WO2014047014A1 - Incorporating additives into fixed abrasive webs for improved cmp performance - Google Patents
Incorporating additives into fixed abrasive webs for improved cmp performance Download PDFInfo
- Publication number
- WO2014047014A1 WO2014047014A1 PCT/US2013/060022 US2013060022W WO2014047014A1 WO 2014047014 A1 WO2014047014 A1 WO 2014047014A1 US 2013060022 W US2013060022 W US 2013060022W WO 2014047014 A1 WO2014047014 A1 WO 2014047014A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- structured abrasive
- abrasive
- nonionic surfactant
- abrasive article
- additive
- Prior art date
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- RGBXDEHYFWDBKD-UHFFFAOYSA-N propan-2-yl propan-2-yloxy carbonate Chemical compound CC(C)OOC(=O)OC(C)C RGBXDEHYFWDBKD-UHFFFAOYSA-N 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000008279 sol Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 229950006451 sorbitan laurate Drugs 0.000 description 1
- 235000011067 sorbitan monolaureate Nutrition 0.000 description 1
- 229950004959 sorbitan oleate Drugs 0.000 description 1
- 229950011392 sorbitan stearate Drugs 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 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 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical class [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
- B24B37/11—Lapping tools
- B24B37/20—Lapping pads for working plane surfaces
- B24B37/24—Lapping pads for working plane surfaces characterised by the composition or properties of the pad materials
- B24B37/245—Pads with fixed abrasives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
- B24D3/00—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents
- B24D3/34—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents characterised by additives enhancing special physical properties, e.g. wear resistance, electric conductivity, self-cleaning properties
- B24D3/342—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents characterised by additives enhancing special physical properties, e.g. wear resistance, electric conductivity, self-cleaning properties incorporated in the bonding agent
- B24D3/344—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents characterised by additives enhancing special physical properties, e.g. wear resistance, electric conductivity, self-cleaning properties incorporated in the bonding agent the bonding agent being organic
-
- 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
- C09K3/1436—Composite particles, e.g. coated particles
-
- 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 relates generally to fixed abrasive webs having improved chemical mechanical planarization (CMP) polishing performance.
- CMP chemical mechanical planarization
- the present invention relates to fixed abrasive webs containing additives that improve CMP polishing performance.
- Abrasive articles are frequently used in microfinishing applications such as semiconductor wafer polishing, microelectromechanical (MEMS) device fabrication, finishing of substrates for hard disk drives, polishing of optical fibers and connectors, and the like.
- semiconductor wafers typically undergo numerous processing steps including deposition of metal and dielectric layers, patterning of the layers, and etching. In each processing step, it may be necessary or desirable to modify or refine an exposed surface of the wafer to prepare it for subsequent fabrication or manufacturing steps.
- the surface modification process is often used to modify deposited conductors (e.g., metals, semiconductors, and/or dielectric materials).
- the surface modification process is also typically used to create a planar outer exposed surface on a wafer having an exposed area of a conductive material, a dielectric material, or a combination.
- One method of modifying or refining exposed surfaces of structured wafers treats a wafer surface with a fixed abrasive article.
- the fixed abrasive article is typically contacted with a semiconductor wafer surface, often in the presence of a working fluid, with a motion adapted to modify a layer of material on the wafer and provide a planar, uniform wafer surface.
- Fixed abrasive articles generally have an abrasive layer of abrasive particles bonded together by a binder and secured to a backing.
- the abrasive layer is composed of discrete raised structural elements (e.g., posts, ridges, pyramids, or truncated pyramids) termed "shaped abrasive composites".
- This type of fixed abrasive article is known in the art variously by the terms “textured, fixed abrasive article” or “structured abrasive article” (this latter term shall be used hereinafter).
- the abrasive articles can include abrasive particles and at least one nonionic polyether surfactant dispersed in a crosslinked polymer binder as disclosed in U.S. S.N. 12/560,797 (Woo et al).
- the present invention is a structured abrasive article including a backing having first and second opposed major surfaces and a structured abrasive layer disposed on and secured to the first major surface of the backing.
- the structured abrasive layer includes a polymeric binder, abrasive particles dispersed in the binder and a first additive dispersed in the binder.
- the first additive may be a multidentate acidic complexing agent, wherein the multidentate acidic complexing agent comprises an amino acid, a dipeptide formed from an amino acid and combinations thereof.
- the structured abrasive layer may include a second additive.
- the second additive comprises a nonionic surfactant, silicon surfactant, fluorosurfactant, water soluble polymer and combinations thereof.
- the additives provide improved chemical mechanical planarization (CMP) polish performance, including high oxide/nitride selectively, high removal rates, lower nitride loss and improved with-in- wafer non-uniformity (WIWNU ).
- CMP chemical mechanical planarization
- the present invention is a method of abrading a workpiece.
- the method includes contacting at least a portion of a structured abrasive article with a surface of a workpiece and moving at least one of the workpiece or the structured abrasive layer relative to the other to abrade at least a portion of the surface of the workpiece.
- the structured abrasive article includes a backing having first and second opposed major surfaces and a structured abrasive layer disposed on and secured to the first major surface.
- the structured abrasive layer includes a polymeric binder, abrasive particles dispersed in the binder and a first additive dispersed in the binder.
- the first additive may be a multidentate acidic complexing agent, wherein the multidentate acidic complexing agent comprises an amino acid, a dipeptide formed from an amino acid and combinations thereof.
- the structured abrasive layer may include a second additive.
- the second additive comprises a nonionic surfactant, silicon surfactant, fluorosurfactant, water soluble polymer and combinations thereof.
- the additives provide improved chemical mechanical planarization (CMP) polish performance, including high oxide/nitride selectively, high removal rates, lower nitride loss and improved WIWNU.
- Fig. 1 is a perspective view of an exemplary structured abrasive article according to one embodiment of the present invention.
- Fig. 2 is a schematic side view of an exemplary method of abrading a surface of a wafer according to the present invention.
- the structured abrasive article of the present invention includes additives within the web itself, allowing increased design control of the final product, increased consistency in downstream polishing processes and elimination of the need for waste treatment of polishing or working fluids.
- the additives provide improved chemical mechanical planarization (CMP) polish performance, including high oxide/nitride selectively, high removal rates, lower nitride loss and improved with-in-wafer non-uniformity (WIWNU ).
- CMP chemical mechanical planarization
- structured abrasive article 100 includes at least backing 110.
- Abrasive layer 120 is disposed on backing 110 and includes a plurality of shaped abrasive composites 130.
- Shaped abrasive composites 130 include abrasive particles (not shown) dispersed in a binder (not shown).
- the backing 110 may be flexible, rigid, or in between. A variety of backing materials are suitable for this purpose, including both flexible backings and backings that are more rigid.
- the backing may be at least a translucent film.
- Useful translucent film backings include backing films selected from polymer films, treated versions thereof, and combinations thereof.
