WO2012032469A1 - Aqueous polishing composition and process for chemically mechanically polishing substrate materials for electrical, mechanical and optical devices - Google Patents
Aqueous polishing composition and process for chemically mechanically polishing substrate materials for electrical, mechanical and optical devices Download PDFInfo
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- WO2012032469A1 WO2012032469A1 PCT/IB2011/053896 IB2011053896W WO2012032469A1 WO 2012032469 A1 WO2012032469 A1 WO 2012032469A1 IB 2011053896 W IB2011053896 W IB 2011053896W WO 2012032469 A1 WO2012032469 A1 WO 2012032469A1
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- Prior art keywords
- acid
- group
- acids
- polishing composition
- mixtures
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- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- QAMMXRHDATVZSO-UHFFFAOYSA-N sulfurothious S-acid Chemical compound OS(O)=S QAMMXRHDATVZSO-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000011885 synergistic combination Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003892 tartrate salts Chemical class 0.000 description 1
- 229920000208 temperature-responsive polymer Polymers 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- 229960004319 trichloroacetic acid Drugs 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 1
- 229960004441 tyrosine Drugs 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
- 229960004295 valine Drugs 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- 229960002675 xylitol Drugs 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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1409—Abrasive particles per se
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/04—Aqueous dispersions
-
- 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
- C09G1/06—Other polishing compositions
- C09G1/14—Other polishing compositions based on non-waxy substances
- C09G1/18—Other polishing compositions based on non-waxy substances on other substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
- C09K3/1463—Aqueous liquid suspensions
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/31051—Planarisation of the insulating layers
- H01L21/31053—Planarisation of the insulating layers involving a dielectric removal step
Definitions
- the present invention is directed to a novel aqueous polishing composition which is particularly suitable for polishing substrate materials for electrical, mechanical and optical devices.
- the present invention is directed to a novel process for polishing substrate materials for manufacturing electrical, mechanical and optical devices.
- the present invention is directed to the novel use of the novel aqueous polishing composition for manufacturing electrical, mechanical and optical devices
- CMP Chemical mechanical planarization or polishing
- ICs integrated circuits
- the technique typically applies CMP compositions or slurries containing abrasives and other additives as an active chemistry between a rotating substrate surface and a polishing pad under an applied load.
- the CMP process couples a physical process such as abrasion with a chemical process such as oxidation or chelation. It is not desirable for the removal or polishing of substrate materials to be comprised of purely physical or purely chemical action, but rather the synergistic combination of both in order to achieve a fast uniform removal.
- a planar, defect-free surface is obtai ned wh ich enables proper multi layer I C device fabrication by subsequent photolithography, patterning, etching and thin-film processing.
- Shallow trench isolation is a specific CMP application which generally requires the selective removal of silicon dioxide to silicon nitride on a patterned wafer substrate.
- etched trenches are overfilled with a dielectric material, e.g., silicon dioxide, which is polished using the silicon nitride barrier film as the stopping layer.
- the CMP process ends with clearing the silicon dioxide from the barrier film while minimizing the removal of exposed silicon nitride and trench silicon oxide.
- Ceria-based CM P slurries have received considerable attention in STI applications because of their ability to achieve a comparatively high oxide-to-nitride selectivity due to the high chemical affinity of ceria to silicon dioxide which is also referred to in the art as the chemical tooth action of ceria. Nevertheless, the oxide-to-nitride selectivity of ceria-based CMP slurries must be improved by additives which "tailor" the selectivity.
- the American patent US 5,738,800, US 6, 042, 741 , US 6, 132,637 and US 6,218,305 B disclose a ceria-based CMP slurry containing complexing agents such as malic acid, tartaric acid, gluconic acid, citric acid, ortho di- and polyhydroxybenzoic acids, phthalic acid, pyrocathechol, pyrogallol, gallic acid, tannic acid and their salts.
- the ceria- based CMP slurry contains an anionic, cationic, amphoteric or nonionic surfactant
- the ceria-based CMP slurry is claimed to have a high oxide-to-nitride selectivity.
- the ceria-based CMP slurry contains water-soluble organic and inorganic salts such as nitrates, phosphates and sulfates.
- the ceria-based CMP slurry is claimed to polish a silicon oxide overfill in preference to a silicon nitride layer.
- the American patent US 6,299,659 B1 discloses a ceria-based CMP slurry wherein the abrasive particles have been treated with a silane, titanate, circonate, aluminum and phosphate coupling agent in order to improve the oxide-to-nitride selectivity.
- the American patent application US 2002/0034875 A1 and the American patent US 6,626,968 B2 disclose a ceria-based CMP slurry containing surfactants, pH adjusting agents such as potassium hydroxide, sulfuric acid , nitric acid , hydrochloric acid or phosphoric acid , and polymers contai ning a hyd rophil ic functional group and a hydrophobic functional group such as polyvinyl methyl ether (PVME), polyethylene glycol (PEG), polyoxyethylene 23 lauryl ether (POLE), polypropanoic acid (PPA), polyacrylic acid (PM), and polyether glycol bis ether (PEGBE).
- PVME polyvinyl methyl ether
- PEG polyethylene glycol
- POLE polyoxyethylene 23 lauryl ether
- PPA polypropanoic acid
- PM polyacrylic acid
- PEGBE polyether glycol bis ether
- the American patent US 6,436,835 B1 discloses a ceria-based CMP slurry for the shallow trench isolation process comprising water-soluble organic compounds having carboxylic acid or carboxylate or sulfonic acid or sulfamic groups such as polyacrylic acid , polymethacrylic acid, naphthalene sulfonic acid-formalin condensate, malic acid, lactic acid, tartaric acid, gluconic acid , citric acid , succinic acid , adipic acid , fumaric acid, aspartic acid , glutamic acid, glycine 4-aminobutyric acid, 6-aminohexanoic acid, 12- aminolauric acid, arginine, glycylglycine, laurylbenzene sulfonic acid and their ammonium salts.
- the ceria-based CMP slurry can have a pH of equal to or less than 4 also a pH of higher than 4 is preferred.
