• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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    • 专利摘要:
    There is provided a method of mechano-chemical polishing of a substrate, comprising: providing a polishing machine having a cylinder; providing a substrate, wherein the substrate has an exposed silicon oxide surface; providing a chemical mechanical polishing felt, comprising: a polyurethane polishing layer; wherein the polyurethane polishing layer composition has an acid number ≥ 0.5 mg (KOH) / g; providing an abrasive suspension, wherein the abrasive suspension comprises water and a cerium oxide abrasive; creating a dynamic contact at an interface between the mechanochemical polishing felt and the substrate; and dispensing the abrasive slurry on the polishing surface of the polyurethane polishing layer of the chemical mechanical polishing pad to or near the interface between the chemical mechanical polishing pad and the substrate; and, polishing the substrate.
    公开号:FR3022815A1
    申请号:FR1555697
    申请日:2015-06-22
    公开日:2016-01-01
    发明作者:Bainian Qian；Marty Degroot；Mark F Sonnenschein
    申请人:Rohm and Haas Electronic Materials CMP Holdings Inc；Dow Global Technologies LLC；Rohm and Haas Electronic Materials LLC；
    IPC主号:
    专利说明:

    [0001] The present invention relates to a method for mechanical-chemical polishing of a substrate. The present invention more particularly relates to a method of mechanical-chemical polishing of a substrate, comprising: providing a polishing machine having a disk (or platinum); providing a substrate, wherein the substrate has an exposed silicon oxide surface; providing a chemical mechanical polishing felt, comprising: a polyurethane polishing layer; wherein the polyurethane polishing layer is selected to have a composition, a bottom surface and a polishing surface; wherein the polyurethane polishing layer composition has an acid value of 0.5 mg (KOH) / g; wherein the polishing surface is adapted to polish a substrate; providing an abrasive suspension, wherein the abrasive suspension comprises water and a cerium oxide abrasive; installing the substrate and the chemical mechanical polishing felt in the polishing machine; creating a dynamic contact at an interface between the chemical mechanical polishing felt and the substrate; and dispensing the abrasive slurry on the polishing surface of the polyurethane polishing layer of the chemical mechanical polishing pad to or near the interface between the chemical mechanical polishing pad and the substrate; and wherein at least a certain amount of the exposed silicon oxide surface is removed by polishing the surface of the substrate. Semiconductor production typically involves several chemical mechanical planarization (CMP) processes. In each CMP process, a polishing felt in combination with a polishing solution, such as a polishing slurry containing an abrasive-free abrasive or reagent liquid, removes excess material so as to planarize or maintain the flatness to receive a subsequent layer. The stack of these layers is combined to form an integrated circuit. The fabrication of these semiconductor devices continues to become more complex due to requirements for devices with higher operating speeds, lower leakage currents and reduced power consumption. In terms of device architecture, it is moving towards finer aspect geometries and higher metallization levels. These ever more stringent requirements for the design of a device lead to the adoption of copper metallization in combination with new dielectric materials having lower dielectric constants. The reduced physical properties, frequently associated with low k and ultra-low k materials, in combination with the higher complexity of the devices, have led to greater demands on CMP consumables, such as polishing felts and polishing solutions. Polyurethane polishing felts are the main chemistry of felts used for various precision polishing applications. Polyurethane polishing felts are effective for polishing silicon wafers, patterned wafers, flat panel displays, and magnetic storage disks. In particular, polyurethane polishing felts provide mechanical integrity and chemical resistance for most polishing operations used to manufacture integrated circuits. Polyurethane polishing felts, for example, have high strength to resist tearing; abrasion resistance to avoid wear problems during polishing; and stability to resist attack by strong and strong caustic acid polishing solutions. A family of polyurethane polishing layers is described by Kulp et al. in U.S. Patent 8,697,239. Kulp et al. disclose a polishing felt suitable for polishing patterned semiconductor substrates containing at least one of copper, a dielectric, a barrier and tungsten, the polishing felt comprising a polymer matrix, the polymer matrix consisting of polyurethane reaction product consisting of a combination of polyols, a polyamine or a mixture of polyamines and a toluene diisocyanate, the combination of polyols being a mixture of 15 to 77 percent by weight total of polypropylene glycol and polytetramethylene ether glycol and the mixture of polypropylene glycol and polytetramethylene ether glycol having a weight ratio of polypropylene glycol to polytetramethylene ether glycol in a ratio of 20 to 1 at a ratio of 1 to 20, the polyamine or the mixture of polyamines consisting of 8 to 50 percent by weight in a liquid mixture, and the toluene diisocyanate being 20 to 30 percent total weight of a toluene diisocyanate monomer or a partially reacted toluene diisocyanate monomer, all based on the total weight of the polymer matrix.
    [0002] There is, however, a continuing need for chemical mechanical polishing processes that exhibit an appropriate balance of properties, which provide the desired rate of shrinkage and provide a high degree of processing tolerance, particularly when using an abrasive slurry. based on cerium oxide.
    [0003] The present invention provides a method for mechanochemical polishing of a substrate, comprising: providing a polishing machine having a disk; providing a substrate, wherein the substrate has an exposed silicon oxide surface; providing a chemical mechanical polishing felt, comprising: a polyurethane polishing layer; wherein the polyurethane polishing layer is selected to have a composition, a bottom surface and a polishing surface; wherein the polyurethane polishing layer composition has an acid number. 0.5 mg (KOH) / g; wherein the polishing surface is adapted to polish a substrate; providing an abrasive suspension, wherein the abrasive suspension comprises water and a cerium oxide abrasive; installing the substrate and the chemical mechanical polishing felt in the polishing machine; creating a dynamic contact at an interface between the chemical mechanical polishing felt and the substrate; and dispensing the abrasive slurry on the polishing surface of the polishing layer of the chemical mechanical polishing felt at or near the interface between the chemical mechanical polishing pad and the substrate; and wherein at least a certain amount of the exposed silicon oxide surface is removed by polishing the surface of the substrate.
    [0004] According to a particular characteristic of this method, the chemical-mechanical polishing felt provided further comprises a layer of pressure-sensitive cylinder adhesive having a stacking side and a cylinder side; the stacking side of the pressure sensitive cylinder adhesive layer being adjacent to the bottom surface of the polyurethane polishing layer.