- Exemplary translucent backing films include films made from polyester (e.g., polyethylene terephthalate or polycaprolactone), co-polyester, polycarbonate, polyimide, polyamide, polypropylene, polyurethane, polyethylene, cellulosic polymers, and blends and combinations thereof.
- the backing can include an elastomeric urethane or a foam.
- the thickness of the backing is typically in a range of from about 20 to about 1000 micrometers, particularly from about 50 micrometers to about 500 micrometers, and more particularly from about 60 micrometers to about 200 micrometers. At least one surface of the backing may be coated with the abrasive layer. In general, the backing is of substantially uniform in thickness. If the backing is not sufficiently uniform in thickness, greater variability in wafer polishing uniformity may occur during wafer planarization.
- the abrasive layer includes a plurality of shaped abrasive composites.
- shaped abrasive composite refers to one of a plurality of shaped bodies comprising abrasive particles dispersed in a binder, the shaped bodies collectively providing a textured, three-dimensional abrasive layer.
- the shaped abrasive composites are "precisely- shaped".
- the term "precisely-shaped abrasive composite” refers to an abrasive composite having a molded shape that is substantially the inverse of a mold cavity used to make it.
- precisely-shaped abrasive composites are substantially free of abrasive particles protruding beyond the exposed surface of the abrasive composite before the structured abrasive article has been used.
- abrasive particles constitute, on a weight basis, at least about 50 percent of the abrasive layer; and may constitute at least about 60, 70, 75, about 80, or about 90 percent by weight of the abrasive layer.
- weight percentage of the abrasive particles in the shaped abrasive composites increases, higher removal rates can be achieved.
- Suitable abrasive particles include fused aluminum oxide, heat treated aluminum oxide, white fused aluminum oxide, black silicon carbide, green silicon carbide, titanium diboride, boron carbide, silicon nitride, tungsten carbide, titanium carbide, diamond, cubic boron nitride, hexagonal boron nitride, garnet, fused alumina zirconia, alumina-based sol gel derived abrasive particles and the like.
- the alumina abrasive particle may contain a metal oxide modifier. Examples of alumina-based sol gel derived abrasive particles can be found in U.S. Pat. Nos. 4,314,827; 4,623,364; 4,744,802; 4,770,671; and 4,881 ,951.
- the diamond and cubic boron nitride abrasive particles may be mono crystalline or
- Suitable inorganic abrasive particles include silica, iron oxide, chromia, ceria, zirconia, titania, tin oxide, gamma alumina, and the like.
- dielectric containing wafer surfaces e.g., silicon dioxide-containing surfaces
- the abrasive particles have a Mohs hardness less than 8. Such particles, when properly incorporated into an abrasive article, provide the desired rate of cut and the desired surface finish on the wafer during pianarization.
- Some harder abrasive particles may impart an undesirably coarse surface finish on the oxide-containing wafer surface, so care should be exercised in selection of the appropriate abrasive material, such being within the ability of one skilled in the art.
- ceria abrasive particles are useful.
- the abrasive particles can include ceria (i.e., cerium oxide) particles having an average particle size, on a volume basis, of less than about 250 nanometers, less than about 150 nanometers, less than about 100 nanometers, or even less than about 50 nanometers.
- the abrasive particles can consist essentially of ceria particles.
- the phrase "consist essentially of used in this context is intended to exclude other (i.e., non-ceria) abrasive particles in amounts that materially affect abrading properties of the structured abrasive article, if used in wafer pianarization of silicon-containing wafers.
- the ceria particles may comprise agglomerates and/or aggregates of smaller primary ceria particles.
- the ceria particles (whether present as primary particle, agglomerates, aggregates, or a combination thereof) may have an average particle size, on a volume basis, in a range of from about 1, about 5, about 10, about 20, about 30, or about 40 nanometers up to about 50, about 60, about 70, about 80, about 90, about 95 nanometers, or more.
- Other nano-scale abrasive particles, on the size scale as that described for ceria, may be employed, including silica, ziconia, titania and alumina.
- the ceria particles can be supplied, for example, in the form of a powder, dispersion, or sol; typically, as a dispersion or sol. Methods and sources for obtaining ceria sols having an average particle size less than about 250 nanometers are well known in the art.
- Ceria dispersions and sols suitable for use in the present disclosure include, for example, ceria sols and dispersions commercially available for suppliers such as Evonik Degussa Corp. of Parsippany, NJ; Rhodia, Inc. of Cranberry, NJ; Ferro Corporation of Independence, OH; and Umicore SA, Brussels, Belgium.
- the abrasive particles may be homogeneously or heterogeneously dispersed in the polymeric binder.
- the term "dispersed” refers to the abrasive particles being distributed throughout the polymeric binder. Dispersing the ceria particles substantially homogeneously in the binder typically increases performance of the structured abrasive article. Accordingly, it is typically useful to treat the ceria particles with a surface modifying agent to facilitate their dispersion and/or reduce aggregation, and enhance subsequent coupling to the binder.
- Surface modifying agents for ceria are well known in the art.
- One type of surface modifying agent includes carboxylic (meth)acrylates.
- Exemplary carboxylic (meth)acrylates include (meth)acrylic acid, monoalkyl esters of maleic acid, fumaric acid, monoalkyl esters of fumaric acid, maleic acid, itaconic acid, isocrotonic acid, crotonic acid, citraconic acid, and ⁇ -carboxyethyl (meth)acrylate.
- a dispersion e.g., a sol
- an aqueous medium e.g., water
- a polyether acid and carboxylic (meth)acrylate in amounts of each that are sufficient to surface treat and thereby stabilize the ceria particles
- a water- miscible organic solvent having a higher boiling point than water.
- the proportion of polyether acid to carboxylic (meth)acrylate is in a range of from about 3:5 to 5:3, although other proportions may be used.
- useful solvents include l-methoxy-2-propanol, dimethylformamide, and diglyme.
- the water is substantially removed by evaporation under reduced pressure resulting in a ceria dispersion in which the ceria particles are stabilized against aggregation by associated carboxylic (meth)acrylate molecules.
- the resultant ceria dispersion can typically be readily combined with a binder precursor, and any additional carboxylic (meth)acrylate that may be included in the binder precursor.
- the polyether acid refers to a compound having a polyether segment covalently to an acidic group or salt thereof.
- Exemplary polyether segments include polyethylene glycol segments, polyethylene glycol segments, and mixed poly(ethylene glycol/propylene glycol) segments.
- Exemplary acidic groups include -C0 2 H, -P0 2 H, -PO 3 H, -SO 3 H, and salts thereof.
- the polyether acids can have up to 12 carbon atoms, inclusive, and are represented by the formula:
- R ⁇ -O X-A wherein R 1 represents H, an alkyl group having from 1 to 6 carbon atoms (e.g., methyl ethyl, or propyl), or an alkoxy group having from 1 to 6 carbon atoms (e.g., methoxy, ethoxyl, or propoxy); each R 2 independently represents a divalent alkylene group having from 1 to 6 carbon atoms (e.g., ethylene, propylene, or butylene); n represents a positive integer (e.g., 1, 2, or 3; and X represents a divalent organic linking group or a covalent bond; and A represents an acidic group (e.g., as described hereinabove).