- the American patent US 6,616,514 B1 discloses a ceria-based CMP slurry containing organic polyols having at least 3 hydroxyl groups that are not dissociable in the aqueous medium; or a polymer formed from at least one monomer having at least 3 hydroxyl groups that are not dissociable in the aqueous medium such as mannitol, sorbitol , mannose, xylitol , sorbose, sucrose, and dextrin for im proving the oxide-to-nitride selectivity.
- the American patent application US 2006/0207188 A1 discloses a ceria-based CMP slurry containing the reaction product of a polymer such as polyacrylic acid or poly(alkyl methacrylate) and a monomer such as acrylamide, methacrylamide, ethyl- methacrylamide, vinylpyridine, or vinylpyrrolidone.
- a polymer such as polyacrylic acid or poly(alkyl methacrylate)
- a monomer such as acrylamide, methacrylamide, ethyl- methacrylamide, vinylpyridine, or vinylpyrrolidone.
- the reaction products are believed to increase also the oxide-to-nitride selectivity.
- the American patent application US 2006/0216935 A1 discloses a ceria-based CMP slurry comprising protein, lysine and/or arginine and a pyrrolidone compounds such as polyvinylpyrrolidone (PVP), N-octyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-hydroxyethyl-2- pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-butyl-2-pyrrolidone, N-hexyl-2-pyrrolidone, N- decyl-2-pyrrolidone, N-octadecyl-2-pyrrolidone, and N-hexadecyl-2-pyrrolidone.
- PVP polyvinylpyrrolidone
- N-octyl-2-pyrrolidone N-ethyl-2-pyrrolidone
- the ceria- based CMP slurry can furthermore contain dispersing agents like polyacrylic acid, glycols and polyglycols. Specific examples use proline, polyvinylpyrrolidone or N-octyl-2- pyrrolidone, PPO/PEO blockcopolymers, and glutaraldehyde.
- the ceria-based CMP slurry is believed to not aggressively remove trench silicon dioxide thereby allowing for extended polishing beyond the endpoint without substantially increasing the minimum step height.
- the American patent application US 2007/0077865 A1 discloses a ceria-based CMP slurry containing polyethyleneoxides/polypropyleneoxide copolymers preferably from the PluronicTM family is sold by BASF.
- the ceria-based CMP slurry can furthermore contain amino alcohols such as 2-dimethylamino-2-methyl-1 -propanol (DMAMP), 2-amino-2-ethyl- 1 -p ro p a n o l (A M P ) , 2-(2-aminoethylamino)ethanol, 2-(isopropylamino)ethanol, 2- (methylamino)ethanol, 2-(diethylamino)ethanol, 2-(2-dimethylamino)ethoxy)ethanol, 1 ,1 '- [[3-(dimethylamino)propyl]imino]-bis-2-propanol, 2-(2-butylamino)ethanol, 2-(tert
- the ceria-based CMP slurry may furthermore contain quaternary ammonium compounds like tetra methyla m m on i u m hyd roxi de , fi l m form i ng agents such as a l kyl a m i nes , alkanolamines, hydroxyl amines, phosphate esters, sodium lauryl sulfate, fatty acids, polyacrylates, polymethacrylates, polyvinylphosphonates, polymalates, polystyrene sulfonate, polyvinyl sulfate, benzotriazole, triazole, and benzoimidazole, and complexing agents such as acetylacetone, acetates, glycolates, lactates, gluconates, gallic acid, oxalates, phthalates, citrates, succinates, tartates, malates, ethylenediaminetetraacetic acid, ethylene glycol
- a ceria-based CMP slurry comprising a polysilicon polishing inhibitor which is selected from water-soluble polymers having a N-monosubstituted or N,N-di-substituted skeleton substituted by any members selected from the group consisting of acrylamide, methacrylamide and alpha- substituted derivatives thereof; polyethylene glycols; polyvinylpyrrolidones; alkyloxylated linear aliphatic alcohols and ethyleneoxide adducts of acetylene-based diols.
- a polysilicon polishing inhibitor which is selected from water-soluble polymers having a N-monosubstituted or N,N-di-substituted skeleton substituted by any members selected from the group consisting of acrylamide, methacrylamide and alpha- substituted derivatives thereof; polyethylene glycols; polyvinylpyrrolidones; alkyloxylated linear aliphatic alcohols and ethyleneoxide
- the ceria- based CMP slurry may contain additional water-soluble polymers such as polysaccharides like alginic acid , pectin acid , carboxymethylcellulose, agar, curdlan, and pullulan; polycarboxylic acids such as polyaspartic acid, polyglutamic acid, polylysine, polymalic acid, polymethacrylic acid, polyimide acid, polymaleic acid, polyitaconic acid, polyfumaric acid , poly(p-styrene carboxylic acid), polyacrylic acid, polyacrylamide, amino polyacrylamide, polyglyoxalic acid and their salts; and vinyl polymers such as polyvinyl alcohol, and polyacrolein.
- the ceria-based CMP slurry is said to have a high silicon oxide over polysilicon selectivity.
- the American patent application US 2007/0191244 A1 discloses a ceria-based CMP slurry containing a compound having a weight-average molecular weight of 30 to 500 and containing hydroxyl groups and a carboxyl group or both such as citrates, malates, gluconates, tartrates, 2-hydroxyisobutyrates, adipates, octanoates, succinates, EDTA- containing compounds, glutarates, methylenesuccinates, mannose, glycero-galacto- heptose, erythro-manno-octose, arabino-galacto-nonose, and glutamine.
- a compound having a weight-average molecular weight of 30 to 500 and containing hydroxyl groups and a carboxyl group or both such as citrates, malates, gluconates, tartrates, 2-hydroxyisobutyrates, adipates, octanoates, succinates
- the ceria-based CMP slurry may furthermore contain linear polymer acids or graft type polymer acids having alkoxypolyalkylene glycol side chains.
- the ceria-based CMP slurry is said to achieve an improved global planarity of the polished wafers.
- the American patent application US 2007/021881 1 A1 discloses a ceria-based CMP slurry having a pH of 4 to 7.5 and containing a dispersing agent, a polycarboxylic acid, and 100 to 1000 ppm of a strong acid having a pKa of its first dissociable acidic group at 3.2 or less.
