CN101525751B - Chemical mechanical polishing composition - Google Patents
Chemical mechanical polishing composition Download PDFInfo
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- CN101525751B CN101525751B CN2008100080142A CN200810008014A CN101525751B CN 101525751 B CN101525751 B CN 101525751B CN 2008100080142 A CN2008100080142 A CN 2008100080142A CN 200810008014 A CN200810008014 A CN 200810008014A CN 101525751 B CN101525751 B CN 101525751B
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- 239000000126 substance Substances 0.000 title abstract description 7
- 238000005498 polishing Methods 0.000 title abstract description 5
- 239000000203 mixture Substances 0.000 title abstract description 4
- 238000005260 corrosion Methods 0.000 claims abstract description 32
- 230000007797 corrosion Effects 0.000 claims abstract description 32
- 239000003112 inhibitor Substances 0.000 claims abstract description 32
- -1 sarcosine compound Chemical class 0.000 claims abstract description 26
- 239000000470 constituent Substances 0.000 claims description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 12
- CVSVTCORWBXHQV-UHFFFAOYSA-N anhydrous creatine Natural products NC(=[NH2+])N(C)CC([O-])=O CVSVTCORWBXHQV-UHFFFAOYSA-N 0.000 claims description 10
- 229960003624 creatine Drugs 0.000 claims description 10
- 239000006046 creatine Substances 0.000 claims description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 239000002512 suppressor factor Substances 0.000 claims description 9
- 239000003921 oil Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 6
- 159000000000 sodium salts Chemical class 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 2
- 150000002462 imidazolines Chemical class 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
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 150000003852 triazoles Chemical class 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 125000000400 lauroyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 239000001103 potassium chloride Substances 0.000 claims 1
- 235000011164 potassium chloride Nutrition 0.000 claims 1
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N N-methylaminoacetic acid Natural products C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 abstract description 24
- 108010077895 Sarcosine Proteins 0.000 abstract description 14
- 229940043230 sarcosine Drugs 0.000 abstract description 14
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 abstract description 13
- 239000012964 benzotriazole Substances 0.000 abstract description 8
- 230000007547 defect Effects 0.000 abstract 1
- 230000001681 protective effect Effects 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 31
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 28
- 229910052802 copper Inorganic materials 0.000 description 28
- 238000012545 processing Methods 0.000 description 24
- 238000000227 grinding Methods 0.000 description 23
- 229910052751 metal Inorganic materials 0.000 description 21
- 239000002184 metal Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 14
- PFNFFQXMRSDOHW-UHFFFAOYSA-N spermine Chemical compound NCCCNCCCCNCCCN PFNFFQXMRSDOHW-UHFFFAOYSA-N 0.000 description 14
- 239000010410 layer Substances 0.000 description 9
- 229960001866 silicon dioxide Drugs 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 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 description 7
- 150000003931 anilides Chemical class 0.000 description 6
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-alanine Chemical compound NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 0.000 description 6
- 230000005764 inhibitory process Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000002131 composite material Substances 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229940000635 beta-alanine Drugs 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 230000009977 dual effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 3
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- BACYUWVYYTXETD-UHFFFAOYSA-N N-Lauroylsarcosine Chemical compound CCCCCCCCCCCC(=O)N(C)CC(O)=O BACYUWVYYTXETD-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013068 control sample Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 1
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 1
- PMZBHPUNQNKBOA-UHFFFAOYSA-N 5-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=CC(C(O)=O)=CC(C(O)=O)=C1 PMZBHPUNQNKBOA-UHFFFAOYSA-N 0.000 description 1
- KUEFXPHXHHANKS-UHFFFAOYSA-N 5-nitro-1h-1,2,4-triazole Chemical compound [O-][N+](=O)C1=NC=NN1 KUEFXPHXHHANKS-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- ZNMORMCUNCEVLD-UHFFFAOYSA-N CCCCCCCCCCCC(N(C)CC(O)=O)O Chemical compound CCCCCCCCCCCC(N(C)CC(O)=O)O ZNMORMCUNCEVLD-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 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
- 241000498779 Myristica Species 0.000 description 1
- 235000009421 Myristica fragrans Nutrition 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 description 1
- 229960002885 histidine Drugs 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 125000001419 myristoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001702 nutmeg Substances 0.000 description 1
- 125000002811 oleoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229940116315 oxalic acid Drugs 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 229940071089 sarcosinate Drugs 0.000 description 1