- Exemplary polyether acids include 2'-(2"-methoxyethoxy)ethyl succinate (monoester), methoxyethoxyethoxyacetic acid, and methoxyethoxyacetic acid.
- the binder can further include a reaction product of components comprising a carboxylic (meth)acrylate and a poly(meth)acrylate. As discussed above, at least a portion of the carboxylic (meth)acrylate is typically combined with the abrasive particles prior to combining the resultant dispersion with the remaining binder components, although this is not a requirement.
- the abrasive layer includes abrasive particles dispersed in a binder.
- the binders for the abrasive articles of this invention are preferably formed from a binder precursor, typically an organic binder precursor.
- the binder precursor has a phase that is capable of flowing sufficiently so as to be coatable, and then solidifying. The solidification can be achieved by curing (e.g., polymerizing and/or crosslinking) and/or by drying (e.g., driving off a liquid), or simply upon cooling.
- the precursor can be an organic solvent-borne, water-borne, or 100% solids (i.e., a substantially solvent-free) composition. Both thermoplastic and thermosetting materials, as well as combinations thereof, can be used as the binder precursor.
- the binder precursor is preferably a curable organic material (i.e., a material capable of polymerizing and/or crosslinking upon exposure to heat and/or other sources of energy, such as E-beam, ultraviolet, visible, etc., or with time upon the addition of a chemical catalyst, moisture, and the like).
- a curable organic material i.e., a material capable of polymerizing and/or crosslinking upon exposure to heat and/or other sources of energy, such as E-beam, ultraviolet, visible, etc., or with time upon the addition of a chemical catalyst, moisture, and the like.
- Binder precursor examples include amino resins (e.g., aminoplast resins) such as alkylated urea-formaldehyde resins, melamine-formaldehyde resins, and alkylated benzoguanamine-formaldehyde resin, acrylate resins (including acrylates and methacrylates) such as vinyl acrylates, acrylated epoxies, acrylated urethanes, acrylated polyesters, acrylated acrylics, acrylated polyethers, vinyl ethers, acrylated oils, and acrylated silicones, alkyd resins such as urethane alkyd resins, polyester resins, reactive urethane resins, phenolic resins such as resole and tiovoiac resins, phenolic/latex resins, epoxy resins such as bisphenoi epoxy resins, isocyanates, isocyanurates, poiysiioxane resins (including alkylalkoxysilane
- the resins may be in the form of monomers, oligomers, polymers, or combinations thereof
- a substantially solvent-free binder precursor is used.
- the abrasive layer is typically formed by mixing low molecular weight reactive materials, such as, monomers and/or oligomers, along with any other desired cure initiators, cure accelerators, cure agents, dispersants, other additives and/or fillers; and abrasive particles.
- the abrasive particles are dispersed in the binder precursor, followed by curing of the binder precursor/abrasive particle mixture to form the abrasive layer.
- the binder precursor/abrasive particle mixture is often referred to as a "slurry".
- Suitable binder precursors are typically in an uncured or uncrosslinked state and are flowable at or near ambient conditions. After addition of the abrasive particles, the binder precursor is then typically exposed to conditions (typically an energy source) that at least partially cure and/or crosslink (i.e., free-radical polymerization) the binder precursor, thereby converting it into a binder capable of retaining the dispersed abrasive particles.
- energy sources include: e-beam, ultraviolet radiation, visible radiation, infrared radiation, gamma radiation, heat, and combinations thereof.
- the binder precursor may include one or more multi-fictional (meth)acrylates.
- Useful multi-functional (meth)acrylates include, but are not limited to, monomers and/or oligomers that have at least two (meth)acrylate groups; for example, tri(meth)acrylates, and
- exemplary poly(methacrylates) include: di(meth)acrylates such as, for example, 1,3-butylene glycol di(meth)acrylate, 1 ,4-butanediol di(meth)acrylate,
- di(meth)acrylate dipropylene glycol di(meth)acrylate, ethoxylated (10) bisphenol A di(meth)acrylate, ethoxylated (3) bisphenol A di(meth)acrylate, ethoxylated (30) bisphenol A di(meth)acrylate, ethoxylated (4) bisphenol A di(meth)acrylate, hydroxypivalaldehyde modified trimethylolpropane di(meth)acrylate, neopentyl glycol di(meth)acrylate,
- oligomeric (meth)acryl compounds such as, for example, polyester (meth)acrylates, epoxy (meth)acrylates; and combinations thereof.
- Such compounds are widely available from vendors such as, for example, Sartomer Co. of Exton, PA; UCB Chemicals Corporation of Smyrna, GA; and Aldrich Chemical Company of Milwaukee, WI.
- the binder precursor may include an effective amount of at least one photoinitiator; for example, in an amount of from about 0.1, about 1, or about 3 percent by weight, up to about 5, about 7, or even about 10 percent by weight, or more.
- Useful photoinitiators include those known as useful for free-radically photocuring (meth)acrylates. Exemplary
- photoinitiators include benzoin and its derivatives such as alpha-methylbenzoin; alpha- phenylbenzoin; alpha-allylbenzoin; alpha-benzylbenzoin; benzoin ethers such as benzil dimethyl ketal (available as IRGACURE 651 from Ciba Specialty Chemicals, Tarrytown, NY), benzoin methyl ether, benzoin ethyl ether, benzoin n-butyl ether; acetophenone and its derivatives such as 2-hy droxy-2 -methyl- 1 -phenyl- 1-propanone (available as DAROCUR 1173 from Ciba Specialty Chemicals) and 1 -hydroxy cyclohexyl phenyl ketone (available as IRGACURE 184 from Ciba Specialty Chemicals); 2-methyl- 1 -[4-(methylthio)phenyl]-2-(4- morpholinyl)- 1-propanone (available as I
- IRGACURE 369 from Ciba Specialty Chemicals
- phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide available as IRGACURE 819 from Ciba Specialty Chemicals, NY.
- Other useful photoinitiators include mono- and bis-acylphosphines (available, for example, from Ciba Specialty Chemicals as IRGACURE 1700, IRGACURE 1800, IRGACURE 1850, and DAROCUR 4265).
- the binder precursor may comprise an effective amount of at least one thermal initiator; for example, in an amount of from about 0.1, about 1, or about 3 percent by weight, up to about 5, about 7, or even about 10 percent by weight, or more.
- thermal free- radical initiators include: azo compounds such as, for example, 2,2-azo-bisisobutyronitrile, dimethyl 2,2'-azobis(isobutyrate), azobis(diphenyl methane), 4,4'-azobis-(4-cyanopentanoic acid), (2,2'-azobis(2,4-dimethylvaleronitrile (available as VAZO 52 from E. I. du Pont de Nemours and Co.