- a dispersing agent e.g., acrylic acid and methacrylic acid
- polyoxyethylene derivatives e.g., polyvinylpyrrolidone is mentioned as a cationic dispersing agent.
- strong acids are sulfuric acid, HCI, nitric acid, phosphoric acid, oxalic acid, maleic acid, picric acid, sulfurous acid, thiosulfurous acid, amidosulfuric acid, chloric acid, perchloric acid, chlorous acid, hydroiodic acid, periodic acid, iodic acid, hydrobromic acid , perbromic acid , chromic acid , nitrous acid , diphosphonic acid, tripolyphosphoric acid, phosphinic acid, picolinic acid, phosphonic acid, isonicotinic acid, nicotinic acid, trichloroacetic acid, dichloroacetic acid, chloroacetic acid, cyanoacetic acid, oxaloacetic acid, nitroacetic acid, bromoacetic acid, fluoroacetic acid, phenoxyacetic acid, o-bromobenzoic acid, o-nitrobenzoic acid, o-chlorobenzoic acid, p
- the American patent applications US 2008/0085602 A1 and US 2008/0124913 A1 disclose a ceria-based CMP slurry containing 0.001 to 0.1 % by weight of the nonionic surfactant selected from ethyleneoxide-propyleneoxide-ethyleneoxide triblock copolymers and polyacrylic acid as dispersing agent.
- the ceria-based slurry he said to have a high silicon oxide and silicon nitride over polysilicon selectivity.
- the fabrication of electrical devices, in particular, semiconductor integrated circuits (ICs); requires high precision methods which involve inter alia high selectivity CMP.
- the prior art ceria-based CMP slurries may have a satisfactory oxide-to-nitride selectivity and may yield polished wafers having a good global and local planarity as exem pl ified by the with in-wafer nonuniformity (WIWNU) and the wafer-to-wafer nonuniformity (WTWNU), the ever decreasing dimensions of the IC architectures, in particular ICs with LSI (large-scale integration) or VLSI (very-large-scale integration), necessitate the constant improvement of the ceria-based CMP slurries in order to and meet the ever increasing technical and economical demands of the manufacturers of integrated circuit devices.
- WIWNU in-wafer nonuniformity
- WTWNU wafer-to-wafer nonuniformity
- a novel aqueous polishing composition in particular a novel chemical mechanical polishing (CMP) composition, especially a novel ceria-based CMP slurry, which no longer exhibits the disadvantages and drawbacks of the prior art polishing compositions.
- CMP chemical mechanical polishing
- the novel aqueous polishing composition in particular the novel chemical mechanical polishing (CMP) composition, especially the novel ceria-based CMP slurry, should exhibit a significantly improved oxide-to-nitride selectivity and yield polished wafers having an excellent global and local planarity as exem plified by the withi n-wafer nonuniformity (WIWNU) and the wafer-to-wafer nonuniformity (WTWNU). Therefore, they should be excellently suited for manufacturing IC architectures, in particular ICs with LSI (large-scale integration) or VLSI (very-large-scale integration), having structures with dimensions below 50 nm.
- CMP chemical mechanical polishing
- novel aqueous polishing composition in particular the novel chemical mechanical polishing (CMP) composition and especially the novel ceria-based CMP slurry should not only be exceptionally useful in the field of integrated circuit devices, but should also be most efficiently and advantageously useful in the fields of manufacturing other electrical devices such as liquid crystal panels, organic electroluminescent panels, printed circuit boards, micro machines, DNA chips, micro plants and magnetic heads; as well as high precision mechanical devices and optical devices, in particular, optical glasses such as photo-masks, lenses and prisms, inorganic electro-conductive films such as indium tin oxide (ITO), optical integrated circuits, optical switching elements, optical waveguides, optical monocrystals such as the end faces of optical fibers and scintillators, solid laser monocrystals, sapphire substrates for blue laser LEDs, semiconductor monocrystals, and glass substrates for magnetic disks.
- optical glasses such as photo-masks, lenses and prisms
- inorganic electro-conductive films such as indium tin oxide (ITO),
- esters of the hydroxycarboxylic acids (b1 ) having at least one group selected from the group consisting of lactone groups, esterified hydroxy groups, esterified carboxylic acid groups and mixtures thereof, with the proviso that at least one hydroxy group is present in (b2); and (b3) mixtures thereof; and
- composition of the invention novel aqueous polishing composition is referred to as the "composition of the invention”.
- composition of the invention for manufacturing electrical, mechanical and optical devices and the novel use of cationically modified flocculants for the stabilization of aqueous dispersions of particles have been found, which uses are hereinafter referred to as the "uses of the invention".
- the composition of the invention exhibited a significantly improved oxide-to-nitride selectivity and yield polished wafers having an excellent global and local planarity as exemplified by the within-wafer nonuniformity (WIWNU) and the wafer-to-wafer nonuniformity (WTWNU). Therefore, they were excellently suited for manufacturing IC architectures, in particular ICs with LSI (large-scale integration) or VLSI (very-large-scale integration), having structures with dimensions below 50 nm. Additionally, the composition of the invention was stable during prolonged transport and storage, which stability significantly improved the logistics and the process management.
- WIWNU within-wafer nonuniformity
- WTWNU wafer-to-wafer nonuniformity
- composition of the invention was not only exceptionally useful in the field of integrated circuit devices, but was also most efficiently and advantageously useful in the fields of manufacturing other electrical devices such as liquid crystal panels, organic electroluminescent panels, printed circuit boards, micro machines, DNA chips, micro plants and magnetic heads; as well as high precision mechanical devices and optical devices, in particular, optical glasses such as photo-masks, lenses and prisms, inorganic electro-conductive films such as indium tin oxide (ITO), optical integrated circuits, optical switching elements, optical waveguides, optical monocrystals such as the end faces of optical fibers and scintillators, solid laser monocrystals, sapphire substrates for blue laser LEDs, semiconductor monocrystals, and glass substrates for magnetic disks.