- 108700004121 sarkosyl Proteins 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- KSAVQLQVUXSOCR-UHFFFAOYSA-M sodium lauroyl sarcosinate Chemical compound [Na+].CCCCCCCCCCCC(=O)N(C)CC([O-])=O KSAVQLQVUXSOCR-UHFFFAOYSA-M 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- ZUFONQSOSYEWCN-UHFFFAOYSA-M sodium;2-(methylamino)acetate Chemical compound [Na+].CNCC([O-])=O ZUFONQSOSYEWCN-UHFFFAOYSA-M 0.000 description 1
- 125000003696 stearoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Landscapes
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
本发明中作为腐蚀抑制剂的肌胺酸化合物为肌胺酸及其盐类化合物，该腐蚀抑制剂用于化学机械研磨组成物，可于化学机械研磨时于加工对象的表面形成一层保护膜，以避免加工对象受到腐蚀，亦可改良因使用习有腐蚀抑制剂(例如苯并三唑；BTA)，而于加工对象表面形成残渣的缺失。以下为本发明最能显示发明特征的化学式。 The sarcosine compound used as the corrosion inhibitor in the present invention is sarcosine and its salt compounds. The corrosion inhibitor is used in the chemical mechanical polishing composition to form a protective film on the surface of the processed object during chemical mechanical polishing to prevent the processed object from being corroded. It can also improve the defect of forming residues on the surface of the processed object due to the use of conventional corrosion inhibitors (such as benzotriazole; BTA). The following is the chemical formula that best shows the characteristics of the present invention.
Description
Technical field
The relevant a kind of musculamine as corrosion inhibitor of the present invention is sour or creatine compound used; Purpose is providing a kind of corrosion inhibitor that is used for the cmp constituent; Can improve the inhibition corrosive power of processing object, and can subject surface is residual not to have a residue grinding.
Background technology
The rapid increase of and the lead number of plies more and more little along with the critical size (Critical Dimension) of electronic package, resistance time lag (RC Time Delay) will have a strong impact on the operating speed of integrated circuit.In order to improve,, replace Al-alloy metal so select the low and high copper conductor material of anti-electronic migration destructiveness of resistivity along with the metal inline line width is dwindled time lag and the electronic migration integrity problem that is caused.Yet,, must change and adopt another kind (Damascene) mode of inlaying and form the copper plain conductor because the copper metal has and be difficult for etched characteristic.
Inlay (Damascene) mode processing procedure and be different from tradition elder generation definition metal pattern is filled out ditch again with dielectric layer metallization process; Its method is earlier after etching the groove of metal wire on the smooth dielectric; Again metal level is inserted; At last unnecessary metal is removed, had the flat structures of damascene in dielectric layer and obtain one.Inserted processing procedure has the following advantages compared with traditional metallization process: (1) can make substrate surface keep smooth at any time; (2) can get rid of the shortcoming that dielectric materials in the conventional process is difficult for inserting the plain conductor gap: (3) can solve the problem, the particularly etching of copper metal that the metallic substance etching is difficult for.
In addition; For contact hole structure in the processing procedure that overcomes traditional interconnect needs to make respectively with wire pattern; Make the shortcoming that whole fabrication steps is extremely complicated, develop in addition at present and a kind of dual damascene (dual damascene) processing procedure that its making processes is to carry out selective etch twice; After respectively lead dielectric substance (line dielectric) and interlayer dielectric substance (via dielectric) erosion being opened; Once finish the barrier layer of metal level and connector, and once conducting metal is inserted interlayer hole and interconnect groove, reach the effect of simplifying fabrication steps.In recent years; Be the development of matable assembly dimension shrinksization and the demand that improves assembly operation speed; Have the copper metal of low resistance constant and high electron mobility impedance, be used to material gradually, replace aluminum metal processing procedure technology in the past as the metal interconnect.The inserted interconnect technology of copper metal not only can reach the downsizing of interconnect and can reduce the RC time lag, has also solved the problem that the metallic copper etching is difficult for simultaneously, has therefore become the main development trend of multiple now interconnect.
No matter be singly to inlay or the copper wiring of dual damascene, after the filling of accomplishing the copper metal, all need carry out the planarization processing procedure, with metal removal unnecessary on the dielectric layer.At present, reach this purpose by the cmp processing procedure usually.Usually with copper-cmp processing procedure, be divided into two steps.Fs removes most copper with grinding rate faster, to increase the unit quantum of output.Subordinate phase is then removed remaining little copper with slower grinding rate mill, uses and avoids the copper in the groove is caused excessive abrasive phenomenon.Usually, the copper of two-stage grinds processing procedure, needs to change the different grinding composites of forming, and grinds demand with the copper that meets different steps.