- peroxides such as, for example, benzoyl peroxide, cumyl peroxide, tert-butyl peroxide, cyclohexanone peroxide, glutaric acid peroxide, and dilauryl peroxide; hydrogen peroxide; hydroperoxides such as, for example, tert butyl hydroperoxide and cumene hydroperoxide; peracids such as, for example, peracetic acid and perbenzoic acid; potassium persulfate; and peresters such as, for example, diisopropyl percarbonate.
- peroxides such as, for example, benzoyl peroxide, cumyl peroxide, tert-butyl peroxide, cyclohexanone peroxide, glutaric acid peroxide, and dilauryl peroxide
- hydrogen peroxide hydrogen peroxide
- hydroperoxides such as, for example, tert butyl hydroperoxide and cumene hydroperoxid
- monoethylenically unsaturated free-radically polymerizable compounds include:
- mono(meth)acrylates include hexyl (meth)acrylate, 2-ethylhexyl acrylate, isononyl
- (meth)acrylate isobornyl (meth)acrylate, phenoxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, dodecyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, n-octyl (meth)acrylate, isobutyl (meth)acrylate, cyclohexyl (meth)acrylate, or octadecyl (meth)acrylate; N-vinyl compounds such as, for example, N-vinylformamide, N-vinylpyrrolidinone, or N-vinylcaprolactam; and
- the abrasive layer may also include one or more additives.
- the additives result in high oxide/nitride selectively, high removal rates, lower nitride loss and improved WIWNU uniformity.
- the additive(s) may actively influence the polishing process by being maintained at the surface of the abrasive layer in contact with the wafer and/or by being released into the working liquid, thereby interacting with the wafer surface being polished.
- the additive(s) typically has/have a molecular weight in a range of from 100 to 1,200 grams per mole, although higher and lower molecular weights may be used.
- the solubility of the additive in the working liquid is influenced by general principles of solubility of a solute in a solvent, as known in the art.
- the chemical structure of the additive(s) preferentially has/have at least one polar functional group or chemical feature, to facilitate solubility in the aqueous, working liquid.
- suitable additives include, but are not limited to: acidic complexing agents, nonionic surfactants, silicon surfactants, fluorosurfactants and water soluble polymers.
- acidic complexing agent is the first additive.
- the second additive is selected from the group consisting of nonionic surfactant, silicon surfactant, fluorosurfactant, water soluble polymer and combinations thereof.
- the additives are added to the binder precursor and are considered part of the binder precursor mixture. After addition of the abrasive particles to the binder precursor mixture, followed by curing, the additives are incorporated into the abrasive layer 120 and the correspondingly formed shaped abrasive composites 130.
- the abrasive layer includes one or more acidic complexing agents, as an additive.
- suitable acidic complexing agents include, but are not limited to, multidentate acidic complexing agents.
- suitable multidentate acidic complexing agents include, but are not limited to, at least one of an amino acid or a dipeptide formed from an amino acid.
- suitable amino acids include, but are not limited to: alanine, proline, glycine, histidine, lysine, arginine, ornithene, cysteine, tyrosine, dipeptides formed from two amino acids, acidic multidentate complexing agents and combinations thereof.
- Particularly suitable amino acids include, but are not limited to, L-Arginine and L-Proline.
- L-Arginine includes, but is not limited to, L-Arginine (Sigma-Aldrich Co. LLC, St. Louis, Missouri).
- L-Proline includes, but is not limited to, L-Proline.
- the acidic complexing agent is generally present in an amount between about 0.1% and about 3% by weight, particularly in an amount between about 0.25%> and about 2% by weight, and more particularly in an amount between about 0.5% and about 1.5% by weight.
- the abrasive layer includes one or more nonionic surfactants, as an additive.
- the non-ionic surfactant may be dispersed in the binder precursor. Typically, there is no covalent chemical bond between the surfactant and the binder.
- the binder precursor can be crosslinked as described further on to help contain the surfactant in the abrasive layer and regulate its release from the abrasive layer.
- the amount of non-ionic surfactant present in the abrasive layer can be in a range of from 0.75 to 2.2, from 1.0 to 2.2, from 1.3 to 2.2 percent by weight, typically from 1.5 to 2.0 percent by weight, based on a total weight of the abrasive layer.
- the nonionic surfactant typically has a molecular weight in a range of from 300 to 1,200 grams per mole, although higher and lower molecular weights may be used.
- the non-ionic surfactant may be a polyether non-ionic surfactant.
- polyether nonionic surfactant refers to one or more nonionic (i.e., not having a permanent charge) surfactant(s) that has/have a polyether segment, typically forming at least a portion of the backbone of the surfactant, although this is not a requirement.
- the polyether nonionic surfactant should not be covalently bound to the binder.
- the polyether nonionic surfactant typically has a molecular weight in a range of from 300 to 1,200 grams per mole, although higher and lower molecular weights may be used.
- polyether nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl-phenyl ethers, polyoxyethylene acyl esters, polyoxyethylene alkylamines, polyoxyethylene alkylamides, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol laurate, polyethylene glycol stearate, polyethylene glycol distearate, polyethylene glycol oleate, oxyethylene-oxypropylene block copolymer, polyoxyethylene sorbitan laurate,
- polyoxyethylene sorbitan stearate polyoxyethylene sorbitan oleate
- polyoxyethylene laurylamide polyoxyethylene laurylamide
- Useful polyether nonionic surfactants also include, for example, condensation products of a higher aliphatic alcohol with about 3 equivalents to about 100 equivalents of ethylene oxide (e.g., those marketed by Dow Chemical Co. under the trade designation TERGITOL 15-S such as, for example, TERGITOL 15-S-20; and those marketed by ICI Americas of Bridgewater, NJ under the trade designation BRIJ such as, for example, BRIJ 58, BRIJ 76, and BRIJ 97).
- BRIJ 97 surfactant is polyoxyethylene (10) oleyl ether
- BRIJ 58 surfactant is polyoxyethylene (20) cetyl ether
- BRIJ 76 surfactant is polyoxyethylene (10) stearyl ether.
- Useful polyether nonionic surfactants also include, for example, polyethylene oxide condensates of an alkyl phenol with about 3 equivalents to about 100 equivalents of ethylene oxide (e.g., those marketed by Rhodia of Cranbury, NJ under the trade designations IGEPAL CO and IGEPAL CA).
- IGEPAL CO surfactants include nonylphenoxy
- poly(ethyleneoxy)ethanols examples include octylphenoxy poly(ethyleneoxy)ethanols.
- Useful polyether nonionic surfactants also include, for example, block copolymers of ethylene oxide and propylene oxide or butylene oxide (e.g., those marketed by BASF Corp. of Mount Olive, NJ under the trade designations PLURONIC (e.g., PLURONIC L10) and TETRONIC).
- PLURONIC surfactants may include propylene oxide polymers, ethylene oxide polymers, and ethylene oxide -propylene oxide block copolymers.
- TETRONIC surfactants include ethylene oxide-propylene oxide block copolymers.