- optical glasses such as photo-masks, lenses and prisms
- inorganic electro-conductive films such as indium tin oxide (ITO)
- ITO indium tin oxide
- optical integrated circuits optical switching elements
- optical waveguides optical monocrystals
- the composition of the invention was exceptionally well-suited for the uses of the invention. Therefore, the composition of the invention was most particularly useful for the process of the invention.
- the process of invention could be most advantageously used for polishing, in particular chemically mechanically polishing, substrate materials for electrical devices such as liquid crystal panels, organic electroluminescent panels, printed circuit boards, micro machines, DNA chips, micro plants and magnetic heads; as well as substrate materials for high precision mechanical devices and optical devices, in particular, optical glasses such as photo-masks, lenses and prisms, inorganic electro-conductive films such as indium tin oxide (ITO), optical integrated circuits, optical switching elements, optical waveguides, optical monocrystals such as the end faces of optical fibers and scintillators, solid laser monocrystals, sapphire substrates for blue laser LEDs, semiconductor monocrystals, and glass substrates for magnetic disks.
- substrate materials for electrical devices such as liquid crystal panels, organic electroluminescent panels, printed circuit boards, micro machines, DNA chips, micro plants and magnetic heads
- the process of the invention was excellently suited for polishing semiconductor wafers containing silicon oxide dielectric films and silicon nitride films.
- the process of the invention yielded polished wafers having an excellent global and local planarity and balance without dishing, cupping or hotspots as exemplified by the within- wafer nonuniformity (WIWNU) and the wafer-to-wafer nonuniformity (WTWNU). Therefore, they were excellently suited for manufacturing IC architectures, in particular ICs with LSI (large-scale integration) or VLSI (very-large-scale integration), having structures with dimensions below 50 nm.
- WIWNU within- wafer nonuniformity
- WTWNU wafer-to-wafer nonuniformity
- composition of the invention is an aqueous composition. This means that it contains water, in particular ultrapure water, as the main solvent and dispersing agent. Nevertheless, the composition of the invention may contain at least one water-miscible organic solvent, however, only in such minor amounts that they do not change the aqueous nature of the composition of the invention.
- the composition of the invention contains water in amounts of from 60 to 99.95% by weight, more preferably 70 to 99.9% by weight, even more preferably 80 to 99.9% by weight and, most preferably, 90 to 99.9% by weight, the weight percentages being based on the complete weight of the composition of the invention.
- Water-soluble means that the relevant component or ingredient of the composition of the invention can be dissolved in the aqueous phase on the molecular level.
- Water-dispersible means that the relevant component or ingredient of the composition of the invention can be dispersed in the aqueous phase and forms a stable emulsion or suspension.
- Polymer or “polymeric” means that the relevant component or ingredient of the composition of the invention consists of more than 12 linked monomeric structural units which all may have the same structure. However, it is also possible that the structural units are selected from at least two different structures.
- the first essential ingredient of the composition of the invention is at least one, preferably one, type of abrasive particles (A).
- the abrasive particles (A) are positively charged when the dispersed in an aqueous medium having a pH in the range of from 3 to 9.
- the positive charge is evidenced by the electrophoretic mobility ⁇ ( ⁇ /s) (V/cm) of the abrasive particles (A).
- the electrophoretic mobility ⁇ can be directly measured with instruments such as Zetasizer Nano from Malvern, Ltd.
- the average particle size of the abrasive particles (A) can vary broadly and, therefore, can be adjusted most advantageously to the particular requirements of a given composition and process of the invention.
- the average particle size as determined by dynamic laser light scattering is in the range of from 1 to 2000 nm, preferably 1 to 1000 nm, more preferably 1 to 750, and, most preferably, 1 to 500 nm.
- the particle size distribution of the abrasive particles (A) can be monomodal, bimodal or multimodal.
- the particle size distribution is monomodal in order to have an easily reproducible property profile of the abrasive particles (A) and easily reproducible conditions during the process of the invention.
- the particle size distribution of the abrasive particles (A) can be narrow or broad.
- the particle size distribution is narrow with only small amounts of small particles and large particles in order to have an easily reproducible property profile of the abrasive particles (A) and easily reproducible conditions during the process of the invention.
- the abrasive particles (A) can have various shapes. Thus, they may be of one or essentially one type of shape. However, it also possible that the abrasive particles (A) have different shapes. In particular, two types of differently shaped abrasive particles (A) may be present i n a given composition of the invention . As regards the shapes themselves, they can be cubes, cubes with chamfered edges, octahedrons, icosahedrons, nodules and spheres with or without protrusions or indentations. Most preferably, the shape is spherical with no or only very few protrusions or indentations. This shape, as a rule, is preferred because it usually increase is the resistance to the mechanical forces the abrasive particles (A) are exposed to it during a CMP process.
- any type of abrasive particles (A) can be used in the composition of the invention as long as they possess the above described property profile.
- the abrasive particles (A) may be organic or inorganic particles or organic-inorganic hybrid particles.
- the abrasive particles (A) are inorganic particles.
- any type of inorganic abrasive particles (A) can be used in the composition of the invention as long as they possess the above described property profile.
- inorganic abrasive particles (A) containing or consisting of ceria are used.
- the abrasive particles (A) which contain ceria can contain minor amounts of other rare earth metal oxides.
- the abrasive particles (A) which contain ceria are composite particles (A) comprising a core containing or consisting of at least one other abrasive particulate material which is different from ceria, in particular alumina, silica titania, zirconia, zinc oxide, and mixtures thereof.
- Such composite particles (A) are known, for example, from WO 2005/035688 A1 , US 6,1 10,396, US 6,238,469 B1 , US 6,645,265 B1 , K. S. Choi et al., Mat. Res. Soc. Symp. Proc. Vol. 671 , 2001 Materials Research Society, M5.8.1 to M5.8.10, S.-H. Lee et al., J. Mater. Res., Vol. 17, No. 10, (2002), pages 2744 to 2749, A. Jindal et al., Journal of the Electrochemical Society, 1 50 (5) G314-G31 8 (2003) , Z. Lu , J ournal of Materials Research, Vol. 18, No. 10, October 2003, Materials Research Society, or S. Hedge et al., Electrochemical and Solid-State Letters, 7 (12) G316-G318 (2004).