    [0005] Advantageously, this felt further comprises at least one additional layer assembled with and interposed between the bottom surface of the polyurethane polishing layer and the stacking side of the pressure-sensitive cylinder adhesive layer. The present invention provides a method for mechano-chemical polishing of a substrate, comprising: providing a polishing machine having a disk; providing a substrate, wherein the substrate has an exposed silicon oxide surface; providing an abrasive treatment agent; providing a chemical-mechanical polishing felt, comprising: a polyurethane polishing layer; wherein the polyurethane polishing layer is selected to have a composition, a bottom surface and a polishing surface; wherein the polyurethane polishing layer composition has an acid value of 0.5 mg (KOH) / g; wherein the polishing surface is adapted to polish a substrate; providing an abrasive suspension, wherein the abrasive suspension comprises water and a cerium oxide abrasive; installing the substrate and the chemical mechanical polishing felt in the polishing machine; creating a dynamic contact at an interface between the chemical mechanical polishing felt and the substrate; distributing the abrasive suspension on the polishing surface of the polishing layer of the chemical mechanical polishing felt at or near the interface between the chemical mechanical polishing felt and the substrate; wherein at least a certain amount of the exposed silicon oxide surface is removed by polishing the surface of the substrate; and, treating the polishing surface with the abrasive treating agent. The present invention provides a method for mechano-chemical polishing of a substrate, comprising: providing a polishing machine having a cylinder; providing a substrate, wherein the substrate has an exposed silicon oxide surface; providing an abrasive treatment agent; providing a chemical mechanical polishing felt, comprising: a polyurethane polishing layer; wherein the polyurethane polishing layer is selected to have a composition, a bottom surface and a polishing surface; wherein the polyurethane polishing layer composition has an acid value of 0.5 mg (KOH) / g; wherein the polishing surface is adapted to polish a substrate and wherein the polishing surface has a processing tolerance of 80%; providing an abrasive suspension, wherein the abrasive suspension comprises water and a cerium oxide abrasive; installing the substrate and the chemical mechanical polishing felt in the polishing machine; creating a dynamic contact at an interface between the chemical mechanical polishing felt and the substrate; distributing the abrasive suspension on the polishing surface of the polishing layer of the chemical mechanical polishing felt at or near the interface between the chemical mechanical polishing felt and the substrate; wherein at least a certain amount of the exposed silicon oxide surface is removed by polishing the surface of the substrate; and, treating the polishing surface with the abrasive treating agent. The present invention provides a method of mechanochemical polishing of a substrate, comprising: providing a polishing machine having a cylinder; providing a substrate, wherein the substrate has an exposed silicon oxide surface; optionally providing an abrasive treating agent, providing a chemical mechanical polishing cloth, comprising: a polyurethane polishing layer; wherein the polyurethane polishing layer is selected to have a composition, a bottom surface and a polishing surface; wherein the composition of the selected polyurethane polishing layer is the ingredient reaction product, comprising: (a) a polyfunctional isocyanate; (b) a hardener system, comprising: (i) a polyfunctional carboxylic acid-containing hardener having an average of at least two active hydrogen and at least one carboxylic acid functional group per molecule; and, (c) optionally, a plurality of microelements; wherein the polyurethane polishing layer composition has an acid value of 0.5 mg (KOH) / g; wherein the polishing surface is adapted to polish a substrate and wherein the polishing surface preferably has a processing tolerance of 80%; providing an abrasive suspension, wherein the abrasive suspension comprises water and a cerium oxide abrasive; installing the substrate and the chemical mechanical polishing felt in the polishing machine; creating a dynamic contact at an interface between the chemical mechanical polishing felt and the substrate; and dispensing the abrasive slurry on the polishing surface of the polishing layer of the chemical mechanical polishing felt at or near the interface between the chemical mechanical polishing pad and the substrate; and wherein at least a certain amount of the exposed silicon oxide surface is removed by polishing the surface of the substrate and optionally treating the polishing surface with the abrasive treating agent. According to a particular characteristic of this process, the above-mentioned hardener system 10 further comprises at least one of a diamine; of a diol; an amine initiated polyol curative; and a high molecular weight polyol hardener having a number average molecular weight, MN, of 2,000 to 100,000, and an average of 3 to 10 hydroxyl groups per molecule. The present invention provides a method for mechanochemical polishing of a substrate, comprising: providing a polishing machine having a cylinder; providing a substrate, wherein the substrate has an exposed silicon oxide surface; providing a chemical mechanical polishing felt, comprising: a polyurethane polishing layer; wherein the polyurethane polishing layer is selected to have a composition, a bottom surface and a polishing surface; wherein the composition of the selected polyurethane polishing layer is the ingredient reaction product, comprising: (a) a polyfunctional isocyanate; (b) a hardener system, comprising: (i) a polyfunctional carboxylic acid-containing hardener having an average of at least two active hydrogens and at least one carboxylic acid functional group per molecule; and, (ii) at least one of a diamine; of a diol; an amine initiated polyol curative; and a high molecular weight polyol curative having a number average molecular weight, MN, of 2,000 to 100,000, and an average of 3 to 10 hydroxyl groups per molecule; and, (c) optionally, a plurality of microelements; wherein the polyurethane polishing layer composition has an acid value of 0.5 mg (KOH) / g; wherein the polishing surface is adapted to polish a substrate; providing an abrasive suspension, wherein the abrasive suspension comprises water and a cerium oxide abrasive; installing the substrate and the chemical mechanical polishing felt in the polishing machine; creating a dynamic contact at an interface between the chemical mechanical polishing felt and the substrate; and dispensing the abrasive slurry on the polishing surface of the polishing layer of the chemical mechanical polishing felt at or near the interface between the chemical mechanical polishing pad and the substrate; and wherein at least a certain amount of the exposed silicon oxide surface is removed by polishing the surface of the substrate.
    [0006] The present invention provides a method of mechanochemical polishing of a substrate, comprising: providing a polishing machine having a cylinder; providing a substrate, wherein the substrate has an exposed silicon oxide surface, optionally providing an abrasive treating agent; providing a chemical mechanical polishing felt, comprising: a polyurethane polishing layer; wherein the polyurethane polishing layer is selected to have a composition, a bottom surface and a polishing surface; wherein the composition of the selected polyurethane polishing layer is the ingredient reaction product, comprising: (a) an isocyanate-terminated urethane prepolymer, wherein the isocyanate-terminated urethane prepolymer is the reaction product of ingredients, comprising: (i) a polyfunctional isocyanate; and, (ii) a polyfunctional carboxylic acid-containing material having an average of at least two active hydrogens and at least one carboxylic acid functional group per molecule; and, (iii) a prepolymer polyol; and, (b) a hardener system, comprising at least one polyfunctional hardener; and, (c) optionally, a plurality of microelements; wherein the polyurethane polishing layer composition has an acid value of 0.5 mg (KOH) / g; wherein the polishing surface is adapted to polish a substrate and wherein the polishing surface preferably has a processing tolerance of 80%; providing an abrasive suspension, wherein the abrasive suspension comprises water and a cerium oxide abrasive; installing the substrate and the chemical mechanical polishing felt in the polishing machine; creating a dynamic contact at an interface between the chemical mechanical polishing felt and the substrate; and dispensing the abrasive slurry on the polishing surface of the polishing layer of the chemical mechanical polishing felt at or near the interface between the chemical mechanical polishing pad and the substrate; and wherein at least a certain amount of the exposed silicon oxide surface is removed by polishing the surface of the substrate, and optionally, treating the polishing surface with the abrasive treating agent. The present invention provides a method for mechanochemical polishing of a substrate, comprising: providing a polishing machine having a cylinder, a light source and a photosensor; providing a substrate, wherein the substrate has an exposed silicon oxide surface; providing a chemical mechanical polishing felt, comprising: a limit point detection window; and, a polyurethane polishing layer; wherein the polyurethane polishing layer is selected to have a composition, a bottom surface and a polishing