Substances 0.000 title claims abstract description 52
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 31
- 239000004094 surface-active agent Substances 0.000 claims abstract description 19
- 229920003086 cellulose ether Polymers 0.000 claims abstract description 16
- 239000002738 chelating agent Substances 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 9
- -1 diethyl pentetic acid Chemical compound 0.000 claims description 34
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 13
- HXMVNCMPQGPRLN-UHFFFAOYSA-N 2-hydroxyputrescine Chemical compound NCCC(O)CN HXMVNCMPQGPRLN-UHFFFAOYSA-N 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- UZBQIPPOMKBLAS-UHFFFAOYSA-N diethylazanide Chemical compound CC[N-]CC UZBQIPPOMKBLAS-UHFFFAOYSA-N 0.000 claims description 6
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 6
- 150000002191 fatty alcohols Chemical class 0.000 claims description 6
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 claims description 6
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 claims description 6
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical class NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 5
- 239000008187 granular material Substances 0.000 claims description 5
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical group OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 239000003945 anionic surfactant Substances 0.000 claims description 4
- 230000031709 bromination Effects 0.000 claims description 4
- 238000005893 bromination reaction Methods 0.000 claims description 4
- 239000003093 cationic surfactant Substances 0.000 claims description 4
- 229960001484 edetic acid Drugs 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 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
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- MXZROAOUCUVNHX-UHFFFAOYSA-N 2-Aminopropanol Chemical compound CCC(N)O MXZROAOUCUVNHX-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 229920001400 block copolymer Polymers 0.000 claims description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 3
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 2
- DMQQXDPCRUGSQB-UHFFFAOYSA-N 2-[3-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CCCN(CC(O)=O)CC(O)=O DMQQXDPCRUGSQB-UHFFFAOYSA-N 0.000 claims description 2
- OYINQIKIQCNQOX-UHFFFAOYSA-M 2-hydroxybutyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCC(O)C[N+](C)(C)C OYINQIKIQCNQOX-UHFFFAOYSA-M 0.000 claims description 2
- JKTORXLUQLQJCM-UHFFFAOYSA-N 4-phosphonobutylphosphonic acid Chemical compound OP(O)(=O)CCCCP(O)(O)=O JKTORXLUQLQJCM-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- VYVKAVOEYGTNNY-UHFFFAOYSA-N C(CCCCCCCCCCC)C1=C(C([N+](C)(C)CCCCCCCCCCCCCCCC)(C)C)C=CC=C1 Chemical compound C(CCCCCCCCCCC)C1=C(C([N+](C)(C)CCCCCCCCCCCCCCCC)(C)C)C=CC=C1 VYVKAVOEYGTNNY-UHFFFAOYSA-N 0.000 claims description 2
- 244000007835 Cyamopsis tetragonoloba Species 0.000 claims description 2
- 229940120146 EDTMP Drugs 0.000 claims description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- OCBHHZMJRVXXQK-UHFFFAOYSA-M benzyl-dimethyl-tetradecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 OCBHHZMJRVXXQK-UHFFFAOYSA-M 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 2
- VICYBMUVWHJEFT-UHFFFAOYSA-N dodecyltrimethylammonium ion Chemical compound CCCCCCCCCCCC[N+](C)(C)C VICYBMUVWHJEFT-UHFFFAOYSA-N 0.000 claims description 2
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 claims description 2
- 229940102253 isopropanolamine Drugs 0.000 claims description 2
- 229910003002 lithium salt Inorganic materials 0.000 claims description 2
- 159000000002 lithium salts Chemical class 0.000 claims description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 2
- 229960003330 pentetic acid Drugs 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 2
- 229940072033 potash Drugs 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 229920005573 silicon-containing polymer Polymers 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 claims description 2
- 229960001124 trientine Drugs 0.000 claims description 2
- 239000004711 α-olefin Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 8
- 230000007547 defect Effects 0.000 abstract description 6
- 238000007517 polishing process Methods 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000000356 contaminant Substances 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 230000003670 easy-to-clean Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 9
- 239000012530 fluid Substances 0.000 description 8
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 239000003082 abrasive agent Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 2
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- ONJQDTZCDSESIW-UHFFFAOYSA-N polidocanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO ONJQDTZCDSESIW-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 229920005682 EO-PO block copolymer Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 244000188472 Ilex paraguariensis Species 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000000138 intercalating agent Substances 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
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- 239000000376 reactant Substances 0.000 description 1
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- 229910000077 silane Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
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- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
The invention discloses a silicon wafer polishing composition in the field of chemical mechanical polishing (CMP). The polishing composition comprises silica, a polishing interface control agent, a surfactant, a chelating agent, an alkaline compound and water, wherein the particle diameter of the silica in the polishing composition is between 1 and 200 nm; the content of the silica is between 0.05 and 50 weight percent; the polishing interface control agent is polyhydroxy cellulose ether; the content of the polishing interface control agent is between 0.001 and 10 weight percent; the content of the surfactant is between 0.001 and 1 weight percent; the content of the chelating agent is between 0.001 and 1 weight percent; the content of the alkaline compound is between 0.001 and 10 weight percent; the balance being water; and the PH value is between 8.5 and 12. The polishing interface control agent can control a polishing interface between abrasive particles and a polishing object in the chemical mechanical polishing process in order that the surface of the polished silicon wafer is more perfect. The polishing composition is in particular suitable for polishing the silicon wafer and has the advantages of rapid polishing speed, little surface defect and high planeness; and the polished silicon wafer has few metal ion contaminants and is easy to clean.