- the com posite particles (A) are raspberry-type coated particles comprising a core selected from the group consisting of alumina, silica titania, zirconia, zinc oxide, and mixtures thereof with a core size of from 20 to 100 nm wherein the core is coated with ceria particles having a particle size below 10 nm.
- the amount of the abrasive particles (A) used in the composition of the invention can vary broadly and, therefore, can be adj usted most advantageously to the particular requirements of a given composition and process of the invention.
- the composition of the invention contains 0.005 to 10% by weight, more preferably 0.01 to 8% by weight and, most preferably 0.01 to 6% by weight of the abrasive particles (A), the weight percentages being based on the complete weight of the composition of the invention.
- composition of the invention contains at least one, preferably one, water-soluble or water dispersible, preferably, water-soluble, hydroxy group containing component (B) as the second essential ingredient.
- the component (B) is selected from the group consisting of (b1 ) aliphatic and cycloaliphatic hydroxycarboxylic acids having at least two, preferably at least three, more preferably at least four, even more preferably at least five and most preferably at least six carbon atoms, at least one, preferably at least two, more preferably at least three and, most preferably, at least four hydroxy group and
- the molar ratio of hydroxy groups to carboxylic acid groups is at least 1 , preferably at least 2, more preferably at least 3 and, most preferably, at least 4;
- esters of the hydroxycarboxylic acids (b1 ) having at least one group selected from the group consisting of lactone groups, esterified hydroxy groups, esterified carboxylic acid groups and mixtures thereof, with the proviso that at least one, hydroxy group, preferably at least two and, most preferably, at least three hydroxy groups is or are present in (b2); and
- the hydroxycarboxylic acids (b1 ) are selected from the group consisting of glycolic acid, lactic acid, quinic acid, sugar acids and mixtures thereof.
- the esters (b2) are selected from the group consisting of glycolic acid, lactic acid, quinic acid and sugar acid esters and lactones and mixtures thereof.
- the sugar acids (b1 ) are selected from the group consisting of aldonic acids, uronic acids, glycuronic acids, aldaric acids, ulusonic acids, neuraminic acids, sialic acids and mixtures thereof. More preferably, the sugar acid esters (b2) are selected from the group consisting of aldonic acid, uronic acid, glycuronic acid, aldaric acid, ulusonic acids, neuraminic acid, sialic acid esters and lactones and mixtures thereof.
- the sugar acids (b1 ) are selected from the group consisting of glyceric acid, tartaric acid, threonic acid, erythronic acid, xylonic acid, glucuronic acid, ascorbic acid, gluconic acid, galacturonic acid, iduronic acid, mannuronic acid, glucuronic acid, guluronic acid, glycuronic acid, glucaric acid, ulusonic acid, neuramic acids, sialic acids, muramic acid, lactobionic acid and mixtures thereof.
- the sugar acid esters (b2) are selected from the group consisting of glyceric acid, tartaric acid, threonic acid, erythronic acid, xylonic acid, glucuronic acid, ascorbic acid, gluconic acid, galacturonic acid, iduronic acid, mannuronic acid, glucuronic acid, guluronic acid, glycuronic acid, glucaric acid, ulusonic acid, neuramic acid, sialic acid , muramic acid and lactobionic acid esters and lactones, glucono-delta-lactone, pangamic acid and mixtures thereof.
- the component (B) is selected from the group consisting of quinic acid, glucuronic acid, lactobionic acid, glucono-delta-lactone and mixtures thereof.
- the concentration of the component (B) in the composition of the invention can vary broad ly and , therefore, can be most advantageously adapted to the particular requirements of a given composition and process of the invention.
- the composition of the invention contains the component (B) in amounts of from to 0.005 is to 5% by weight, more preferably 0.01 to 4% by weight, and most preferably 0.01 to 3% by weight, the weight percentages being based on the complete weight of the composition of the invention.
- the composition of the invention contains at least one, preferably two, water-soluble or water-dispersible, preferably water-soluble, is selected from the group consisting of polymer component(s) (C).
- the component (C) is selected from the group consisting of
- the alkylene oxide homopolymer or copolymer (b1 ) is selected from the group consisting of linear and branched ethyleneoxide and propyleneoxide homopolymers and copolymers.
- the ethyleneoxide-propyleneoxide copolymers (b1 ) can be random copolymers, alternating copolymers or blockcopolymers containing polyethyleneoxide blocks and polypropyleneoxide blocks.
- the polyethyleneoxide blocks preferably have hydrophile-lipophile-balance (HLB) values from 10 to 15.
- HLB hydrophile-lipophile-balance
- the polypropyleneoxide blocks may preferably have a HLB values of from 28 to about 32.
- the alkylene oxide homopolymers (b1 ) are ethyleneoxide polymers, such as polyethylene glycol (PEG).
- PEG polyethylene glycol
- the water-soluble polymers (b1 ) have a weight average molecular weight of from 2000 to 1 ,000,000 Dalton, more preferably 5000 to 500,000 Dalton and , most preferably, 10,000 to 250,000 Dalton.
- the water-soluble polymers (b1 ) are customary and known, commercially available materials. Suitable water-soluble polymers (b1 ) are described in the Japanese patent application J P 2001 -240850 A, claim 2 in conjunction with the paragraphs [0007] to [0014], the American patent application US 2007/0077865 A1 , column page 1 , paragraph [0008] to page 2, paragraph [0010], the American patent application US 2006/0124594 A1 , page 3, paragraphs [0036] and [0037] and the American patent application US 2008/0124913 A1 , page 3, paragraphs [0031] to [0033] in conjunction with the claim 14 or they are sold under the trademarks PluronicTM, TetronicTM and BasensolTM by BASF Corporation and BASF SE as evidenced by the company brochure of BASF Corporation "PluronicTM & TetronicTM Block Copolymer Surfactants, 1996" or the American patent US 2006/0213780 A1 .
- polyethylene glycol PEG
- PEG polyethylene glycol
- the aliphatic and cycloaliphatic N-vinylamide monomers which are the building blocks of the linear and branched , aliphatic and cycloaliphatic poly(N-vinylamide) homopolymers and copolymers (c2), are selected from the group consisting of N- vinylacetamide, N-vinylpyrrolidone, N-vinylvalerolactam, N-vinylcaprolactam, N- vinylsuccinimide and mixtures thereof.