surface; wherein the polyurethane polishing layer composition has an acid value of 0.5 mg (KOH) / g; wherein the polishing surface is adapted to polish a substrate; providing an abrasive suspension, wherein the abrasive suspension comprises water and a cerium oxide abrasive; installing the substrate and the chemical mechanical polishing felt in the polishing machine; creating a dynamic contact at an interface between the chemical mechanical polishing felt and the substrate; and dispensing the abrasive slurry on the polishing surface of the polishing layer of the chemical mechanical polishing felt at or near the interface between the chemical mechanical polishing pad and the substrate; wherein at least a certain amount of the exposed silicon oxide surface is removed by polishing the surface of the substrate; and, determining a polishing boundary point by transmitting light from the light source through the boundary point detection window and analyzing reflected light from the substrate surface back through the incident point detection window incident on the photosensor. BRIEF DESCRIPTION OF THE DRAWING Figure 1 is a graphical representation of the results of the marathon polishing experiments discussed herein in the Examples. DETAILED DESCRIPTION In conventional chemical mechanical polishing processes using cerium oxide polishing suspensions, the choice of the treatment disc may be essential to facilitate the formation and preservation of an appropriate texture on the surface. polishing the polishing layer of the chemical-mechanical polishing felt for polishing. For conventional polishing methods using conventional polyurethane polishing layers for use with cerium oxide polishing suspensions, the choice of the treatment disc has a large impact on the removal rate achieved during polishing. That is, conventional polyurethane polishing layers are known to have limited process tolerance, particularly when used with cerium oxide polishing suspensions. Stable removal rates can thus be difficult to obtain in practice. The Applicant has surprisingly found that a method for chemical mechanical polishing using cerium oxide polishing slurries, wherein the polyurethane polishing layer is selected to have an acid value of 0.5 mg. (KOH) / g provides 80% treatment tolerance. The term "polyurethane" as used herein and in the appended claims includes (a) polyurethanes formed by the reaction of (i) isocyanates and (ii) polyols (including diols); and (b) polyurethane formed from the reaction of (i) isocyanates with (ii) polyols (including diols) and (iii) water, amines (including diamines and polyamines) or a combination of water and amines (including diamines and polyamines). The term "acid number" as used herein and in the accompanying claims with reference to a polyurethane polishing layer composition is a determination of the acidic constituents in the raw material polyols used in the formation of the polishing layer composition. polyurethane expressed in milligrams of potassium hydroxide needed to neutralize one gram of raw materials, mg (KOH) / g, as determined by ASTM Test Method D7253-06 (Reapproved in 2011). The term "process tolerance" as used herein and in the appended claims with reference to the polishing surface of a polyurethane polishing layer is determined according to the following equation: CT = [(TEOSA / TE0Sm) * 100% ] where 0- is the processing tolerance (in%); TEOSA is the TEOS removal rate (in λ / min) for the polyurethane polishing layer measured according to the procedure given in the Examples using an aggressive treatment disc; and, TEOSM is the TEOS removal rate (in  / min) for the polyurethane polishing layer measured according to the procedure given in the Examples using a mild treatment disk. The chemical mechanical polishing method of a substrate of the present invention comprises: providing a polishing machine having a disk; providing a substrate, wherein the substrate has an exposed silicon oxide surface (such as a TEOS-type silicon oxide surface produced by chemical vapor deposition using tetraethyl orthosilicate as precursor); providing a chemical mechanical polishing felt, comprising: a polyurethane polishing layer; wherein the polyurethane polishing layer is selected to have a composition, a bottom surface and a polishing surface; wherein the polyurethane polishing layer composition has an acid number of 0.5 mg (KOH) / g (preferably 0.5 to 25 mg (KOH) / g, more preferably 2.5 to 20 mg (KOH) / g, more preferably 5 to 15 mg (KOH) / g, particularly preferably 10 to 15 mg (KOH) / g); wherein the polishing surface is adapted to polish a substrate; providing an abrasive suspension, wherein the abrasive suspension contains water and a cerium oxide abrasive; installing the substrate and the chemical mechanical polishing felt in the polishing machine; creating a dynamic contact at an interface between the chemical mechanical polishing felt and the substrate; and dispensing the abrasive slurry on the polishing surface of the polishing layer of the chemical mechanical polishing felt at or near the interface between the chemical mechanical polishing pad and the substrate; and wherein at least a certain amount of the exposed silicon oxide surface is removed by polishing the surface of the substrate. The present invention provides a method for mechano-chemical polishing of a substrate which comprises: providing a polishing machine having a disk; providing a substrate, wherein the substrate has an exposed silicon oxide surface; providing an abrasive treatment agent; providing a chemical mechanical polishing felt, comprising: a polyurethane polishing layer; wherein the polyurethane polishing layer is selected to have a composition, a bottom surface and a polishing surface; wherein the polyurethane polishing layer composition has an acid number of 0.5 mg (KOH) / g; wherein the polishing surface is adapted to polish a substrate and wherein the polishing surface has a processing tolerance of 80% (preferably 85%, even more preferably 90%, more preferably 95%); providing an abrasive suspension, wherein the abrasive suspension contains water and a cerium oxide abrasive; installing the substrate and the chemical mechanical polishing felt in the polishing machine; creating a dynamic contact at an interface between the chemical mechanical polishing felt and the substrate; distributing the abrasive suspension on the polishing surface of the polishing layer of the chemical mechanical polishing felt at or near the interface between the chemical mechanical polishing felt and the substrate; wherein at least a certain amount of the exposed silicon oxide surface is removed by polishing the surface of the substrate; and, treating the polishing surface with the abrasive treating agent. The chemical-mechanical polishing felt provided preferably comprises a polyurethane polishing layer, wherein the polyurethane polishing layer is selected to have a composition, a bottom surface and a polishing surface; wherein the composition of the selected polyurethane polishing layer is the ingredient reaction product, comprising: (a) a polyfunctional isocyanate; (b) a hardener system, comprising: (0) a polyfunctional carboxylic acid-containing hardener having an average of at least two active hydrogens and at least one carboxylic acid functional group per molecule; and, (c) optionally, more than one The chemical mechanical polishing pad provided further comprises a polyurethane polishing layer, wherein the polyurethane polishing layer is selected to have a composition, a bottom surface and a polishing surface; the selected polyurethane polishing layer is the reaction product of ingredients, comprising: (a) a polyfunctional isocyanate; (b) a hardener system, comprising: (i) a polyfunctional hardener containing a carboxylic acid having a mean of at least two active hydrogen and at least one carboxylic acid functional group per molecule, and, (ii) at least one of: a diamine; a diol; an amine initiated polyol hardener; and, a high molecular weight polyol curing agent having a number average molecular weight, MN, of 2,000 to 100,000 and an average of 3 to 10 hydroxyl groups per molecule; and, (c) optionally, more than one microelement.
    [0007] The chemical-mechanical polishing felt provided preferably comprises a polyurethane polishing layer, wherein the polyurethane polishing layer is selected to have a composition, a bottom surface and a polishing surface; wherein the composition of the selected polyurethane polishing layer is the ingredient reaction product, comprising: (a) an isocyanate-terminated urethane prepolymer, wherein the isocyanate-terminated urethane prepolymer is the reaction product of ingredients, comprising: (i) a polyfunctional isocyanate; and, (ii) a polyfunctional carboxylic acid-containing material having an average of at least two active hydrogen and at least one carboxylic acid functional group per molecule; and, (iii) a prepolymer polyol; and, (b) a hardener system, comprising at least one polyfunctional hardener; and, (c) optionally, a plurality of microelements.
    [0008] The polyurethane polishing layer selected for use in the method of the present invention is selected to have a polishing surface adapted to polish a substrate, wherein the substrate has an exposed silicon oxide surface (such as a surface of TEOS type silicon oxide produced by chemical vapor deposition using tetraethyl orthosilicate as a precursor). The polished substrate in the process of the present invention is preferably selected from at least one of a magnetic substrate, an optical substrate and a semiconductor substrate. The polished substrate in the process of the present invention is still more preferably a semiconductor substrate.