Description
Technical field
The present invention relates to a kind of polishing composition that is used for silicon wafer polishing in chemico-mechanical polishing (CMP) field.
Background technology
With silicon materials is that main semiconductor materials has been the most important basic function material of electronics and information industry, in national economy and war industry, occupies very consequence.Having more than 95% in the global semiconductor device is to process with silicon materials, and wherein 85% integrated circuit also is fabricated from a silicon.At present, the IC technology has got into the nanoelectronic epoch of live width less than 0.1 μ m, and is more and more high to the suface processing quality requirement of silicon single-crystal polishing plate, and traditional polishing fluid can not satisfy silicon single crystal flake polishing requirement.In order to ensure higher machining accuracies such as silicon polished angularity, surface local evenness, surface roughnesses, must develop polishing fluid and the glossing that makes new advances.Obtaining the higher silicon wafer of Surface Machining precision is the important step of making integrated circuit, is directly connected to the qualification rate of integrated circuit.
Simple chemical polishing, polishing speed are slow, surface accuracy is higher, damage is low, good in integrity, but it can not revise surperficial surface precision, and the polishing consistency is also relatively poor; Simple mechanical polishing high conformity, surface smoothness is high, and polishing speed is higher, but the damage layer depth, surface accuracy is lower; Chemico-mechanical polishing both can obtain perfectly surface, can obtain higher polishing speed again, was the unique method that can realize overall planarization.Traditional CMP system is made up of following three parts: the silicon chip clamping device of rotation, workbench, polishing fluid (slurry) supply system of carrying polishing pad.During polishing; The workpiece of rotation imposes on the polishing pad that rotates with workbench with certain pressure; Polishing fluid flows between workpiece and polishing pad, and produces chemical reaction at surface of the work, and the chemical reactant that surface of the work forms is removed by the mechanical friction effect of abrasive material.In the alternation procedure of chemical membrane and mechanical striping, remove layer of material as thin as a wafer through the chemistry and the acting in conjunction of machinery from surface of the work, finally realize ultra-precision surface processing.Therefore, realize high efficiency, high-quality polishing, must make chemical action process and mechanism process realize good coupling.
For realize that the silicon wafer polishing liquid polishing speed is fast, few surface defects, target that evenness is high, adopted multiple mode to attempt both at home and abroad, and obtained certain progress.
People such as Trednnick disclose a kind of polishing fluid (patent US3715842) that is used for the silicon finishing polish; It is included in the silica dioxide granule that size in the water is not more than 100nm; Add the ammonia of 0.05wt% or bigger concentration, add 0.05～2.5wt% CMC (HMC), hydroxyethylcellulose (HEC) and hydroxypropyl cellulose (HPC); The people such as show that drip Lu disclose a kind of composition (patent WO2004053968) that is used for the silicon finishing polish, and it contains the cataloid of 2～10wt% particle size range, 30～80nm, the ammonia of 0.5～1.5wt%, the hydroxylated cellulose of 0.2～1wt%, the polyoxyethylene alkyl amine ether of 0.03～0.5wt%.These methods have all reduced silicon wafer surface defect, but polish removal rate is not high, only are applicable to the silicon finishing polish.
People such as hillside plot equating disclose a kind of silicon rough polishing composition (patent JP2003313838 and JP2001110760) that is used for; The polishing fluid that contains the EO-PO block copolymer is disclosed; Improved the silicon chip surface quality; But the information that provides is less, the undeclared concrete mechanism of action that adds block copolymer.