- the poly(N-vinylamide) copolymers (c2) may contain monomeric units derived from customary and known olefinically unsaturated monomers other than the N-vinylamides, as for example, vinyl esters and ethers, acrylic and methacrylic esters, allylic esters and ethers, olefins which may be substituted by halogen atoms or nitrile groups, and styrenic monomers, provided that such monomeric units are only contained in such amounts that the water-solubility is not jeopardized.
- customary and known olefinically unsaturated monomers other than the N-vinylamides, as for example, vinyl esters and ethers, acrylic and methacrylic esters, allylic esters and ethers, olefins which may be substituted by halogen atoms or nitrile groups, and styrenic monomers, provided that such monomeric units are only contained in such amounts that the water
- the water-soluble polymers (c2) have a weight average molecular weight of from 2000 to 1 ,000,000 Dalton, more preferably 5000 to 500,000 Dalton and, most preferably, 10,000 to 250,000 Dalton.
- the cationic polymeric flocculant (c3) is selected from the group consisting of cationically modified polyacrylamides, polyamines, polyethyleneimines, poly(diallyl-N,N- dialkylammonium halide) and mixtures thereof.
- the cationic groups are selected from the group consisting of quaternary ammonium groups, sulfonium groups, phosphonium groups and mixtures thereof. Most preferably, quaternary ammonium groups are used.
- the alkyl group of the poly(diallyl-N,N-dialkylammonium halide) (c3) is selected from the group consisting of methyl, ethyl, propyl and isopropyl and mixtures thereof. Most preferably, methyl groups are used. More preferably, the halide is selected from the group consisting of fluoride, chloride and bromide. Most preferably, chloride is used. Most preferably, poly(diallyl-N,N-dimethylammonium chloride) (poly-DADMAC) is used.
- the concentration of the cationically modified flocculant (c3) in the composition of the invention can vary broadly and, therefore, can be adapted most advantageously to the particular requirements of a given composition and process of the invention.
- the flocculant (c3) is used in amounts of from 0.0001 to 1 % by weight, preferably 0.0002 to 1 % by weight, and most preferably 0.0003 to 1 % by weight, the weight percentages being based on the complete weight of the composition of the invention.
- the cationically modified flocculants (c3) are customary and known materials which are commercially available, for example, from BASF SE under the trademark SedipurTM C. It was most surprising that, according to one of the uses of the invention, the cationically modified flocculants (c3) can be used to stabilize the aqueous dispersions of the abrasive particles (A).
- composition of the invention can contain at least one functional component (D) which is materially different from the ingredients (A), (B) and (C).
- the functional component (D) is selected from the group of compounds customarily used in ceria-based CMP slurries.
- Examples of such compounds (D) are disclosed in, for example, by Y. N. Prasad et al. in Electrochemical and Solid-State Letters, 9 (12) G337-G339 (2006), Hyun-Goo Kang et al. in Journal of Material Research, volume 22, No. 3, 2007, pages 777 to 787, S. Kim et al. in Journal of Colloid and Interface Science, 319 (2008), pages 48 to 52, S. V. Babu et al. in Electrochemical and Solid-State Letters, 7 (12) G327-G330 (2004), Jae-Dong Lee et al.
- the functional component (D) is selected from the group consisting of organic, inorganic and hybrid organic-inorganic abrasive particles being different from the particles (D), polyhydric alcohols with at least two hydroxy groups, materials having a lower critical solution temperature LCST or an upper critical solution temperature UCST, oxidizing agents, passivating agents, charge reversal agents, complexing or chelating agents, frictive agents, stabilizing agents, rheology agents, surfactants, metal cations and organic solvents.
- Suitable organic abrasive particles (D) and their effective amounts are known, for example, from the American patent application US 2008/0254628 A1 , page 4, paragraph [0054] or from the international application WO 2005/014753 A1 , wherein solid particles consisting of melamine and melamine derivatives such as acetoguanamine, benzoguanamine and dicyandiamide are disclosed.
- Suitable inorganic abrasive particles (D) and their effective amounts are known, for example, from the international patent application WO 2005/014753 A1 , page 12, lines 1 to 8 or the American patent US 6,068,787, column 6, line 41 to column 7, line 65.
- Suitable hybrid organic-inorganic abrasive particles (D) and their effective amounts are known, for example, from the American patent applications US 2008/0254628 A1 , page 4, paragraph [0054] or US 2009/001 3609 A1 , page 3, paragraph [0047] to page 6, paragraph [0087].
- Suitable polyhydric alcohols (D) are diols such as ethylene glycol and propylene glycol, triols such as glycerol, pentaerythritol, alditols, cyclitols and dimers and oligomers of glycerol, trimethylolpropane, pentaerythritol, alditols and cyclitols.
- Suitable oxidizing agents (D) and their effective amounts are known, for example, from the European patent application EP 1 036 836 A1 , page 8, paragraphs [0074] and [0075] or from the American patents US 6,068,787, column 4, line 40 to column 7, line 45 or US 7,300,601 B2, column 4, lines 18 to 34.
- organic and inorganic peroxides are used.
- hydrogen peroxide is used.
- Suitable passivating agents (D) and their effective amounts are known, for example, from the American patent US 7,300,601 B2, column 3, line 59 to column 4, line 9 or from the American patent application US 2008/0254628 A1 , the paragraph [0058] bridging the pages 4 and 5.
- amino acids in particular glycine, and, moreover, dicyandiamide and triazines containing at least one, preferably two and, more preferably, three primary amino groups such as melam ine and water-soluble guanamines, particularly melamine, formoguanamine, acetoguanamine and 2,4-diamino-6-ethyl-1 ,3,5-triazine, are most particularly preferably used.
- Suitable stabilizing agents (D) and their effective amounts are known, for example, from the American patent US 6,068,787, column 8, lines 4 to 56.
- Suitable rheology agents (D) and their effective amounts are known, for example, from the American patent application US 2008/0254628 A1 , page 5, paragraph [0065] to page 6, paragraph [0069].