Generally speaking; The cmp of metal level (copper) all carries out (different under alkaline condition with dielectric layer) under about about 4 the acid range of pH value; And the cmp constituent can add small amounts agent (like hydrogen peroxide) usually, to improve grinding rate.Yet; Because the copper metal corroded and very easily oxidation easily, and copper can't look like aluminium and can form the self-protection zone of oxidation, therefore after grinding under such condition; Final copper conductor usually receives the corrosive situation, thereby badly influences the quality of interconnect.
For addressing the above problem, prior art is in process of lapping, to add a corrosion inhibitor, like benzotriazole (1H-benzotriazole; BTA), to avoid copper metal or its alloy under acidic medium, to be corroded.Yet; Grinding later, this benzotriazole can have residue in processing object (chip) remained on surface; And this residue is not easy to be removed by clean-out systems such as deionized waters, makes this processing object (chip) surface formed uneven surface by residue, and influences the successive process of this processing object (chip).
Summary of the invention
Main purpose of the present invention is promptly providing a kind of corrosion inhibitor that is used for the cmp constituent, can improve the inhibition corrosive power of processing object, and can not grind the residual corrosion inhibitor that residue is arranged of subject surface.
Take off purpose on reaching; Be musculamine acid and salt compounds thereof as the creatine compound used of corrosion inhibitor among the present invention; This corrosion inhibitor is used for the cmp constituent; Can be when cmp form layer protecting film, corroded, also can improve to practise and utilize corrosion inhibitor (benzotriazole for example to avoid processing object in the surface of processing object; BTA), can form the disappearance of residue in the processing object surface.
Embodiment
Characteristics of the present invention can be consulted the detailed description of the graphic and embodiment of this case and obtained to be well understood to.
The present invention is creatine compound used as corrosion inhibitor; This corrosion inhibitor is creatine compound used or its mixtures such as musculamine acid and salt compounds thereof; And this corrosion inhibitor is used for the cmp constituent; Can when cmp, form layer protecting film in the surface in processing object, corroded, can improve the inhibition corrosive power of processing object to avoid processing object; This cmp constituent also further includes except corrosion inhibitor: abrasive particle, oxygenant, accelerator, suppressor factor and solvent.
The instance of this abrasive particle comprises, but the non-silicon-dioxide that is limited to calcination; The silicon dioxide gel that forms from water glass or potassium silicate hydrolysis or silane hydrolyzate and condensation; The aluminium dioxide of deposition or calcination; The titanium oxide of deposition or calcination; Macromolecular material; And MOX and macromolecular material mixtinite (hybrid).The preferably is a silicon dioxide gel.If the abrasive particle consumption is low excessively, be unfavorable for mechanical mill, can't reach desired grinding clearance; On the other hand, if the too high effect of then can acceleration mechanical grinding of abrasive particle consumption, increase the clearance of barrier layer and insulating oxide, also be easy to generate the grinding defective of surface abrasion.In a specific examples, this silicon sol accounts for constituent gross weight 0.01 to 30 weight %, preferable 0.1 to the 15 weight % that accounts for.
With regard to the cmp constituent that grinds the copper layer, preferable use hydrogen peroxide is as oxygenant.Usually, this oxygenant accounts for 0.25 to 5 weight % of constituent gross weight, preferable 0.5 to the 3 weight % that accounts for.
The instance that is used for the accelerator of this cmp constituent comprises, but non-Hydrocerol A, oxalic acid, tartrate, histidine, Beta Alanine or the glycine of being limited to.This accelerator is used to promote metal to be ground, for example the dissolving of copper.Improve the accelerator addition in the grinding composite, help to promote the grinding clearance of metal level, be applicable to that the metal level of fs grinds.Yet, improve the accelerator addition in the grinding composite, also can increase static etched speed simultaneously, be unfavorable for the trickle polishing of subordinate phase.In a specific examples, this accelerator accounts for 0.01 to 10 weight % of constituent gross weight, preferable 0.1 to the 5 weight % that accounts for, better 0.3 to the 3 weight % that accounts for.