People such as Sasaki disclose a kind of silicon wafer polishing composition that contains silane coupler modified Ludox (patent EP0371147B1, JP09324174); The rapids clear rich people such as grade in river discloses a kind of silicon wafer polishing composition (patent WO2004042812) that adds chelating agent; Adopted the silica dioxide granule of ceria coating and aluminum oxide coating layer among patent US5876490 and the US3922393; Patent US4664679 has adopted the method for modifying that reduces cataloid surface silicon alcohol groups.These processing have all obtained certain effect to defect Control, but for the monocrystalline silicon buffing liquid of requirements at the higher level of new generation, also there is certain limitation in above method.
Summary of the invention
The present invention overcome the blemish that the traditional silicon wafer polishing fluid causes in polishing process easily many, remove the difficult problem that speed is high, metal residual many and be difficult for cleaning.The invention discloses that a kind of polishing speed is fast, few surface defects, high, the few and easy cleaned silicon wafer polishing composition of polishing back silicon chip contaminant metal ions of evenness.
To achieve these goals, the present invention has adopted its cellulose ether of many hydroxyls at may command polishing interface, has prevented the generation at the polishing interface of easy generation polishing defect, has improved the functioning efficiency of polishing abrasive particle.In order further to improve the performance of polishing composition in polishing process, in polishing composition, also added other material, make that abrasive material can keep good dispersity in the polishing composition, have good stability.
The said polishing composition that is used for silicon wafer polishing, its component and proportioning are:
Silica dioxide granule 0.05～50wt%
Alkali compounds 0.001～10wt%
Intercalating agent 0.001～1wt%
Surfactant 0.001%～1wt%
Polishing Interface Control agent 0.001%～10wt%
The deionized water surplus
Said silicon dioxide is cataloid, and the silica dioxide granule particle diameter is 1～500nm.
Said alkali compounds is a potassium hydroxide; NaOH; Ammonium carbonate; Carbonic hydroammonium; Saleratus; Potash; Sodium acid carbonate; Sodium carbonate; TMAH; Ammonia; Methyl amine; Dimethyl amine; Trimethylamine; Ethylamine; Diethylamide; Triethylamine; Isopropanolamine; Aminopropanol; Tetraethyl amine; Monoethanolamine; Diethyl triamine; The triethyl group tetramine; AEEA; Hexamethylene diamine; Diethylenetriamines; Trien; Piperazine anhydrous; In the anthalazine one or more.
Said chelating agent is ethylenediamine tetra-acetic acid, trimethylen-edinitrilo-tetraacetic acid, diethyl pentetic acid, triethyl group tetramine six acetate, ethylenediamine tetraacetic ethylidene phosphonic acids, ethylenediamine tetramethylene phosphonic acid, Diethylenetriamine five ethylidene phosphonic acids, Diethylenetriamine pentamethylene phosphonic acids, three second tetramines, six ethylidene phosphonic acids, propane diamine four ethylidene phosphonic acids and propane diamine tetramethylene phosphonic acid, and in their ammonium salt, sylvite, sodium salt and the lithium salts one or more.
Said surfactant is one or more in non-ionic surface active agent, anion surfactant or the cationic surfactant.
The agent of said polishing Interface Control is the polyhydroxy cellulose ether, and its structural formula is:
Wherein, n is >=2 integer.
Said non-ionic surface active agent is one or more in dimethyl silicone polymer, dimethyl polysiloxane copolyether, polyoxyethylene (9) lauryl alcohol, AEO, NPE, OPEO, polyoxyethylene polyoxypropylene block copolymer, the polyacrylamide; Anion surfactant is neopelex, dodecyl sodium sulfate, one or more in alpha-olefin sodium sulfonate, succinate sodium 2-ethylhexyl, fatty alcohol (10) polyoxyethylene, ether carboxylic acid sodium, the sodium sulfate of polyethenoxy ether of fatty alcohol; Cationic surfactant is one or more in myristyl dimethyl benzyl ammonium chloride, DTAC, guar hydroxypropyl trimonium chloride, bromination dodecyl trimethyl ammonium, the bromination dodecyl dimethyl hexadecyldimethyl benzyl ammonium.
Said polyhydroxy cellulose ether is the dihydroxypropyl cellulose ether, and R is a kind of in the following group in its structural formula:
R is
Said dihydroxypropyl cellulose ether amount is 30～3,000,000.