- Suitable surfactants (D) and their effective amounts are known, for example, from the international patent application WO 2005/014753 A1 , page 8, line 23, to page 10, line 17 or from the American patent US 7,300,601 B2, column 5, line 4 to column 6, line 8.
- Suitable polyvalent metal ions (D) and their effective amounts are known, for example, from the European patent application EP 1 036 836 A1 , page 8, paragraph [0076] to page 9, paragraph [0078].
- Suitable organic solvents (D) and their effective amounts are known, for example, from the American patent US 7,361 ,603 B2, column 7, lines 32 to 48 or the American patent application US 2008/0254628 A1 , page 5, paragraph [0059].
- Suitable materials (D) exhibiting a lower critical solution temperature LCST or an upper critical solution temperature UCST are described, for example, in the article of H. Mori, H. Iwaya, A. Nagai and T. Endo, Controlled synthesis of thermoresponsive polymers derived from L-proline via RAFT polymerization, in Chemical Communication, 2005, 4872-4874; or in the article of D.
- any known charge reversal agent (D) customarily used in the field of CMP can be used.
- the charge reversal agent (D) is selected from the group consisting of monomeric, oligomeric and polymeric compounds containing at least one anionic group selected from the group consisting of carboxylate, sulfonate, sulfate and phosphonate groups.
- the functional component (D) can be contained in varying amounts.
- the total amount of (D) is not more than 10 wt.% ("wt.%" means "percent by weight"), more preferably not more than 2 wt.%, most preferably not more than 0.5 wt.%, particularly not more than 0.1 wt.%, for example not more than 0.01 wt.%, based on the total weight of the corresponding CMP composition.
- the total amount of (D) is at least 0.0001 wt. % , more preferably at least 0.001 wt. % , most preferably at least 0.008 wt. % , particularly at least 0.05 wt.%, for example at least 0.3 wt.%, based on the total weight of the corresponding composition.
- the composition of the invention can optionally contain at least one pH-adjusting agent or buffering agent (E) which is materially different from the ingredients (A), (B) and (C).
- pH-adjusting agents or buffering agents (E) and their effective amounts are known, for example, from the European patent application EP 1 036 836 A1 , page 8, paragraphs [0080] , [0085] and [0086] , the international patent application WO 2005/014753 A1 , page 12, lines 19 to 24, the American patent application US 2008/0254628 A1 , page 6, paragraph [0073] or the American patent US 7,300,601 B2, column 5, lines 33 to 63.
- pH-adjusting agents or buffering agents (E) are potassium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide (TMAH), nitric acid, and sulfuric acid.
- the pH-adjusting agent or buffering agent (E) can be contained in varying amounts.
- the total amount of (E) is not more than 20 wt.%, more preferably not more than 7 wt.%, most preferably not more than 2 wt.%, particularly not more than 0.5 wt.%, for example not more than 0.1 wt.%, based on the total weight of the corresponding CMP composition.
- the total amount of (E) is at least 0.001 wt.%, more preferably at least 0.01 wt.%, most preferably at least 0.05 wt.%, particularly at least 0.1 wt.%, for example at least 0.5 wt.%, based on the total weight of the corresponding composition.
- the pH of the composition of the invention is set between 2.5 and 4, preferably using the aforementioned pH-adjusting agents (E).
- the preparation of the composition of the invention does not exhibit any particularities but can be carried out by dissolving or dispersing the above-described ingredients (A), (B) and (C) and optionally (D) and/or (E) in an aqueous medium, in particular, de-ionized water.
- an aqueous medium in particular, de-ionized water.
- the customary and standard mixing processes and mixing apparatuses such as agitated vessels, in-line dissolvers, high shear impellers, ultrasonic mixers, homogenizer nozzles or counterflow mixers, can be used .
- the composition of the invention thus obtained can be filtered through filters of the appropriate mesh aperture, in order to remove coarse-grained particles such as the agglomerates or aggregates of the solid, finely dispersed abrasive particles (A).
- compositions of the invention are excellently suited for the process of the invention.
- a substrate material for electrical, mechanical and optical devices in particular, electrical devices, most preferably, integrated circuit devices, is contacted at least once with a composition of the invention and polished, in particular, chemically and mechanically polished, until the desired planarity is achieved.
- the process on the invention exhibits its particular advantages in the CMP of silicon semiconductor wafers having isolating layers consisting of low-k or ultra-low-k silicon oxide materials and silicon nitride layers as stopping or barrier layers.
- Suitable low-k or ultra-low-k materials and suitable methods of preparing the insulating dielectric layers are described in, for example, the American patent applications US 2005/0176259 A1 , page 2, paragraphs [0025] to [0027], US 2005/0014667 A1 , page 1 , paragraph [0003], US 2005/0266683 A1 , page 1 , paragraph [0003] and page 2, paragraph [0024] or US 2008/0280452 A1 , paragraphs [0024] to [0026] or in the American patent US 7,250,391 B2, column 1 , lines 49 to 54 or in the European patent application EP 1 306 415 A2, page 4, paragraph [0031 ].
- the process of the invention is particularly suited for the shallow trench isolation (STI) which requires the selective removal of silicon dioxide over silicon nitride on a patterned wafer substrate.
- etched trenches are overfilled with the dielectric material, e.g., silicon dioxide, which is polished using the silicon nitride barrier film as the stopping layer.
- the process of the invention ends with clearing the silicon dioxide from the barrier film while minimizing the removal of exposed silicon nitride and trench silicon oxide.
- the process of the invention exhibits an oxide-to-nitride selectivity greater than 50, preferably greater than 75 and most preferably greater than 100.
- the process of the invention exhibits no particularities but can be carried out with the processes and the equipment customarily used for the CMP in the fabrication of semiconductor wafers with ICs.
- a typical equipment for the CMP consists of a rotating platen which is covered with a polishing pad.
- the wafer is mounted on a carrier or chuck with its upper side down facing the polishing pad .
- the carrier secures the wafer in the horizontal position.
- This particular arrangement of polishing and holding device is also known as the hard-platen design.
- the carrier may retain a carrier pad which lies between the retaining surface of the carrier and the surface of the wafer which is not being polished. This pad can operate as a cushion for the wafer.