- polyether nonionic surfactants can include polyoxyethylene sorbitan fatty acid esters (e.g., polyoxyethylene sorbitan monooleates), which may have differing degrees of ethoxylation such as, for example, 20 ethylene oxide units per molecule (e.g., marketed as TWEEN 60) or 20 ethylene oxide units per molecule (e.g., marketed as TWEEN 80)) and polyoxyethylene stearates (e.g., those marketed under the trade
- TWEEN surfactants include poly(ethylene oxide) C 12 -C 18 sorbitan monoesters.
- MYRJ surfactants include poly(ethylene oxide) stearates.
- the polyether nonionic surfactant is the only surfactant present in the shaped abrasive composites or in the aqueous fluid during abrading. In some cases, it may be desirable to add lesser quantities of anionic surfactants such as an anionic phosphate polyether ester available as TRITON H55 from Dow Chemical Co.
- the nonionic surfactant exhibits a calculated hydrophile-lipophile balance (i.e. HLB), calculated as the weight percent of hydrophile in the surfactant molecule divided by 5, of at least about 4, particularly at least about 6, more particularly at least about 8, and more particularly at least about 10.
- HLB hydrophile-lipophile balance
- the nonionic surfactant may be advantageously selected from linear primary alcohol ethoxylate, secondary alcohol ethoxylate, branched secondary alcohol ethoxylate, octylphenol ethoxylate, acetylenic primary alcohol ethoxylate, acetylenic primary di-alcohol ethoxylate, alkane di-alcohol, hydroxyl-terminated ethylene oxide-propylene oxide random copolymer, fluoroaliphatic polymeric ester, and mixtures thereof.
- suitable commercially available ethylene oxide nonionic surfactants include, but are not limited to, Tergitol 15-S-7 (Sigma- Aldrich Co. LLC, St.
- the abrasive layer includes one or more silicon surfactants, as an additive.
- An example of a suitable commercially available silicon surfactant includes, but is not limited to, Silwet L-7200, Silwet L-7280 (Momentive Performance Material, Friendly, West Virginia).
- the silicon surfactant is generally present in an amount between about 0.1% and about 3% by weight, particularly in an amount between about 0.25% and about 2% by weight, and more particularly in an amount between about 0.5% and about 1.5% by weight.
- the abrasive layer includes one or more fluorosurfactants, as an additive.
- fluorosurfactants include, but are not limited to, FC 9 (3M Company, St. Paul, Minnesota) and Zonyl (Dupont, Wilmington, Delaware).
- FC 9 Commercially available fluorosurfactants
- Zonyl Zero-(Dupont, Wilmington, Delaware).
- the fluorosurfactant is generally present in an amount between about 0.1% and about 3% by weight, particularly in an amount between about 0.25% and about 2% by weight, and more particularly in an amount between about 0.5% and about 1.5% by weight.
- the abrasive layer includes one or more water soluble polymers, as an additive.
- suitable water soluble polymers include, but are not limited to, polymeric acids, e.g. polyacrylic acids and polyphosphoric acids.
- the water soluble polymer is generally present in an amount between about 0.1% and about 3% by weight, particularly in an amount between about 0.25% and about 2% by weight, and more particularly in an amount between about 0.5% and about 1.5% by weight.
- Combinations of one or more of the additives may be used.
- a preferred combination is an acidic complexing agent with a nonionic surfactant.
- a multidentate acidic complexing agent comprising an amino acid, a dipeptide formed from an amino acid and combinations thereof, is used in conjunction with a nonionic surfactant.
- the amino acid may be selected from the group consisting of: alanine, proline, glycine, histidine, lysine, arginine, ornithene, cysteine, tyrosine, and combinations thereof.
- the nonionic surfactant may be a polyether nonionic surfactant.
- the nonionic surfactant may be selected from the group consisting of: linear primary alcohol ethoxylate, secondary alcohol ethoxylate, branched secondary alcohol ethoxylate, octylphenol ethoxylate, acetylenic primary alcohol ethoxylate, acetylenic primary di-alcohol ethoxylate, alkane di- alcohol, hydroxyl-terminated ethylene oxide-propylene oxide random copolymer, fluoroaliphatic polymeric ester, and mixtures thereof.
- abrasive layer can be included in the abrasive layer, including one or more of an antioxidant, a colorant, a heat and light stabilizer, or a filler (the filler having substantially no impact on abrading performance).
- an antioxidant e.g., a colorant, a heat and light stabilizer, or a filler (the filler having substantially no impact on abrading performance).
- a filler the filler having substantially no impact on abrading performance.
- Provided structured abrasive articles that include shaped abrasive composites, can be made by general methods well-known in the art. For example, in one embodied method a binder precursor and abrasive particles, in the form of a slurry, can be urged into
- the translucent film backing can be brought into contact with the slurry and, in some instances, the production tool.
- the binder precursor can be at least sufficiently cured to remove the shaped abrasive composites from the production tool.
- the production tool, at least translucent film backing, and slurry can be simultaneously fed through a nip.
- further curing e.g., thermal post curing
- further curing can be carried out at this stage to further advance the degree of cure and thereby improve the binder properties.
- Individual shaped abrasive composites can have the form of any of a variety of geometric solids or be irregularly shaped.
- the shaped abrasive composites are precisely-shaped (as defined above).
- the shaped abrasive composite is formed such that the base of the shaped abrasive composite, the portion of the shaped abrasive composite in contact with the translucent film backing, is secured to the translucent film backing.
- the proximal portion of the shaped abrasive composite typically has the same or larger a larger surface area than that portion of the shaped abrasive composite distal from the base or backing.
- Precisely-shaped abrasive composites may be of any three-dimensional shape that results in at least one of a raised feature or recess on the exposed surface of the abrasive layer.
- Useful shapes include, for example, cubic, prismatic (e.g., hexagonal prisms), pyramidal (e.g., square pyramidal or hexagonal pyramidal), truncated pyramidal, conical, frustoconical, hemispherical, cross, or post-like cross sections with a distal end.
- Composite pyramids may have four sides, five sides or six sides. Combinations of differently shaped and/or sized abrasive composites may also be used.
- the abrasive layer of the structured abrasive may be continuous or discontinuous.
- the shaped abrasive composites may be arranged in rows, in concentric circles, in helices, or in lattice fashion, or may be randomly placed. Further details concerning structured abrasive articles having precisely-shaped abrasive composites, and methods for their manufacture may be found, for example, in U.S. Pat. Nos. 5,435,816 (Spurgeon et al); 5,454,844 (Hibbard et al); 5,851,247 (Stoetzel et al); and 6,139,594 (Kincaid et al).
- the sides forming the shaped abrasive composites may be perpendicular relative to the backing, tilted relative to the backing or tapered with diminishing width toward the distal end. However, if the sides are tapered, it may be easier to remove the shaped abrasive composite from the cavities of a mold or production tool. The substantially perpendicular angles are preferred because this results in a consistent nominal contact area as the composite wears.
- each shaped abrasive composite is typically substantially the same, but it is envisaged to have composites of varying heights in a single structured abrasive article.