    [0009] The polishing surface preferably has a macro texture selected from at least one of perforations and grooves. The perforations may extend from the polishing surface in part or all through the thickness of the polyurethane polishing layer. Grooves are preferably disposed on the polishing surface so that upon rotation of the electrochemical polishing felt during polishing, at least one groove sweeps the surface of the substrate to be polished. The polishing surface preferably has a macrotexture including at least one groove selected from the group consisting of curved grooves, linear grooves, and combinations thereof. The polyurethane polishing layer selected for use in the method of the present invention preferably has a polishing surface adapted to polish the substrate, wherein the polishing surface has a macrotexture comprising a groove pattern formed therein. The groove pattern preferably comprises a plurality of grooves. The groove pattern is even better selected from a groove design. The groove design is preferably selected from the group consisting of concentric grooves (which may be circular or helical), curved grooves, hatched grooves (for example arranged as an XY grid across the felt surface), others regular designs (eg, hexagons, triangles), tire tread patterns, irregular designs (eg, fractal patterns), and combinations thereof. The groove pattern is even more preferred in the group consisting of random grooves, concentric grooves, helical grooves, hatched grooves, XY grid grooves, hexagonal grooves, triangular grooves, fractal grooves, and combinations of grooves. them. The polishing surface is much more preferably a helical groove pattern formed therein. The groove profile is preferably selected from a rectangular profile with linear side walls or the cross section of grooves may be "V" shaped, "U" shaped, sawtooth, and combinations thereof. The polyfunctional isocyanate used in the formation of the polyurethane polishing layer selected for use in the process of the present invention preferably contains an average of at least two reactive isocyanate groups (i.e., NCO) per molecule. The polyfunctional isocyanate used in the formation of the polyurethane polishing layer selected for use in the process of the present invention further contains an average of two reactive isocyanate groups (i.e., NCO) per molecule. The polyfunctional isocyanate used in the formation of the polyurethane polishing layer selected for use in the process of the present invention is preferably selected from the group consisting of a polyfunctional aliphatic isocyanate, a polyfunctional aromatic isocyanate, and a mixture of these. The polyfunctional isocyanate used in the formation of the polyurethane polishing layer selected for use in the process of the present invention is even more preferably selected from the group consisting of a diisocyanate selected from the group consisting of diisocyanate of 2, 4- toluene; 2,6-toluene diisocyanate; 4,4'-diphenylmethane diisocyanate; 1,5-naphthalene diisocyanate; tolidine diisocyanate; para-phenylene diisocyanate; xylylene diisocyanate; isophorone diisocyanate; hexamethylene diisocyanate; 4,4'-dicyclohexylmethane diisocyanate; cyclohexane diisocyanate; and, mixtures thereof. The polyfunctional isocyanate used in the formation of the polyurethane polishing layer selected for use in the process of the present invention is even better 4,4'-dicyclohexyl methane diisocyanate. The polyfunctional isocyanate is preferably combined with certain other components to form an isocyanate-terminated urethane prepolymer which is then used in forming the polyurethane polishing layer selected for use in the process of the present invention. The isocyanate-terminated urethane prepolymer used in the formation of the polyurethane polishing layer selected for use in the process of the present invention is preferably the reaction product of ingredients, comprising: a polyfunctional isocyanate; and, at least one of (i) a polyfunctional carboxylic acid-containing hardener having an average of at least two active hydrogens and at least one carboxylic acid functional group per molecule; and, (ii) a prepolymer polyol. The isocyanate-terminated urethane prepolymer used in the formation of the polyurethane polishing layer selected for use in the process of the present invention is even more preferably the ingredient reaction product, comprising: a polyfunctional isocyanate; a polyfunctional hardener containing a carboxylic acid having an average of at least two active hydrogen and at least one carboxylic acid functional group per molecule; and, a prepolymer polyol. The polyfunctional carboxylic acid-containing material used to form the isocyanate-terminated urethane prepolymer is preferably selected from the group of materials having an average of at least two active hydrogen and at least one carboxylic acid functional group per molecule, wherein the at least one carboxylic acid functional group survives the reaction to form the isocyanate-terminated urethane prepolymer. The polyfunctional carboxylic acid-containing material is even more preferably selected from the group consisting of (a) materials having a mean of two hydroxyl groups and a carboxylic acid functional group per molecule, wherein the at least one functional group of carboxylic acid survives the reaction to form the isocyanate-terminated urethane prepolymer; and (b) materials having an average of two active amine hydrogen and one carboxylic acid functional group per molecule, wherein the at least one carboxylic acid functional group survives the reaction to form the prepolymer of urethane with isocyanate terminations. The polyfunctional carboxylic acid-containing material is most preferably selected from the group consisting of materials having an average of two hydroxyl groups and one carboxylic acid functional group per molecule, wherein the at least one carboxylic acid functional group survives. the reaction to form the isocyanate-terminated urethane prepolymer. The polyfunctional carboxylic acid-containing material is even more preferably selected from the group consisting of linear polyester saturates saturated with a pendant carboxylic acid functional group, having the general formula where m and n are integers independently selected from the group consisting of from 0 to 100 (preferably from 1 to 50, more preferably from 2 to 25, most preferably from 4 to 10). The prepolymer polyol used in the preparation of the isocyanate-terminated urethane prepolymer is preferably selected from the group consisting of diols, polyols, polyol diols, copolymers thereof, and mixtures thereof. The prepolymer polyol is preferably selected from the group consisting of polyether polyols (for example poly (oxytetramethylene) glycol, poly (oxypropylene) glycol, poly (oxyethylene) glycol); polycarbonate polyols; polyester polyols; polycaprolactone polyols; mixtures thereof; and mixtures thereof with one or more low molecular weight polyols selected from the group consisting of ethylene glycol (EG); 1,2-propylene glycol; 1,3-propylene glycol; 1,2-butanediol; 1,3-butanediol; 2-methyl-1,3-propanediol; 1,4-butanediol (BDO); neopentyl glycol; 1,5-pentanediol; 3-methyl-1,5-pentanediol; 1,6-hexanediol; diethylene glycol; dipropylene glycol; and, tripropylene glycol. The prepolymer polyol is even more preferably selected from the group consisting of at least one of polycaprolactone polyols; polytetramethylene ether glycol (PTMEG); polypropylene ether glycols (PPG), and polyethylene ether glycols (PEG); optionally mixed with at least one low molecular weight polyol selected from the group consisting of ethylene glycol (EG); 1,2-propylene glycol; 1,3-propylene glycol; 1,2-butanediol; 1,3-butanediol; 2-methyl-1,3-propanediol; 1,4-butanediol (BDO); neopentyl glycol; 1,5-pentanediol; 3-methyl-1,5-pentanediol; 1,6-hexanediol; diethylene glycol; dipropylene glycol; and, tripropylene glycol. The prepolymer polyol further comprises at least one of polycaprolactone diol; ethylene glycol (EG); 1,2-propylene glycol; 1,3-propylene glycol; 1,2-butanediol; 1,3-butanediol; 2-methyl-1,3-propanediol; 1,4-butanediol (BDO); neopentyl glycol; 1,5 pentanediol; 3-methyl-1,5-pentanediol; 1,6-hexanediol; diethylene glycol; dipropylene glycol; and, tripropylene glycol. The hardener system used in forming the polyurethane polishing layer selected for use in the process of the present invention preferably comprises: at least one polyfunctional hardener. The polyfunctional hardener is selected from the group consisting of (i) diamines, (ii) diols, (iii) polyfunctional carboxylic acid-containing hardeners having an average of at least two active hydrogens and at least one carboxylic acid functional group per molecule ; (iv) amine initiated polyol curatives; and, (y) high molecular weight polyol curing agents having a number average molecular weight, MN, of 2,000 to 100,000 and an average of 3 to 10 hydroxyl groups per molecule; and mixtures thereof. The diamines are preferably selected from the group consisting of diethyltoluenediamine (DETDA); 3,5-dimethylthio-2,4-toluenediamine and isomers thereof; 3,5-diethyltoluene-2,4-diamine and isomers thereof (e.g., 3,5-diethyltoluene-2,6-diamine); 4,4'-bis- (sec-butylamino) -diphenylmethane; 1,4-bis- (secbutylamino) benzene; 4,4'-methylene-bis- (2-chloroaniline); 4,4'-methylene-bis- (3-chloro-2,6-diethylaniline) (MCDEA); poly (tetramethylene oxide) -di-p-aminobenzoate; N, N'-dialkyldiaminodiphenylmethane; p, p'-methylenedianiline (MDA); m-phenylenediamine (MPDA); 4,4'-methylene-bis- (2-chloroaniline) (MBOCA); 4,4'-methylene-bis- (2,6-diethylaniline) (MDEA); 4,4'-methylene-bis- (2,3-dichloroaniline) (MDCA); 4,4'-diamino-3,3'-diethyl-5,5'-dimethyl-diphenylmethane; 2,2 ', 3,3'-tetrachlorodiaminodiphenylmethane; trimethylene glycol dip-aminobenzoate; isomers thereof; diols; and mixtures thereof. The diamine is preferably 4,4'-methylene-bis- (2-chloroaniline) (MBOCA).