The said concrete steps that are used for the polishing composition preparation method of silicon wafer polishing do,
1) cataloid is scattered in it in water with blender, obtains the slurries that abrasive concentration is 0.05～50wt%;
2) add the agent of polishing Interface Control; Account for 0.001%～10wt% of polishing composition; The agent of polishing Interface Control is fully mixed with cataloid, and the mass ratio with the agent of polishing Interface Control of cataloid is 10～500 in the polishing composition;
3) add surfactant, chelating agent successively, account for the 0.001%～1wt% and the 0.001～1wt% of polishing composition respectively, keep stable to guarantee the polishing composition system;
4) add alkali compounds, account for 0.001～10wt% of polishing composition, and polishing composition pH is adjusted to 8.5～12;
5) using the aperture is that the core of gaining life experience of 0.5 μ m filters polishing composition, to remove the large granular impurity in the polishing composition, promptly obtains polishing composition of the present invention.
The present invention compared with prior art has following advantage:
1) contains polishing Interface Control agent in the polishing composition of the present invention, result from the cut of polish abrasive and the blemish of gel deposition formation in can the strong inhibition polishing composition;
2) polishing composition of the present invention has been realized the matched well of chemical action and mechanism in the CMP process, has realized high efficiency, high-quality polishing.
3) polishing composition of the present invention has also further reduced the deposition of particle in metallic pollution and the air of silicon chip surface, has improved polishing back cleaning efficiency.
4) polishing composition of the present invention is raw materials used is easy to get, and carries out large-scale industrial production easily.
Description of drawings
Back AFM (AFM) photo of silicon chip of (embodiment 14) polishing when Fig. 1 matees with other component for polishing composition of the present invention polishing controlling agent.
The AFM photo of the silicon chip when Fig. 2 polishes controlling agent for not containing in the polishing composition of the present invention after (embodiment 1) polishing.
Fig. 3 is the AFM photo of the silicon chip of polishing controlling agent in the polishing composition of the present invention after polish (embodiment 9) when relatively poor with other components do match.
Embodiment
Through embodiment and comparative example (not adding the polished surface controlling agent in the present composition) the present invention is done further elaboration below, the scope that in no case should be construed as limiting the invention certainly.
(1) preparation embodiment
Said polishing composition preparation, according to concrete polishing enforcement needs, each embodiment disposes the 6000g polishing composition and is used for polishing experiments; The cataloid of wherein being selected for use is for buy voluntarily; People chemical plant, Guangzhou product, particle diameter 40nm, dioxide-containing silica 30%:
Embodiment 1
Be that 30% cataloid is scattered in it in 5464.4g deionized water with blender with the 400g dioxide-containing silica; Add the aqueous solution 120g that contains polishing Interface Control agent dihydroxypropyl cellulose ether 2%, the agent of polishing Interface Control is fully mixed with cataloid; Add surfactant D C-193 (dimethyl polysiloxane copolyether) 2.4g, chelating agent EDTA (ethylenediamine tetra-acetic acid) 1.2g more successively; Add alkali compounds TETA (trivinyl tetramine) 12g, using the aperture at last is that the filter core of 0.5 μ m filters polishing composition, as shown in table 1.
Embodiment 2～3
The preparation process is identical with embodiment 1, and the amount of the aqueous solution of the polishing Interface Control agent dihydroxypropyl cellulose ether 2% that is added is respectively 180g and 240g, and is as shown in table 1.
Embodiment 4
The preparation process is identical with embodiment 1; Be that 30% cataloid is scattered in it in 5270.6g deionized water with blender with the 400g dioxide-containing silica; Add the aqueous solution 300g that contains polishing Interface Control agent dihydroxypropyl cellulose ether 2%, the agent of polishing Interface Control is fully mixed with cataloid; Add surfactant A EO-9 (polyoxyethylene (9) lauryl alcohol) 3.6g, chelating agent TTHP (three second tetramines, six ethylidene phosphonic acids) 1.8g more successively; Add two kinds of alkali compounds DETA (trivinyl tetramine) and PIZ (Piperazine anhydrous), be respectively 12g and 6g, using the aperture at last is that the filter core of 0.5 μ m filters polishing composition, as shown in table 1.
Embodiment 5
Be that 30% cataloid is scattered in it in 5077.8g deionized water with blender with the 600g dioxide-containing silica; Add the aqueous solution 300g that contains polishing Interface Control agent dihydroxypropyl cellulose ether 2%, the agent of polishing Interface Control is fully mixed with cataloid; Add surfactant A EO-9 (polyoxyethylene (9) lauryl alcohol) 1.2g, chelating agent EDTEP (ethylenediamine tetraacetic ethylidene phosphonic acids) 2.4g more successively; Add two kinds of alkali compounds PHA (potassium hydroxide) and DEA (diethylamide), be respectively 12g and 6g, using the aperture at last is that the filter core of 0.5 μ m filters polishing composition, as shown in table 1.