The corrosion inhibitor of this cmp constituent and suppressor factor; Grind at height under the condition of clearance; Effectively suppress static etch rate, to be applicable to the grinding and polishing processing procedure of fs and subordinate phase, corrosion inhibitor of the present invention can be creatine compound used for musculamine acid and salt compounds thereof etc.; The instance of this musculamine acid and its esters comprises, but non-be limited to musculamine acid (sarcosine),
Formula one
(CH
3NHCH
2COOH，CAS＝107-97-1)
Bay vinegar musculamine acid (lauroyl sarcosine),
Formula two
(C
15H
29NO
3，CAS?97-78-9)
N-acyl sarcosine (N-acyl? Sarcosine), coconut acyl sarcosine (cocoyl? Sarcosine), oil acyl sarcosine (oleoyl? Sarcosine), stearyl acyl sarcosine (stearoyl? Sarcosine) , and nutmeg acyl sarcosine (myristoyl? sarcosine) or a lithium salt, sodium salt, potassium salt, or amine salt or a mixture thereof; acyl sarcosine such as sodium lauryl (Sodium? n-Lauroyl? Sarcosinate).
Formula three
【CH
3(CH
2)
10CON(CH
3)CH
2COONa，CAS?137-16-6】
Generally speaking, this corrosion inhibitor accounts for 0.0005 to 1% of constituent gross weight, preferable 0.001 to 0.5% of the constituent gross weight that accounts for, better 0.005 to 0.1% of the constituent gross weight that accounts for.
The instance of this suppressor factor comprises, but the non-imidazolines that is limited to; Triazole class compounds and verivate thereof, for example 1,2,4-triazole, 3-amido-1,2,4-triazole, 3-nitro-1,2,4-triazole, 3-amido-1H-1,2,4-triazole-5-carboxylic acid, 1-H-benzotriazole or 5-methyl isophthalic acid, 2,3-benzotriazole.Generally speaking, this suppressor factor accounts for 0.0001 to 1% of constituent gross weight, preferable 0.005 to 0.8% of the constituent gross weight that accounts for, better 0.01 to 0.5% of the constituent gross weight that accounts for.
Constituent of the present invention can make water as solvent, and preferable use deionized water is as the solvent of this grinding composite.
Below further specify characteristics of the present invention and effect by particular specific embodiment, but non-ly be used to limit category of the present invention.
Embodiment one
Listed according to table one; Use comprises silicon dioxide gel abrasive particle, Beta Alanine, the hydrogen peroxide, 1 of the about 90nm of median size; 2,4-triazole (suppressor factor), cocounut oil anilide musculamine acid sodium (corrosion inhibitor) and solvent are that the ground slurry constituent control sample of water is tested.Wherein, the chemical formula of this cocounut oil anilide musculamine acid sodium is suc as formula four:
Formula four
(RCON(CH
3)CH
2COONa，CAS?61791-59-1)
| ? | Oxygenant (hydrogen peroxide) (wt %) | Accelerator (Beta Alanine) (wt%) | Suppressor factor (wt%) | Abrasive particle (silicon dioxide gel) (wt %) | Corrosion inhibitor ppm |
| Reference examples 1 | 0.7 | 2.4 | 0.025 | 0.1 | 0 |
| Reference examples 2 | 0.7 | 2.4 | 0.025 | 0.1 | 50 |
| Reference examples 3 | 0.7 | 2.4 | 0 | 0.1 | 0 |
| Reference examples 4 | 0.7 | 2.4 | 0 | 0.1 | 50 |
Table one
Grinding test is to carry out according to following condition, grind clearance (Removal Rate, RR) and the MV result of etch-rate (Etch Rate) be embedded in table two.
Grinder station: Mirra polisher (Applied Materials)
Type of wafer: 8 inch cover copper film wafer (Ramco Co)
Grind overdraft: 2psig
Platform rotating speed: 90rpm
Carrier rotating speed: 85rpm
Grinding pad: IC 1010 (Rohm and Haas)
Grind slurry flow velocity: 200ml/min.
| ? | Cu?RR1.5psi | Cu?RR3psi | Etch-rate, A/min |
| Reference examples 1 | 4930 | 9790 | 915 |
| Reference examples 2 | 3257 | 7729 | 319 |
| Reference examples 3 | 7458 | ＞15425 | 3023 |
| Reference examples 4 | 1470 | ＞15425 | 578 |
Table two
Can know that according to table two result in this reference examples 1 and the reference examples 2, the copper grinding clearance of reference examples 1 and etch-rate are greater than reference examples 2; And in reference examples 3 and the reference examples 4, the copper of reference examples 3 grinding clearance and etch-rate are greater than reference examples 4, and the result can know thus; If use cocounut oil anilide musculamine acid sodium as corrosion inhibitor; Can significantly reduce copper and grind clearance and etch-rate,, can avoid processing object to be corroded effectively so this corrosion inhibitor can provide preferable inhibition corrosive power.