- the height of the composites with respect to the backing or to the land between the composites generally may be less than about 2,000 micrometers; for example, in a range of from about 10 micrometers to about 250 micrometers.
- the base dimension of an individual shaped abrasive composite may be about 5,000 micrometers or less, particularly about 1,000 micrometers or less, and more particularly less than 500 micrometers.
- the base dimension of an individual shaped abrasive composite is typically greater than about 50 micrometers, particularly greater than about 100 micrometers.
- the base of the shaped abrasive composites may abut one another, or may be separated from one another by some specified distance.
- Adjacent shaped composites may share a common shaped abrasive composite land or bridge-like structure which contacts and extends between facing sidewalls of the composites.
- the land structure has a height of no greater than about 33 percent of the vertical height dimension of each adjacent composite.
- the shaped abrasive composite land may be formed from the same slurry used to form the shaped abrasive composites.
- the composites are "adjacent" in the sense that no intervening composite may be located on a direct imaginary line drawn between the centers of the composites. At least portions of the shaped abrasive composites may be separated from one another so as to provide the recessed areas between the raised portions of the composites.
- the linear spacing of the shaped abrasive composites may range from about 1 shaped abrasive composite per linear cm to about 200 shaped abrasive composites per linear cm.
- the linear spacing may be varied such that the concentration of composites may be greater in one location than in another. For example, the concentration may be greatest in the center of the abrasive article.
- the areal density of the composite may range, in some embodiments, from about 1 to about 40,000 composites per square centimeter.
- One or more areas of the backing may be exposed, i.e., have no abrasive coating contacting the at least translucent film backing.
- the shaped abrasive composites are typically set out on a backing in a predetermined pattern or set out on a backing at a predetermined location, although this is not a requirement.
- the predetermined pattern of the composites will correspond to the pattern of the cavities on the production tool.
- the pattern may be thus reproducible from article to article.
- the shaped abrasive composites may form an array or arrangement, by which may be meant that the composites are in a regular array such as aligned rows and columns, or alternating offset rows and columns.
- one row of shaped abrasive composites may be directly aligned in front of a second row of shaped abrasive composites.
- one row of shaped abrasive composites may be offset from a second row of shaped abrasive composites.
- the shaped abrasive composites may be set out in a "random" array or pattern. By this it may be meant that the composites are not in a regular array of rows and columns as described above.
- the shaped abrasive composites may be set out in a manner as disclosed in U. S. Pat. Nos. 5,672,097 and 5,681,217 (both to
- this "random" array may be a predetermined pattern in that the location of the composites on the abrasive article may be predetermined and corresponds to the location of the cavities in the production tool used to make the abrasive article.
- Exemplary production tools include rolls, endless belts, and webs, and may be made of a suitable material such as for example, metal (e.g., in the case of rolls) or polymer films (e.g., in the cases of endless belts and webs).
- Provided structured abrasive articles may be generally circular in shape, e.g., in the form of an abrasive disc. Outer edges of the abrasive disc are typically smooth, or may be scalloped.
- the structured abrasive articles may also be in the form of an oval or of any polygonal shape such as triangular, square, rectangular, and the like.
- the abrasive articles may be in the form of a belt.
- the abrasive articles may be provided in the form of a roll, typically referred to in the abrasive art as abrasive tape rolls. In general, the abrasive tape rolls may be indexed or moved continuously during the wafer planarization process.
- the abrasive article may be perforated to provide openings through the abrasive coating and/or the backing to permit the passage of the working fluid before, during and/or after use; although, in advantageous embodiments the structured abrasive articles are substantially free of, or even completely free of, such perforations.
- the abrasive layer can be applied to a front surface, i.e. a first major surface, of a backing.
- the second major surface of the backing i.e. the side of the backing opposite the abrasive layer can typically be contacted with a subpad during use.
- the structured abrasive article can be secured to the subpad.
- An attachment interface layer may be directly bonded to the second major surface of the backing.
- the attachment interface layer may be used to bond the structured abrasive article to another substrate, e.g. a subpad or a platen.
- the attachment interface layer can be an adhesive, a pressure-sensitive adhesive or an adhesive transfer tape (i.e. a double sided tape), which can be applied to the opposing surface of the backing.
- Suitable mechanical fastening device(s) may also be used.
- Suitable subpads are disclosed, for example, in U.S. Pat. Nos. 5,692,950 and 6,007,407 (both to Rutherford et al).
- the subpad, and any platen on which it rests should have at least one appropriately sized window (e.g., an opening or transparent insert) to permit a continuous optical path from a light source (e.g., a laser) through the platen and subpad.
- a light source e.g., a laser
- structured abrasive articles may be used for abrading and/or polishing workpieces such as wafers containing silicon (e.g., silicon wafers, glass wafers, etc.) or other metals and including those wafers having an oxide layer on an outer surface thereof.
- the structured abrasive articles may be useful in abrading and/or polishing a dielectric material deposited on the wafer and/or the wafer itself.
- the provided abrasive article can be useful in abrading or polishing other materials such as sapphire or other minerals.
- Variables that affect the wafer polishing rate and characteristics include, for example, the selection of the appropriate contact pressure between the wafer surface and abrasive article, type of working fluid, relative speed and relative motion between the wafer surface and the abrasive article, and the flow rate of the working fluid. These variables are interdependent, and are typically selected based upon the individual wafer surface being processed.
- Structured abrasive articles according to the present disclosure may be conditioned, for example, by abrading the surface using a pad conditioner (e.g., with diamond grits held in a metal matrix) prior to and/or intermittently during the wafer planarization process.
- a pad conditioner e.g., with diamond grits held in a metal matrix
- One useful conditioner is a CMP pad conditioner (typically mounted on a rigid backing plate), part no. CMP-20000TS, available from Morgan Advanced Ceramics of Hayward, CA.
- the semiconductor fabrication industry expects that the process will provide a relatively high removal rate of material.
- the material removal rate obtained with a particular abrasive article will typically vary depending upon the machine conditions and the type of wafer surface being processed.
- the conductor or dielectric material removal rate may be selected such that it does not compromise the desired surface finish and/or topography of the wafer surface.
- polishing apparatus 200 is used in an exemplary method of abrading a surface of a wafer.
- structured abrasive article 100 contacts and is secured to subpad 210, which is in turn secured to platen 220.
- Subpad 210 which may comprise a foam (e.g., a polyurethane foam) or other compressible material, has first window 212 therein, and platen 220 has second window 222 therein.
- Wafer holder 233 is mounted to a head unit 231 that is connected to a motor (not shown).
- Gimbal chuck 232 extends from head unit 231 to wafer holder 233.
- Wafer holder 233 helps secure wafer 240 to head unit 231 and also prevent the semiconductor wafer from becoming dislodged during planarization.
- Wafer holder 233 extends alongside of wafer 240 at ring portion 233 a.
- Ring portion 233 a (which is optional) may be a separate piece or may be integral with wafer holder 233.
- Wafer 240 is brought into contact with the abrasive layer 120 of structured abrasive article 100, and the wafer 240 and abrasive layer 120 are moved relative to one another.