    [0010] The diols are preferably selected from the group consisting of polycaprolactone diol; ethylene glycol (EG); 1,2-propylene glycol; 1,3-propylene glycol; 1,2-butanediol; 1,3-butanediol; 2-methyl-1,3-propanediol; 1,4-butanediol (BDO); neopentyl glycol; 1,5-pentanediol; 3-methyl-1,5-pentanediol; 1,6-hexanediol; diethylene glycol; dipropylene glycol; tripropylene glycol; and, mixtures thereof. The diols are even better selected from the group consisting of polycaprolactone diol; ethylene glycol (EG); 1,2-propylene glycol; 1,3-propylene glycol; 1,2-butanediol; 1,3-butanediol; 2-methyl-1,3-propanediol; 1,4-butanediol (BDO); neopentyl glycol; 1,5-pentanediol; 3-methyl-1,5-pentanediol; i, hexanediol; diethylene glycol; dipropylene glycol; tripropylene glycol; and, mixtures thereof. The diols are even better selected from the group consisting of polycaprolactone diol; ethylene glycol (EG); 1,2butanediol; 1,3-butanediol; and, mixtures thereof. The polycaprolactone diol is preferably a polycaprolactone diol initiated with ethylene glycol. Polycaprolactone diol is even more preferably selected from materials having the general formula n OR where m and n are integers independently selected from the group consisting of 1 to 100 (preferably 1 to 50, more preferably 2 to 25; better still from 4 to 10). The polycaprolactone diol used preferably has a number average molecular weight, MM, of 1,000 to 10,000 (more preferably 1,000 to 5,000, most preferably 1,500 to 3,000).
    [0011] The polyfunctional hardeners containing a carboxylic acid are preferably selected from the group of materials having an average of at least two active hydrogen and at least one carboxylic acid functional group per molecule, wherein the at least one functional group of carboxylic acid is The carboxylic acid survives the reaction to form the polyfunctional isocyanate-terminated urethane prepolymer. Polyfunctional hardeners containing a carboxylic acid are even more preferably selected from the group consisting of (a) materials having an average of two hydroxyl groups and one carboxylic acid functional group per molecule, wherein the at least one carboxylic acid functional group survives the reaction to form the polyfunctional isocyanate-terminated urethane prepolymer; and, (b) materials having an average of two active amine hydrogen and a carboxylic acid functional group per molecule, wherein the at least one carboxylic acid functional group survives the reaction to form the prepolymer of urethane with polyfunctional isocyanate terminations. Polyfunctional hardeners containing a carboxylic acid are more preferably selected from the group consisting of materials having an average of two hydroxyl groups and one carboxylic acid functional group per molecule, wherein the at least one carboxylic acid functional group survives. the reaction to form the polyfunctional isocyanate-terminated urethane prepolymer. Polyfunctional hardeners containing a carboxylic acid are more preferably selected from the group consisting of linear polyester saturated saturated with a pendant carboxylic acid functional group, having the general formula where m and n are integers independently selected from the group 0 to 100 (preferably 1 to 50, more preferably 2 to 25, more preferably 4 to 10). The amine-initiated polyol curing agent preferably contains an average of at least one nitrogen atom (preferably one to four nitrogen atoms, more preferably two to four nitrogen atoms, and still more preferably two atoms). nitrogen) per molecule and an average of at least three (preferably three to six, more preferably three to five, most preferably four) hydroxyl groups per molecule. The amine-initiated polyol curing agent preferably has a number average molecular weight, MN, 5 700 (more preferably 150 to 650, more preferably 200 to 500, particularly preferably 250 to 300). The amine-initiated polyol curing agent preferably has a hydroxyl number (as determined by ASTM test method D4274-11) of 350 to 1200 mg KOH / g (more preferably 400 to 1000 mg KOH / g much better still 600 to 850 mg KOH / g). Examples of commercially available amine-initiated polyol curatives include the Voranol family of amine initiated polyols (available from The Dow Chemical Company); Quadrol® Specialty Polyols (N, N, N ', N'-tetrakis (2-hydroxypropylethylenediamine)) (available from BASF); Pluracol® amine-based polyols (available from BASF); Multranol® amine-based polyols (available from Bayer MaterialScience LLC); triisopropanolamine (TIPA) (available from The Dow Chemical Company); and, triethanolamine (TEA) (available from Mallinckrodt Baker Inc.). Many preferred amine-initiated polyol curatives are listed in TABLE 1. TABLE 1 Polyol Hardener Initiated by Number of MN Hydroxyl Number One amine OH groups per (mg KOH / g) molecule Triethanolamine 3 149 1130 Triisopropanolamine 3 192 877 Polyol MULTRANOL® 9138 3 240 700 Polyol MULTRANOL® 9170 3 481 350 Polyol VORANOL® 391 4 568 391 Polyol VORANOL® 640 4 352 638 Polyol VORANOL® 800 4 280 801 Polyol QUADROL® 4 292 770 Polyol MULTRANOL® 4050 4 356 630 Polyol MULTRANOL® 4063 4 488 460 Polyol MULTRANOL® 8114 4 568 395 Polyol MULTRANOL® 8120 4 623 360 Polyol MULTRANOL® 9181 4 291 770 Polyol VORANOL® 202 5 590 475 3022 815 21 The high molecular weight polyol hardener preferably has an average from three to ten (still more preferably from four to eight, more preferably from five to seven, particularly preferably six) hydroxyl groups per molecule. The high molecular weight polyol curing agent preferably has a number average molecular weight, MN, of from 2,000 to 100,000 (more preferably from 2,500 to 100,000, most preferably from 5,000 to 50,000; 7,500 to 15,000). Examples of commercially available high molecular weight polyol hardeners include Specflex® polyols, Voranol® polyols, and Voralux® polyols (available from The Dow Chemical Company); Multranol® Specialty Polyols and Ultracel® Flexible Polyols (available from Bayer MaterialScience LLC); and Plucarol® Polyols (available from BASF). Many preferred high molecular weight polyol hardeners are listed in TABLE 2.
    [0012] TABLE 2 Mass Polyol Hardener Number of MN High Molecular Hydroxyl Number OH Groups by (mg KOH / g) Molecular Polyol Multranol® 3901 3.0 6,000 28 Polyol Pluracol® 1385 3.0 3 200 50 Polyol Pluracol® 380 3 , 0 6 500 25 Polyol Pluracol® 1123 3.0 7000 24 Polyol ULTRACEL® 3000 4.0 7 500 30 Polyol SPECFLEX® NC630 4.2 7 602 31 Polyol SPECFLEX® NC632 4.7 8 225 32 Polyol VORALUX® HF 505 6.0 11 400 Polyol MULTRANOL® 9185 6.0 3 366 100 Polyol VORANOL® 4053 6.9 12 420 31 The stoichiometric ratio of the reactive hydrogen groups (i.e., the sum of the amine (NH 2) and hydroxyl (OH) groups in the unreacted isocyanate (NCO) hardener system in the polyfunctional isocyanate is 0.6 to 1.4, (more preferably 0.80 to 1.30; much better still 1.1 to 1.25). The polishing layer composition optionally further comprises a plurality of microelements. The plurality of micronutrients are preferably uniformly dispersed throughout the polishing layer selected for use in the process of the present invention. The plurality of microelements are preferably selected from entrapped gas bubbles, hollow core polymeric materials, liquid filled hollow core polymer materials, water soluble materials, and insoluble phase material (e.g. mineral oil) and a combination thereof. The multiple microelements are even more preferably selected from entrapped gas bubbles and hollow core polymer materials uniformly distributed across the polishing layer. The plurality of microelements preferably have a mass average diameter of less than 150 μm (more preferably less than 50 μm, more preferably 10 to 50 μm). The plurality of microelements preferably comprise polymeric microballoons with shell walls of either polyacrylonitrile or a polyacrylonitrile copolymer (eg Expancel® from Akzo Nobel).