Embodiment two
Listed according to table three; Reference examples 5 is used silicon dioxide gel abrasive particle, hydrogen peroxide, Pottasium Hydroxide, the benzotriazole (corrosion inhibitor) that comprises the about 90nm of median size; Reference examples 6 is then used the silicon dioxide gel abrasive particle that comprises the about 90nm of median size, hydrogen peroxide, Pottasium Hydroxide, cocounut oil anilide musculamine acid sodium (corrosion inhibitor) and the solvent ground slurry constituent as water; Be that control sample is tested under 11 the environment in the pH value.
| ? | Oxygenant (hydrogen peroxide) (wt%) | Abrasive particle (silicon dioxide gel) (wt %) | BTAppm | Corrosion inhibitor ppm | KOH (wt％) | pH |
| Reference examples 5 | 0.5 | 30.0 | 50 | 0 | 0.1 | 11 |
| Reference examples 6 | 0.5 | 30.0 | 0 | 50 | 0.1 | 11 |
Table three
Grinding test carries out according to following condition, and (Removal Rate, MV result RR) is embedded in table four to grind clearance.
Grinder station: Applied Material Mirra Polisher, (San Jose, CA)
Type of wafer: 8 inch cover copper, TEOS, tantalum films wafer
Grind overdraft: 2psig
Platform rotating speed: 70rpm
Carrier rotating speed: 65rpm
Grinding pad: IC 1010 (Rohm and Haas)
Grind slurry flow velocity: 200ml/min.
| ? | Ox grinds clearance (A/min) | Cu grinds clearance (A/min) | Ta grinds clearance (A/min) |
| Reference examples 5 | 1244 | 657 | 633 |
| Reference examples 6 | 1223 | 556 | 601 |
Table four
Can know according to table four result; The copper of this reference examples 5 grinds clearance and tantalum (Ta) grinds clearance greater than reference examples 6; The result can know thus, if use cocounut oil anilide musculamine acid sodium as corrosion inhibitor, can significantly reduce the grinding clearance of copper and tantalum (Ta); So as corrosion inhibitor preferable inhibition corrosive power (compared to benzotriazole as corrosion inhibitor) can be provided with cocounut oil anilide musculamine acid sodium, can avoid processing object to be corroded effectively.
Can know that by above-mentioned each embodiment the present invention utilizes creatine compound used (like musculamine acid and salt compounds thereof) as the corrosion inhibitor in the cmp constituent, utilizes benzotriazole (1H-benzotriazole with habit; BTA) compare as corrosion inhibitor, have preferable inhibition corrosive power, can avoid processing object to be corroded, and also can be in grinding the residual situation generation that residue is arranged of subject surface.
Technology contents of the present invention and technical characterstic the sixth of the twelve Earthly Branches disclose as above, yet the personage who is familiar with this technology still possibly do various replacement and the modifications that spirit is invented in this case that do not deviate from based on announcement of the present invention.Therefore, protection scope of the present invention should be not limited to embodiment announcement person, and should comprise various do not deviate from replacement of the present invention and modifications, and is contained by following claim.
Claims (8)
1. cmp constituent comprises abrasive particle, oxygenant, accelerator, suppressor factor, solvent and creatine compound used or its salt as corrosion inhibitor, and wherein this creatine compound usedly has a following formula:
Wherein R is hydrogen, N-acyl, lauroyl, cocoyl, oleyl, stearyl group or a myristyl group;
Wherein this suppressor factor is selected from the cohort that is made up of imidazolines and triazole class compounds.
2. cmp constituent according to claim 1, wherein this salt is selected from the group that is made up of lithium salts, sodium salt, sylvite and amine salt.
3. cmp constituent according to claim 1, wherein this creatine compound used or its salt is the acid of lauryl musculamine or its sodium salt.
4. cmp constituent according to claim 1, wherein this creatine compound used or its salt is the acid of cocounut oil acyl musculamine or its sodium salt.
5. cmp constituent according to claim 1, wherein this abrasive particle is a silicon dioxide gel, and this abrasive particle accounts for 0.01 to 30% of constituent gross weight.
6. cmp constituent according to claim 1, wherein this accelerator accounts for 0.01 to 5% of constituent gross weight.
7. cmp constituent according to claim 1, wherein this suppressor factor accounts for 0.0001 to 1% of constituent gross weight.
8. cmp constituent according to claim 1, wherein this corrosion inhibitor accounts for 0.0001 to 1% of constituent gross weight.
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