- polishing/abrading is monitored using laser beam 250 which passes through second window 222, first window 212, and structured abrasive article 100 and is reflected off oxide surface 242 of wafer 240 and then retraces its path.
- Optional working fluid 260 may be used to facilitate the abrading process.
- Reservoir 237 holds optional working fluid 260 which is pumped through tubing 238 into the interface between semiconductor wafer and the abrasive layer.
- Useful working fluids include, for example, those listed in U.S. Pat. No. 5,958,794 (Bruxvoort et al.).
- wafer surface finishes that are substantially free of scratches and defects are desired.
- the surface finish of the wafer may be evaluated by known methods.
- One method is to measure the Rt value, which provides a measure of roughness, and may indicate scratches or other surface defects.
- the wafer surface is typically modified to yield an Rt value of no greater than about 0.4 nanometers, more typically no greater than about 0.2 nanometers, and even more typically no greater than about 0.05 nanometers.
- Rt is typically measured using a laser interferometer such as a Wyko RST PLUS interferometer (Wyko
- Wafer surface processing may be conducted in the presence of a working fluid, which may be selected based upon the composition of the wafer surface.
- the working fluid typically comprises water. The working fluid may aid processing in
- the working fluid may react with the outer or exposed wafer surface. Then during the mechanical portion of processing, the abrasive article may remove this reaction product.
- abrasive articles that can polish wafers that have very small features without producing defects.
- Some exemplary devices have features as small as 32 nm, 28 nm or even 20 nm.
- the abrasive article it is important that the abrasive article be able to create a smooth surface with very few defects at a relatively high rate.
- the wafer which can be 100 mm or more in diameter, needs to have a uniform profile with minimal dishing.
- structured abrasive articles that include an abrasive layer having an acidic complexing agent and optionally, a nonionic surfactant, dispersed therein, can remove material from thermal oxide wafers at rates exceeding 500 A/min with low defects, low nitride removal rate and good WIWNU.
- a wetting and dispersing additive available under the trade designation
- Trimethylolpropane triacrylate available under the trade designation
- Phenothiazine available from Cytec Industries, Woodland Park,
- IRG 819 phosphine oxide available under the trade designation "IRGACURE
- VAZO 52 available under the trade designation "VAZO 52" from E. I. du Pont de
- the fixed abrasive webs were used to polish 300 mm diameter thermal silicon oxide, and PECVD silicon nitride blanket wafers, as well as, oxide/nitride pattern wafers with an MIT764 test pattern using a CMP polisher available under the trade designation
- REFLEXION polisher from Applied Materials, Inc. of Santa Clara, CA.
- One of the polishing stations of the web tool was fitted with a web carriage suitable for mounting and running FA webs on the polishing tool.
- a subpad available under the trade designation "3M CMP FIXED ABRASIVE P7100 SUB PAD" from the 3M Company, St. Paul, Minnesota, was mounted to the platen of the polisher.
- a fixed abrasive web was mounted in the carriage assembly of the polisher, such, that, the web lined up with and over the subpad mounted on the platen.
- the process conditions were as follows:
- Head Pressures Retaining Ring 4.2 psi, Zone 1 3.4 psi, Zone2 1.9 psi, Zone3 2.0 psi, Zone4 2.0 psi and Zone5 2.0 psi.
- Polishing time 60 sec. per blanket wafers and 30 sec. per pattern wafer.
- Polishing Fluid (standard): 2.5 wt% L-Proline in DI Water at pH 10.5.
- an additive was added to the standard polishing solution described above, see Table 1 for the various additives and concentrations used.
- the pH of the solution was adjusted to 10.5 using potassium hydroxide Oxide removal rate and non-uniformity was measured on 300 mm blanket oxide wafers.
- the average silicon nitride loss on a 50 ⁇ line on a silicon oxide and silicon nitride pattern wafer is shown in Table 1.
- the oxide and nitride removal rate measurements for both blanket and pattern wafers were made using a NovaScan 3060 ellipsometer which is integrated with the REFLEXION polisher and was supplied by Applied Materials. Blanket oxide and nitride wafers were measured with a 25 -pt diameter scan with 3 mm edge exclusion. Nitride loss measurements were made near the center lines of 50 micron lines/50 micron space arrays. The pattern wafers were measured at 7 different die starting at the wafer center and moving to the outermost die. Each new web was tested with a minimum of 25 blanket oxide wafers, followed by the pattern wafer, and then the blanket nitride wafer. The average removal rate from the last 10 blanket oxides was reported as the oxide removal rate.
- Nitride removal rate data and nitride loss data was obtained from the single nitride blanket wafer and pattern wafer, respectively. If additional testing was done on the same web, using a different polishing fluid, the same test sequence was used, except only 10 blanket oxide wafers were polished and the average of the last 5 wafers was reported for the oxide removal rate.
- Example 1 Fixed Abrasive Web with L-Arginine in the Binder
- a ceria dispersion was prepared as follows: 11.4045 kg Ce-A was poured into a mixing vessel and then 703 g of 2-2-MEEAA, 568 g of ⁇ -CEA, and 2.7907 kg of l-M-2-Pr were slowly added while mixing using a polytetrafluoroethylene-coated blade. The mixture was heated to 50°C and mixed overnight. The mixture was then transferred into a rotary evaporator and excess water was removed under reduced pressure. The resultant dispersion, Ceria Dispersion 1, had a solids content of 49.54 percent. Preparation of Slurry 1
- Ceria Dispersion 1 1,243.4 g, and 18.5 g of D-l 11 were added to a mixing vessel and mixed.
- the mixture was mixed using a polytetrafluoroethylene-coated blade for 30 minutes and then transferred to a rotary evaporator to remove the l-M-2-Pr. After solvent removal, the slurry was cooled to room temperature, and then 0.71 g of IRG 819, 0.71 g of VAZO 52 and 0.18 g of HQME were added, followed by mixing for two hours, yielding Slurry 1.
- abrasive articles of the present invention were formed using a microreplication fabricating technique as described in U.S. Pat. No. 5,152,917 (Pieper et al).
- a roll of polypropylene production tool 30 inches (76 cm) in width, was provided.
- the polypropylene production tool was polypropylene film that had a hexagonal array (350 micrometers on center) of hexagonal columnar cavities (125 ⁇ wide and 30 ⁇ deep), corresponding to a 10 percent cavity area.
- the production tool was essentially the inverse of the desired shape, dimensions, and arrangement for the abrasive composites in the final structured abrasive article.
- Slurry 1 was coated between the cavities of production tool and Backing 1 using a casting roll and a nip roll (nip force of 1,300 pounds (5.78 kN) and then passed through a UV curing station having an UV light source (V Bulb, Model EPIQ available from Fusion UV Systems, Inc., Gaithersburg, Maryland), at a line speed of 10 feet/min (3.0 m/min) and a total exposure of 6.0 kW/inch (15.2 kW/cm).