Embodiment 6～9
The preparation method is identical with embodiment 5, and is as shown in table 1.
To add abrasive particle all be 30% cataloid for the 600g dioxide-containing silica; Add polishing Interface Control agent amount all contain the aqueous solution of dihydroxypropyl cellulose ether 2% for 600g;
Wherein add surfactant D BS (neopelex) 2.4g among the embodiment 6, add chelating agent DTPA (diethylene triamine pentacetic acid (DTPA)) 1.8g, add alkali compounds AEEA (AEEA) 12g.
Add surfactant D BS (neopelex) 2.4g among the embodiment 7, add chelating agent DTPA (diethylene triamine pentacetic acid (DTPA)) 1.8g, add two kinds of alkali compounds AEEA (AEEA) and each 12g of PIZ (Piperazine anhydrous).
Add surfactant OP-10 (OPEO) 1.2g among the embodiment 8, AEO-9 (polyoxyethylene (9) lauryl alcohol) 0.6g adds chelating agent PDTEP (propane diamine four ethylidene phosphonic acids) 1.8g, adds alkali compounds AEEA (AEEA) 12g.
Add surfactant OP-10 (OPEO) 1.2g among the embodiment 9; AEO-9 (polyoxyethylene (9) lauryl alcohol) 0.6g; Add chelating agent PDTEP (propane diamine four ethylidene phosphonic acids) 1.8g, add among alkali compounds AEEA (AEEA) 12g DEA (diethylamide) 18g.
Comparative example 1～4
Except that not adding polishing Interface Control of the present invention agent, other configuration comparative example is identical with the embodiment layoutprocedure, wherein comparative example 1 and embodiment 1 in comparative example; Comparative example 2 and embodiment 4; Comparative example 3 and embodiment 5; Comparative example 4 is corresponding with embodiment 8, and is as shown in table 1.
(2) test example
Polishing composition after the configuration is used for polishing experiments, and the polishing experiments parameter is following:
Polishing machine: single side polishing machine, be furnished with 4 rubbing heads, each rubbing head can be thrown 4 silicon chips;
Polish pressure: 32kPa;
Polishing rotary speed: 90 commentaries on classics/min;
Rubbing head rotating speed: 100 commentaries on classics/min;
Polished silicon single-chip specification: P type < 100 >, diameter 100mm, resistivity: 0.1～100. Ω cm;
Polishing time: 20min;
Polishing pad: polyurethane foam solidifies polishing pad, the MH Pad S-15 of Rodel company;
Polishing fluid flow: 230ml/min;
Polish temperature: 20 ℃
Polishing speed: polish removal rate obtains through the change calculations of silicon chip core thickness before and after the polishing, is the mean value of four silicon chip center thickness differences, and its available micrometer records, and polishing speed is the ratio of polishing clearance and polishing time.
Polishing back silicon chip surface quality testing: use AFM to detect the surface roughness of polishing back silicon wafer.The AFM that experiment is adopted is Vecco 3100, and the probe radius is 10nm, and its vertical resolution is 0.01nm, and scanning frequency is 1.5Hz.Adhere to the influence of impurity for what avoid that silicon chip surface exists, before experiment, silicon chip is carried out ultrasonic cleaning respectively in acetone, absolute ethyl alcohol, deionized water experimental result.
Can find out from the polishing experiments result of table 1 embodiment and comparative example; Compare with conventional polishing composition, the polishing composition among the present invention has high polishing clearance and has improved polishing back silicon wafer surface quality simultaneously greatly owing to containing polishing Interface Control agent (DHPC).Through allotment polished surface controlling agent content in polishing composition, and adjust other component kind and content in the polishing composition simultaneously, can make its unique effect of polishing Interface Control agent performance performance.
Visible by the foregoing description; Each constituent content is in the best polishing composition under polishing technological conditions according to the invention: polishing Interface Control content is 0.1%; Contain surfactant A EO-9 0.06%, contain alkali compounds DETA0.3%, PIZ 0.1%, when containing chelating agent TTHP 0.03%; Silicon chip surface roughness after the polishing composition polishing is low to cause 0.24nm, goes speed to reach 1.35 μ m/min.