    [0013] The several microelements are preferably incorporated in the polishing layer at a porosity of 0 to 35% in flight (even better a porosity of 10 to 25% in flight). The polyurethane polishing layer composition selected for use in the process of the present invention has an acid value of 0.5 mg (KOH) / g. The polyurethane polishing layer composition selected for use in the process of the present invention preferably has an acid value of 0.5 to 25 mg (KOH) / g (more preferably 2.5 to 20 mg (KOH)). more preferably 5 to 15 mg (KOH) / g, particularly preferably 10 to 15 mg (KOH) / g).
    [0014] The polyurethane polishing layer selected for use in the process of the present invention preferably has a polishing surface which has a processing tolerance. 80%. The polyurethane polishing layer selected for use in the process of the present invention preferably has a polishing surface which has a process tolerance of 85% (even more preferably 90%, most preferably 95%).
    [0015] The polishing layer selected for use in the process of the present invention may be provided in both porous and non-porous (i.e., unfilled) configurations. The polishing layer selected for use in the process of the present invention preferably has a density greater than 0.6 g / cm 3 measured according to ASTM D1622. The polishing layer selected for use in the process of the present invention even more preferably has a density of 0.6 to 1.5 g / cm 3 (even more preferably 0.7 to 1.3 g / cm 3; 0.95 to 1.25 g / cm 3) measured according to ASTM D 1622.
    [0016] The polishing layer selected for use in the process of the present invention preferably has a Shore D hardness of from 5 to 80 measured according to ASTM D2240. The polyurethane polishing layer selected for use in the process of the present invention further has a Shore D hardness of 40 to 80 (more preferably 50 to 70, most preferably 60 to 70) measured according to ASTM D2240. The polishing layer selected for use in the process of the present invention preferably has an elongation at break of 100 to 500% measured according to ASTM D412. The polyurethane polishing layer selected for use in the process of the present invention preferably has an elongation at break of 100 to 450% (more preferably 125 to 450%) measured according to ASTM D412. The polyurethane polishing layer selected for use in the process of the present invention preferably contains <1 ppm of abrasive particles incorporated therein. The chemical mechanical polishing felt provided for use in the process of the present invention is preferably adapted to operate with a cylinder of a polishing machine. The chemical mechanical polishing felt provided for use in the process of the present invention is preferably adapted to be assembled with the cylinder of the polishing machine. The chemical mechanical polishing felt provided for use in the process of the present invention may preferably be assembled with the cylinder using at least one pressure sensitive adhesive and vacuum. The chemical mechanical polishing felt provided for use in the method of the present invention preferably further comprises a pressure sensitive cylinder adhesive to facilitate attachment to the barrel. Those skilled in the art will know how to choose a pressure sensitive adhesive suitable for use as the pressure sensitive cylinder adhesive. The chemical mechanical polishing felt provided for use in the process of the present invention will preferably also include a release protector applied to the pressure sensitive cylinder adhesive. The chemical mechanical polishing felt provided for use in the process of the present invention optionally further comprises at least one additional layer joined with the polyurethane polishing layer. An important step in substrate polishing operations is the determination of a process end point. A popular in situ method for limit point detection involves providing a chemical mechanical polishing felt with a window, which is transparent to select wavelengths of light. During polishing, a beam of light is directed through the window to the wafer surface, where it is reflected back through the window to a sensor (e.g. a spectrophotometer). On the basis of the feedback signal, the properties of the substrate surface (e.g. the film thickness thereon) can be determined for the endpoint detection. The chemical mechanical polishing felt of the present invention further optionally includes a limit point detection window to facilitate such boundary-point methods on the basis of light. The limit point detection window is preferably selected from an integral window incorporated in the polyurethane polishing layer; and, a plug window block in place embedded in the chemical mechanical polishing felt. Those skilled in the art will be able to choose a suitable building material for the end point detection window to be used in the projected polishing process. The abrasive suspension provided for use in the process of the present invention preferably comprises a cerium oxide abrasive and water (preferably at least one of deionized water and distilled water). The ceria abrasive abrasive in the abrasive suspension provided for use in the process of the present invention preferably has an average particle size of 3 to 300 nm dispersion (preferably 25 to 250 nm; from 50 to 200 nm, more preferably from 100 to 150 nm). The abrasive suspension provided for use in the process of the present invention preferably has a cerium oxide abrasive content of 0.001 to 10% by weight (more preferably 0.01 to 5% by weight; 0.1 to 1% by weight). The pH of the abrasive suspension provided for use in the process of the present invention preferably has a pH of 2 to 13 (preferably 4 to 9, more preferably 5 to 8, most preferably 5 to 6).
    [0017] The abrasive suspension provided for use in the process of the present invention optionally further comprises a dispersing agent (for example a poly (acrylic acid), an ammonium salt of a poly (acrylic acid)), a stabilizer, a oxidizing agent, a reducing agent, a pH adjusting agent (for example inorganic acids, such as nitric acid, organic acids, such as citric acid), a pH buffer (for example, quaternary ammonium hydroxide, such as tetramethylammonium hydroxide); and, an inhibitor. Some embodiments of the present invention will now be described in detail in the following examples.
    [0018] Comparative Examples C1-C2 and Examples 1-6 Preparation of a Polyurethane Polishing Layer The polyurethane polishing layer according to Comparative Example C1 was prepared by the controlled mixture of (a) the end-urethane prepolymer. isocyanate at 51 ° C; (b) the hardener system; and, (c) the several microelements (i.e. Expancel® 551DE20d60 pore-forming agent) cited in TABLE 3. The ratio of isocyanate-terminated urethane prepolymer and hardener system was attached so that the stoichiometry, as defined by the ratio of the active hydrogen groups (i.e., the sum of -OH groups and -NH 2 groups) in the unreacted isocyanate group hardener system. (NCO) in the isocyanate-terminated urethane prepolymer was as shown in TABLE 3. The several microelements were mixed in the isocyanate-terminated urethane prepolymer prior to addition of the hardener system. The isocyanate-terminated urethane prepolymer with the several microelements incorporated and the hardener system were then mixed together using a high shear mixing head. After the release of the mixing head, the combination was dispensed over a period of five minutes in a circular mold with a diameter of 86.4 cm (34 inches) to provide a total pouring thickness of approximately 8 cm (3 inches). . The dispensed combination was allowed to gel for 15 minutes before placing the mold in a curing oven. The mold content was then cured in the curing oven using the following cycle: 30 minute ramp from oven temperature adjustment point point from room temperature to 104 ° C, then hold for 15, 5 hours with a furnace adjustment point temperature of 104 ° C, and then ramp 2 hours of furnace adjustment point temperature of 104 ° C reducing to 21 ° C.