- the larger diameter platen is also generally horizontally positioned and presents a surface parallel to that of the wafer to be polished. Its polishing pad contacts the wafer surface during the planarization process.
- the composition of the invention is applied onto the polishing pad as a continuous stream or in dropwise fashion.
- Both the carrier and the platen are caused to rotate around their respective shafts extending perpendicular from the carrier and the platen.
- the rotating carrier shaft may remain fixed in position relative to the rotating platen or may oscillate horizontally relative to the platen.
- the direction of rotation of the carrier typically, though not necessarily, is the same as that of the platen.
- the speeds of rotation for the carrier and the platen are generally, though not necessarily, set at different values.
- the temperature of the platen is set at temperatures between 10 and 70°C.
- compositions of the comparative aqueous polishing compositions C1 to C5 are compiled in the Table 1 .
- Polishing apparatus AMAT Mirra (rotary type):
- substrates 2000 nm thermal silicon dioxide coated blanket wafers from SKW and 500 nm silicon nitride coated blanket wafers from Montco Silicon; examples 20 to 22: TEOS silicon dioxide coated blanket wafers;
- polishing time 1 minute.
- the material removal rates MRRs were measured with a reflectometer. The results obtained are compiled in the Table 2.
- compositions of the aqueous polishing compositions of the examples 1 to 4 and of the comparative aqueous polishing compositions C6 and C7 are compiled in the Table 3.
- Table 3 The Compositions of the Aqueous Polishing Compositions 1 to 4 and of the
- polyethylene glycol PEG- ⁇ having an average molecular weight of 10,000 Dalton
- polyvinylpyrrolidone PVPI 7 K having an average molecular weight of 17,000 Dalton
- Polishing apparatus in the the examples 1 and 2 and the comparative experiment C6 AMAT Mirra (rotary type);
- substrates 2000 nm thermal silicon dioxide coated blanket wafers from SKW and 500 nm silicon nitride coated blanket wafers from Montco Silicon;
- the material removal rates (MRRs) were measured by Therma Wave Optiprobe 2600 and before and after CMP.
- the initial topography or step height in silicon oxide-silicon nitride-field oxide patterned wafers STI 3-2 from SKW were polished using a commercially available CMP Slurry (Cabot SS25, 1 :1 dilution), in order to "knock out” the topography.
- the applied down force was 5 psi (341 .66 mbar).
- the aim of this P1 process was to achieve near planarization with a few amounts of oxide thickness left atop the silicon nitride stopping layer.
- the patterned wafer measurements were done on two sites, namely (i) at the active oxide site to measure the remaining oxide left and (ii) at the field oxide site to measure the trench oxide.
- the blanket wafers were polished under the above-mentioned conditions.
- the material removal rates MRRs obtained were used to calculate the time to remove the active oxide left atop the silicon nitride stopping layer after the P1 process. This time was referred to as “endpoint (EP)” and any additional polishing time after the endpoint was referred to as “overpolishing (OP)”.
- a cationically modified flocculant (SedipurTM CL 520 from BASF SE) was added in various amounts to an aqueous polishing composition having a pH of 3 and containing 0.5% by weight ceria and 0.025% by weight of glucuronic acid.
- the average particle sizes were measured with a Horiba Instrument particle size analyzer. The obtained results are compiled in the Table 5.
- An aqueous polishing composition having a pH of 3 and containing 0.5% by weight ceria and 0.025% by weight of glucuronic acid was used for the comparative experiment C8.
- An aqueous polishing composition having a pH of 3 and containing 0.5% by weight ceria, 0.025% by weight of glucuronic acid and 70 ppm SedipurTM CL 520 was used for the example 6.
- Silicon dioxide coated blanket wafers and silicon nitride coated blanket wafers were polished as described hereinbefore in the comparative experiments C1 to C5.
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Abstract
Description
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KR1020137009004A KR101907863B1 (en) | 2010-09-08 | 2011-09-06 | Aqueous polishing composition and process for chemically mechanically polishing substrate materials for electrical, mechanical and optical devices |
US13/821,757 US20130161285A1 (en) | 2010-09-08 | 2011-09-06 | Aqueous polishing composition and process for chemically mechanically polishing substrate materials for electrical, mechanical and optical devices |
JP2013527720A JP6196155B2 (en) | 2010-09-08 | 2011-09-06 | Aqueous abrasive composition and method for polishing substrate materials for electrical, mechanical and optical devices |
EP11823142.2A EP2614123B1 (en) | 2010-09-08 | 2011-09-06 | Aqueous polishing composition and process for chemically mechanically polishing substrate materials for electrical, mechanical and optical devices |
RU2013115235/05A RU2577281C2 (en) | 2010-09-08 | 2011-09-06 | Water polishing composition and method of chemical-mechanical polishing of substrate materials for electric, mechanical and optical devices |
CN201180053056.8A CN103189457B (en) | 2010-09-08 | 2011-09-06 | For moisture polishing composition and the method for chemically machinery polished electronics, machinery and optics base material |
SG2013017264A SG188460A1 (en) | 2010-09-08 | 2011-09-06 | Aqueous polishing composition and process for chemically mechanically polishing substrate materials for electrical, mechanical and optical devices |
IL225085A IL225085A (en) | 2010-09-08 | 2013-03-07 | Aqueous polishing composition and process for chemically mechanically polishing substrate materials for electrical, mechanical and optical devices |
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Also Published As
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US20130161285A1 (en) | 2013-06-27 |
KR20130133177A (en) | 2013-12-06 |
TW201211223A (en) | 2012-03-16 |
EP2614123A4 (en) | 2014-07-30 |
RU2013115235A (en) | 2014-10-20 |
SG188460A1 (en) | 2013-04-30 |
TWI538989B (en) | 2016-06-21 |
MY164859A (en) | 2018-01-30 |
CN103189457A (en) | 2013-07-03 |
IL225085A (en) | 2017-09-28 |
SG10201506220PA (en) | 2015-09-29 |
KR101907863B1 (en) | 2018-10-15 |
JP2013540851A (en) | 2013-11-07 |
CN103189457B (en) | 2015-12-09 |
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