The foregoing description proves absolutely that polishing composition of the present invention is that a kind of CMP of function admirable uses polishing material, is particularly suitable for silicon wafer polishing.
Claims (10)
1. polishing composition that is used for silicon wafer polishing, its component and proportioning are:
The agent of said polishing Interface Control is the polyhydroxy cellulose ether.
2. the polishing composition that is used for silicon wafer polishing according to claim 1 is characterized in that, said silicon dioxide is cataloid, and the silica dioxide granule particle diameter is 1～500nm.
3. the polishing composition that is used for silicon wafer polishing according to claim 1; It is characterized in that said alkali compounds is one or more in potassium hydroxide, NaOH, ammonium carbonate, carbonic hydroammonium, saleratus, potash, sodium acid carbonate, sodium carbonate, TMAH, ammonia, dimethyl amine, Trimethylamine, ethylamine, diethylamide, triethylamine, aminopropanol, tetraethyl amine, monoethanolamine, diethyl triamine, triethyl group tetramine, AEEA, hexamethylene diamine, diethylenetriamines, trien, Piperazine anhydrous, the anthalazine.
4. the polishing composition that is used for silicon wafer polishing according to claim 3 is characterized in that, said aminopropanol is an isopropanolamine.
5. the polishing composition that is used for silicon wafer polishing according to claim 1; It is characterized in that; Said chelating agent is ethylenediamine tetra-acetic acid, trimethylen-edinitrilo-tetraacetic acid, diethyl pentetic acid, triethyl group tetramine six acetate, ethylenediamine tetraacetic ethylidene phosphonic acids, ethylenediamine tetramethylene phosphonic acid, Diethylenetriamine five ethylidene phosphonic acids, Diethylenetriamine pentamethylene phosphonic acids, three second tetramines, six ethylidene phosphonic acids, propane diamine four ethylidene phosphonic acids and propane diamine tetramethylene phosphonic acid, and in their ammonium salt, sylvite, sodium salt and the lithium salts one or more.
6. the polishing composition that is used for silicon wafer polishing according to claim 1 is characterized in that, said surfactant is one or more in non-ionic surface active agent, anion surfactant or the cationic surfactant.
7. the polishing composition that is used for silicon wafer polishing according to claim 1 is characterized in that, said polyhydroxy cellulose ether is the dihydroxypropyl cellulose ether, and structural formula is:
Wherein, n is >=2 integer;
R is a kind of in the following group in the structural formula:
R is
8. the polishing composition that is used for silicon wafer polishing according to claim 6, said non-ionic surface active agent are one or more in dimethyl silicone polymer, dimethyl polysiloxane copolyether, polyoxyethylene (9) lauryl alcohol, AEO, NPE, OPEO, polyoxyethylene polyoxypropylene block copolymer, the polyacrylamide; Anion surfactant is neopelex, dodecyl sodium sulfate, one or more in alpha-olefin sodium sulfonate, succinate sodium 2-ethylhexyl, fatty alcohol (10) polyoxyethylene, ether carboxylic acid sodium, the sodium sulfate of polyethenoxy ether of fatty alcohol; Cationic surfactant is one or more in myristyl dimethyl benzyl ammonium chloride, DTAC, guar hydroxypropyl trimonium chloride, bromination dodecyl trimethyl ammonium, the bromination dodecyl dimethyl hexadecyldimethyl benzyl ammonium.
9. the polishing composition that is used for silicon wafer polishing according to claim 7 is characterized in that, said dihydroxypropyl cellulose ether amount is 30～3,000,000.
10. a preparation method who is used for the polishing composition of silicon wafer polishing is characterized in that, said method concrete steps do,
1) cataloid is scattered in it in deionized water with blender, obtains the slurries that abrasive concentration is 0.05～50wt%;
2) add the agent of polishing Interface Control; Account for 0.001%～10wt% of polishing composition; The agent of polishing Interface Control is fully mixed with cataloid; And the mass ratio with the agent of polishing Interface Control of cataloid is 10～500 in the polishing composition, and the agent of said polishing Interface Control is the polyhydroxy cellulose ether;
3) add surfactant, chelating agent successively, account for the 0.001%～1wt% and the 0.001～1wt% of polishing composition respectively, keep stable to guarantee the polishing composition system;
4) add alkali compounds, account for 0.001～10wt% of polishing composition, and polishing composition pH is adjusted to 8.5～12;
5) using the aperture is that the filter core of 0.5 μ m filters polishing composition, to remove the large granular impurity in the polishing composition, promptly obtains polishing composition of the present invention.
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