    [0019] The cured polyurethane cake was then removed from the mold and sliced (cut using a moving blade) at a temperature of 30 to 80 ° C in multiple polyurethane polishing layers according to Comparative Example C.1. average thickness, Tp_moy, 2.0 mm (80 thousandths of an inch). Slicing was initiated from the top of the cake. The polyurethane polishing layers were prepared according to Comparative Example C2 and Examples 1-6 as single sheets using a deposition technique. A vortex mixer was used to mix (a) the isocyanate-terminated prepolymer at 60 ° C; (b) the hardener system; and, (c) the several microelements (ie Expancel® 551DE20d60 pore-forming agent) cited in TABLE 3 respectively for each of Examples 1-6. The ratio of isocyanate-terminated urethane prepolymer and hardener system was set so that stoichiometry, as defined by the ratio of active hydrogen groups (i.e. the sum of OH groups and NH 2 groups ) in the unreacted isocyanate group (NCO) hardener system in the isocyanate-terminated urethane prepolymer was as shown in TABLE 3. The several microelements were mixed in the isocyanate-terminated urethane prepolymer before the addition of the hardener system. The isocyanate-terminated urethane prepolymer with the several microelements incorporated and the hardener system were then mixed together using a vortex mixer for 30 seconds. After mixing, the combination was cast into a sheet of approximately 60 by 60 cm (24 by 24 inches) with a thickness of approximately 2 mm (80 thousandths of an inch) using a deposition bar or doctor blade. The dispensed combination was allowed to gel for 15 minutes before placing the mold in a curing oven. The contents of the mold were then cured in the curing oven using the following cycle: 30-minute ramp from the temperature of the oven adjustment point from room temperature to 104 ° C, then hold for 15, 5 hours with a furnace adjustment point temperature of 104 ° C, and then 2 hour ramp from the oven adjustment point temperature of 104 ° C reducing to 21 ° C.
    [0020] Analysis of the properties of the polyurethane polishing layer The non-grooved polyurethane polishing layer material prepared according to Comparative Examples C1-C2 and Example 1 was analyzed each time with the addition of the polyurethane polishing agent. pore (Expancel® material) and according to Examples 1-6 without the addition of the pore-forming agent (Expancel® material) to determine the physical properties mentioned in TABLE 4. It is noted that the density quoted was determined compared to pure water according to ASTM D1622; the Shore D hardness quoted was determined according to ASTM D2240.
    [0021] The tensile properties of the polyurethane polishing layer (ie, average tensile strength, average elongation at break, average modulus, toughness) were measured according to ASTM D412 using an Alliance mechanical test device. RT / 5 available from MTS Systems Corporation as traverse speed of 50.8 cm / min. The entire test was conducted in a temperature and humidity controlled laboratory adjusted to 23 ° C and a relative humidity of 50%. All test samples were processed under the laboratory conditions cited for 5 days prior to testing. The cited average tensile strength (MPa) and the average elongation at break (%) for the polyurethane polishing layer material were determined from stress-strain curves of five duplicate samples. The storage modulus, G ', and the loss module, G ", were measured for the polyurethane polishing layer material according to ASTM D5279-08 using a TA Instruments ARES Rheometer with torsion fixings. used liquid nitrogen which was connected to the instrument for temperature control below ambient temperature The linear viscoelastic response of the samples was measured at a test frequency of 10 rad / sec (1.59 Hz) with a temperature ramp of 3 ° C / min from -100 ° C to 200 ° C. Test samples were punched from the polyurethane polishing layer using a 47.5 mm x 7 mm die on an Indusco hydraulic swing arm cutting machine and then cut to a length of approximately 35 mm using scissors TABLE 3 Ex No. Isocyanate Hardener set (% by weight) Stoichiometry (Active H / NCO) Agent of Polyfunctional Training Agent Ex Pore Formation pore pancel® (% by weight) Diamines Diols MBOCA BDO EG EF Cl A 100 - - - 0.97 551DE20d60 2.0 C2 D - - 16.6 83.4 1.0 551DE20d60 2.3 1 D - - 16.6 83.4 - 1.0 551DE20d60 2.3 2 Combination at 60/40% - 100 - - - 0.95 551DE20d60 2.7 in weight of B and D 3 C 66.9 33.1 - - 1.0 551DE20d60 2.7 4 Combination at 55.6 / 44.4% by weight of Cet D - 100 - - - 0.95 551DE20d60 2, 7 D - - 16.6 19.2 64.3 1.0 551DE20d60 2.4 6 D - - 16.6 3.9 79.5 1.0 551DE20d60 2.4 A is a prepolymer of isocyanate-terminated urethane with 7% NCO comprising a 50/50% by weight combination of Adiprene LFG963A and Adiprene® LF750D available from Chemtura. B is an isocyanate-terminated urethane prepolymer with 9.69% NCO formed as the reaction product of 39.4% by weight of 4,4'-dicyclohexylmethane diisocyanate and 60.6% by weight of a polyfunctional material containing a carboxylic acid having the general formula wherein m and n are integers from 4 to 10 (commercially available from GEO Specialty Chemical as functional saturated polyester polyol DICAP® 2020). C is an isocyanate-terminated urethane prepolymer with 9.60% NCO formed as the reaction product of 45.0% by weight 4,4'-dicyclohexylmethane diisocyanate; 51.5% by weight of a polycaprolactone diol having the general formula COOH O CH, wherein m and n are integers from 4 to 10, wherein the polycaprolactone diol has a number average molecular weight, MN of 2000 ( commercially available from The Perstorp Group as linear polycaprolactone diol CAPA® 2201A); and 3.4% by weight of dimethylolpropionic acid (DMPA). D is an MDI prepolymer having 23.0% NCO available from The Dow Chemical Company as Isonate 181. E is a polyfunctional carboxylic acid-containing material having the general formula CH, where m and n are integers from 4 to (Commercially available from GEO Specialty Chemical as DICAP® 2020 acid saturated functional polyol). F is a polycaprolactone diol having the general formula wherein m and n are integers from 10 to 20, wherein the polycaprolactone diol has a number average molecular weight, MN, of 2,000 (commercially available from The Perstorp Group as polycaprolactone) linear diol CAPA® 2209). TABLE 4 Ex. No. of polishing layer Properties Density Shore D hardness (15 s) Resistance to elongation at break G 'to G' to modulus (MPa) Toughness (MPa) tensile strength (%) 30 ° C 30 ° C / G '(MPa) (MPa) at 90 ° C Cl 0.82 47 19.0 230 - 2.7 185 35.3 C2 0.79 49 12.9 52 148 2.5 156 5.1 1 0 , 80 44 13.7 130 62 4.5 119 14.9 2 1.14 62 28.4 127 200.0 7.2 263 30.1 3 1.14 60 33.0 206 145.0 8.0 295 50.6 4 1.13 68 33.1 29 264.0 12.6 535 7.4 5 1.21 59 30.4 417 118.0 3.1 189 95.9 6 1.21 59 31.5 412 133.0 2.8 191 97.7 COOH Comparative Example PC2 and Example Pl Marathon Polishing Examples The polyurethane polishing layers prepared according to Comparative Example C2 and Example 1 were laminated to a SubaTM IV sub-felt ( commercially available from Rohm and Haas CMP Electronic Materials Inc.) using a pressure-sensitive adhesive for each of Comparative Example PC2 and Example P1. Each of the examples of Marathon polishing was performed using Eighty (80) 200-mm 200-mm TEOS sheet wafers from Novellus Systems. An Applied Materials 200 mm Mirra® polishing device was used. All polishing experiments were performed using a downward force of 20.7 kPa (3 psi), a chemical mechanical polishing slurry feed rate of 150 ml / min, a table spin speed of 93 rpm. min and a carrier rotation speed of 87 rpm. The chemical mechanical polishing slurry composition used was a 1: 1 dilution of Asahi CES 333 slurry with deionized water, a pH of 5.1 and a 1.5 μm line adjuster. A CG181060 diamond felt treating agent (commercially available from Kinik Company) was used to treat the polishing surface. The polishing surface was broken with the treating agent using a 7 pounds (3.18 kg) down force for 40 minutes. The polishing surface was further processed in situ during polishing at 10 sweeps / min from 1.7 to 9.2 inches from the center of the polishing felt with a high progeny of 7 pounds (3.18 kg). Shrinkage rates were determined by measuring film thickness before and after polishing using a KLA-Tencor FX200 metrology tool using a 49-point helical scan with an edge exclusion of 3 mm. The results of the Marathon withdrawal speed experiments are provided in Figure 1.