- the polypropylene tooling was separated from backing 1, resulting in a cured, abrasive layer, having precisely-shaped abrasive composite, adhered to backing 1, Fixed Abrasive Web 1, i.e., Example 1. Polishing results for wafers polished with Example 1 are shown in Table 1.
- a fixed abrasive web was fabricated using the identical procedure as that described in Example 1 , except Slurry 2 was used in place of Slurry 1.
- the resulting fixed abrasive was designated Fixed Abrasive Web 2, i.e. Example 2. Polishing results for wafers polished with Example 2 are shown in Table 1.
- Ceria Dispersion 1 1,253.8 g, and 18.5 g of D-l 11 were added to a mixing vessel and mixed.
- the mixture was mixed using a
- a fixed abrasive web was fabricated using the identical procedure as that described in Example 1 , except Slurry 3 was used in place of Slurry 1.
- the resulting fixed abrasive was designated Fixed Abrasive Web 3, i.e. Example 3. Polishing results for wafers polished with Example 3 are shown in Table 1.
- Ceria Dispersion 1 1,243.4 g, and 18.5 g of D-l 11 were added to a mixing vessel and mixed. To this mixture was added 3.48 g 2-HEMA, 8.85 g SR 339, 67.86 g SR 351, 3.81 grams of ⁇ -CEA, and 0.42 grams of Phth dissolved in 20 g of l-M-2-Pr. The mixture was mixed using a polytetrafluoroethylene-coated blade for 30 minutes and then transferred to a rotary evaporator to remove the l-M-2-Pr. The slurry was cooled to room temperature and then 0.74 g of IRG 81, 0.74 g of VAZO 52 and 0.18 g of HQME were added, followed by mixing for two hours, yielding Slurry 4.
- a fixed abrasive web was fabricated using the identical procedure as that described in
- Example 1 except Slurry 4 was used in place of Slurry 1.
- the resulting fixed abrasive was designated Comparative Fixed Abrasive Web 4, i.e. Comparative Example 4. Polishing results for wafers polished with Comparative Example 4 are shown in Table 1. It should be noted that the general composition of Example 1 and Example 3, i.e. without the indicated variation, is comparable to that of Comparative Example 4.
- Example 5 A fixed abrasive web was fabricated using the identical procedure as that described in Example 1 , except Slurry 5 was used in place of Slurry 1.
- the resulting fixed abrasive was designated Comparative Fixed Abrasive Web 5, i.e. Comparative Example 5. Polishing results for wafers polished with Comparative Example 5 are shown in Table 1. It should be noted that the general composition of Example 2, i.e. without the indicated variations, is comparable to that of Comparative Example 5. Table 1
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Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2015533125A JP2015532895A (ja) | 2012-09-21 | 2013-09-17 | Cmp性能を改善するための固定研磨ウェブへの添加剤の配合 |
KR1020157009287A KR20150058302A (ko) | 2012-09-21 | 2013-09-17 | 개선된 cmp 성능을 위한 고정 연마 웹으로의 첨가제의 혼입 |
SG11201502225XA SG11201502225XA (en) | 2012-09-21 | 2013-09-17 | Incorporating additives into fixed abrasive webs for improved cmp performance |
CN201380049086.0A CN104822495A (zh) | 2012-09-21 | 2013-09-17 | 向固定磨料幅材中引入添加剂以改善cmp性能 |
EP13838975.4A EP2897767A4 (en) | 2012-09-21 | 2013-09-17 | INTEGRATION OF ADDITIONS IN FIXED SLOPES FOR IMPROVED CMP PERFORMANCE |
US14/425,697 US20150217424A1 (en) | 2012-09-21 | 2013-09-17 | Incorporating additives into fixed abrasive webs for improved cmp performance |
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US201261703815P | 2012-09-21 | 2012-09-21 | |
US61/703,815 | 2012-09-21 |
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WO2014047014A1 true WO2014047014A1 (en) | 2014-03-27 |
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PCT/US2013/060022 WO2014047014A1 (en) | 2012-09-21 | 2013-09-17 | Incorporating additives into fixed abrasive webs for improved cmp performance |
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US (1) | US20150217424A1 (ja) |
EP (1) | EP2897767A4 (ja) |
JP (1) | JP2015532895A (ja) |
KR (1) | KR20150058302A (ja) |
CN (1) | CN104822495A (ja) |
SG (1) | SG11201502225XA (ja) |
TW (1) | TW201420706A (ja) |
WO (1) | WO2014047014A1 (ja) |
Cited By (1)
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WO2019011251A1 (zh) * | 2017-07-13 | 2019-01-17 | 安集微电子科技(上海)股份有限公司 | 化学机械抛光液 |
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US9649741B2 (en) * | 2014-07-07 | 2017-05-16 | Jh Rhodes Company, Inc. | Polishing material for polishing hard surfaces, media including the material, and methods of forming and using same |
US9873180B2 (en) | 2014-10-17 | 2018-01-23 | Applied Materials, Inc. | CMP pad construction with composite material properties using additive manufacturing processes |
US11745302B2 (en) | 2014-10-17 | 2023-09-05 | Applied Materials, Inc. | Methods and precursor formulations for forming advanced polishing pads by use of an additive manufacturing process |
US10875153B2 (en) | 2014-10-17 | 2020-12-29 | Applied Materials, Inc. | Advanced polishing pad materials and formulations |
CN117283450A (zh) * | 2016-01-19 | 2023-12-26 | 应用材料公司 | 多孔化学机械抛光垫 |
CN106947396B (zh) * | 2017-03-23 | 2019-02-26 | 河南联合精密材料股份有限公司 | 研磨液用悬浮体系、研磨液及其制备方法 |
CN108747876B (zh) * | 2018-06-11 | 2021-03-19 | 河北思瑞恩新材料科技有限公司 | 一种漆面研磨砂碟的制备方法 |
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2013
- 2013-09-17 WO PCT/US2013/060022 patent/WO2014047014A1/en active Application Filing
- 2013-09-17 EP EP13838975.4A patent/EP2897767A4/en not_active Withdrawn
- 2013-09-17 CN CN201380049086.0A patent/CN104822495A/zh active Pending
- 2013-09-17 US US14/425,697 patent/US20150217424A1/en not_active Abandoned
- 2013-09-17 SG SG11201502225XA patent/SG11201502225XA/en unknown
- 2013-09-17 KR KR1020157009287A patent/KR20150058302A/ko not_active Application Discontinuation
- 2013-09-17 JP JP2015533125A patent/JP2015532895A/ja active Pending
- 2013-09-18 TW TW102133978A patent/TW201420706A/zh unknown
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Also Published As
Publication number | Publication date |
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EP2897767A4 (en) | 2016-07-27 |
TW201420706A (zh) | 2014-06-01 |
CN104822495A (zh) | 2015-08-05 |
EP2897767A1 (en) | 2015-07-29 |
US20150217424A1 (en) | 2015-08-06 |
JP2015532895A (ja) | 2015-11-16 |
SG11201502225XA (en) | 2015-05-28 |
KR20150058302A (ko) | 2015-05-28 |
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