    [0022] Comparative Example MPC1 and Examples MP2-MP6 Polishing Examples with Gentle Treatment The polyurethane polishing layers prepared according to Comparative Example C1 and Examples 2-6 were laminated to a SubaTM IV sub-felt (commercially available from Rohm and Haas 3022 815 32 Electronic Materials CMP Inc.) using a pressure-sensitive adhesive for each of comparative example MPC1 and MP2-MP6 examples. The polishing shrinkage velocity experiments were performed on 200-mm 200-mm TEOS sheet wafers from Novellus Systems. An Applied Materials 200 mm Mirra® polishing device was used. All polishing experiments were performed using a downward force of 20.7 kPa (3 psi), a chemical mechanical polishing slurry feed rate of 150 ml / min, a table spin speed of 93 rpm. min and a carrier rotation speed of 87 rpm. The chemical mechanical polishing slurry composition used was a 1: 3 dilution of Asahi CES333F slurry with deionized water and a pH of 5.1. A CS211250-1FN diamond felt treating agent (commercially available from Kinik Company) was used to treat the polishing surface. The polishing surface was broken with the treating agent using a 7 pounds (3.18 kg) down force for 40 minutes. The polishing surface was further processed in situ during polishing at 10 sweeps / min from 1.7 to 9.2 inches from the center of the polishing felt with a strong 7 pound descendant (3.18 kg). Shrinkage rates were determined by measuring the film thickness before and after polishing using a KLA-Tencor FX200 metrology tool using a 49-point helical scan with an edge exclusion of 3 mm. The results of the withdrawal rate experiments with treatment are provided in TABLE 5.
    [0023] TABLE 5 EX Polishing layer TEOS removal rate (λ / min) MPC1 Cl 1 905 MP2 2 2 542 MP3 3 2 474 MP4 4 2 948 MP5 5 2 260 MP6 6 2 023 Comparative Example APC1 and Examples AP2-AP6 Examples Polishing with Aggressive Treatment The polyurethane polishing layers prepared according to Comparative Example C1 and Examples 2-6 were laminated to SubaTM IV Sub-felt (commercially available from Rohm and Haas Electronic Materials CMP Inc.). using a pressure-sensitive adhesive for each of Comparative Example APC1 and Examples AP2-AP6. Polishing shrinkage speed experiments were performed on 200-mm 200-mm TEOS control wafers from Novellus Systems. Applied Materials 200 mm Mirra® polishing device was used. All polishing experiments were performed using a downward force of 20.7 kPa (3 psi), a 150 ml chemical mechanical polishing slurry flow rate. / min, a table speed of 93 rpm and a rotational speed of 87 rpm. The chemical mechanical polishing slurry composition used was a 1: 3 dilution of Asahi CES33F slurry with deionized water and a pH of 5.1. An 8031C1 diamond felt treating agent (commercially available from Saesol Diamond Ind. Co., Ltd.) was used to treat the polishing surface. The polishing surface was broken with the treating agent using a 7 pounds (3.18 kg) down force for 40 minutes. The polishing surface was further processed in situ during polishing at 10 sweeps / min from 1.7 to 9.2 inches from the center of the polishing felt with a strong 7 pound descendant (3.18 kg). Shrinkage rates were determined by measuring the film thickness before and after polishing using a KLA-Tencor FX200 metrology tool using a 49-point helical scan with an edge exclusion of 3 mm. The results of the aggressive shrinkage speed experiments are provided in TABLE 6. The polishing layer processing tolerance calculated from the shrink rate experiments is given in TABLE 7.
    [0024] TABLE 6 Ex Polishing layer Removal rate of TEOS (λ / min) APC1 Cl 1 228 AP2 2 2 382 AP3 3 2 333 AP4 4 2 814 AP5 5 2 011 AP6 6 1 704 TABLE 7 Polishing layer Tolerance of treatment (%) Cl 64.5 2 93.7 3 94.3 4 95.5 89.0 6 84.2
    权利要求:
    Claims (10)
    [0001]
    REVENDICATIONS1. A process for mechanical-chemical polishing of a substrate characterized in that it comprises: providing a polishing machine having a cylinder; providing a substrate, wherein the substrate has an exposed silicon oxide surface; providing a chemical mechanical polishing felt, comprising: a polyurethane polishing layer; wherein the polyurethane polishing layer is selected to have a composition, a bottom surface and a polishing surface; wherein the polyurethane polishing layer composition has an acid value of 0.5 mg (KOH) / g; wherein the polishing surface is adapted to polish a substrate; providing an abrasive suspension, wherein the abrasive suspension comprises water and a cerium oxide abrasive; installing the substrate and the chemical-mechanical polishing felt in the polishing machine; creating a dynamic contact at an interface between the chemical mechanical polishing felt and the substrate; and dispensing the abrasive slurry on the polishing surface of the polyurethane polishing layer of the chemical mechanical polishing felt at or near the interface between the chemical mechanical polishing pad and the substrate; and wherein at least a certain amount of the exposed silicon oxide surface is polished off the surface of the substrate.
    [0002]
    2. Method according to claim 1, characterized in that the substrate provided is selected from at least one magnetic substrate, an optical substrate and a semiconductor substrate.
    [0003]
    The method of claim 1, further comprising: providing an abrasive treating agent; and, treating the polishing surface with the abrasive treating agent.
    [0004]
    4. Method according to claim 3, characterized in that the polishing surface has a processing tolerance of 80%.
    [0005]
    The method of claim 4, characterized in that the composition of the polyurethane polishing layer is the ingredient reaction product, comprising: (a) a polyfunctional isocyanate; (b) a hardener system comprising: (i) a polyfunctional carboxylic acid-containing hardener having an average of at least two active hydrogens and at least one carboxylic acid functional group per molecule; and, (c) optionally, more than one microelement.
    [0006]
    6. Method according to claim 5, characterized in that the hardener system further comprises at least one of: a diamine; a diol; an amine initiated polyol curing agent; and a high molecular weight polyol curing agent having a number average molecular weight, MN, of 2,000 to 100,000 and an average of 3 to 10 hydroxyl groups per molecule.
    [0007]
    The method of claim 4, characterized in that the composition of the selected polyurethane polishing layer is the ingredient reaction product, comprising: (a) an isocyanate-terminated urethane prepolymer, wherein the prepolymer isocyanate-terminated urethane is the reaction product of ingredients, comprising: (i) a polyfunctional isocyanate; and, (ii) a polyfunctional carboxylic acid-containing material having an average of at least two active hydrogen and at least one carboxylic acid functional group per molecule; and, (iii) a prepolymer polyol; and, (b) a hardener system comprising at least one polyfunctional hardener; and, (c) optionally, more than one microelement.
    [0008]
    8. The method of claim 1, characterized in that the polishing machine provided further has a light source and a photosensor; the chemical-mechanical polishing felt provided further comprises a limit point detection window; and, the method further comprises: determining a polishing boundary point by transmitting light from the light source through the boundary point detection window and analyzing the light reflected from the surface of the light source. substrate back through the incident point detection window incident on the photosensor.
    [0009]
    The method of claim 1, characterized in that the chemical-mechanical polishing felt provided further comprises: a pressure-sensitive cylinder adhesive layer having a stacking side and a cylinder side; the stacking side of the pressure sensitive cylinder adhesive layer being adjacent to the bottom surface of the polyurethane polishing layer.
    [0010]
    10. A method according to claim 9, characterized in that the provided chemical mechanical polishing felt further comprises: at least one additional layer joined with and interposed between the bottom surface of the polyurethane polishing layer and the side of the polyurethane polishing layer; stacking of the pressure sensitive cylinder adhesive layer.
    类似技术:
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    同族专利:
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    优先权:
    申请号 | 申请日 | 专利标题
    US14314355|2014-06-25|
    US14/314,355|US20150375361A1|2014-06-25|2014-06-25|Chemical mechanical polishing method|
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