MECANO-CHEMICAL POLISHING FELT WITH FLEXIBLE WINDOW AND TREATMENT-FRIENDLY

专利摘要:
There is provided a chemical mechanical polishing felt (10) having a polishing layer (20); and a window (30) incorporated in the polishing layer; wherein the polishing layer comprises an ingredient reaction product, comprising: a polishing layer prepolymer and a polishing layer hardener system; wherein the polishing layer hardener system comprises an amine initiated polyol polishing layer hardener, a high molecular weight polyol polishing layer hardener and a difunctional polishing layer hardener; and wherein the window comprises an ingredient reaction product comprising: a window prepolymer and a window hardener system; wherein the window hardener system comprises a difunctional window hardener; an amine initiated polyol window hardener and a high molecular weight polyol window hardener; and, wherein the polishing layer has a density ≥ 0.6 g / cm3; a Shore D hardness of 5 to 40; an elongation at break of 100 to 450%; and, a cutting speed of 25 to 150 μm / h.
公开号:FR3019077A1
申请号:FR1552552
申请日:2015-03-26
公开日:2015-10-02
发明作者:Bainian Qian；Marty W Degroot；Michelle K Jensen；James Murnane；Jeffrey J Hendron；John G Nowland；David B James；Fengji Yeh
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 chemical mechanical polishing felts and methods of making and using them. The present invention more particularly relates to a chemical-mechanical polishing felt comprising a polishing layer and a limit-point detection window incorporated in the polishing layer, wherein the polishing layer has a density greater than 0.6 g / cm 3 ; a Shore D hardness of 5 to 40; an elongation at break of 100 to 450%; and, a cutting speed of 25 to 150 pm / hr; and wherein the polishing layer has a polishing surface adapted to polish a substrate. In the manufacture of integrated circuits and other electronic devices, multiple layers of conductive, semiconductor and dielectric materials are deposited on and removed from a surface of a semiconductor wafer. Thin layers of conductive, semiconductor and dielectric materials can be deposited by many deposition techniques. Conventional deposition techniques in modern wafer processing include physical vapor deposition (PVD), also known as sputtering, chemical vapor deposition (CVD), plasma enhanced chemical vapor deposition (PECVD) and electro-chemical plating, among others. Typical shrinkage techniques include wet and dry isotropic and anisotropic etching, among others. When the layers of materials are successively deposited and removed, the upper surface of the slab becomes non-planar. Since the subsequent processing of the semiconductor (eg metallization) requires the wafer to have a flat surface, the wafer must be planarized. Planarization is useful for removing unwanted surface topography and surface defects, such as rough surfaces, agglomerated materials, crystal lattice deterioration, scratches, and polluted layers or materials.
[0002] Mechano-chemical planarization, or mechano-chemical polishing (CMP) is a conventional technique used to planarize or polish machined parts, such as semiconductor wafers. In a conventional CMP, a wafer carrier, or polishing head, is attached to a carrier assembly. The polishing head supports the wafer and positions the wafer in contact with a polishing layer of a polishing felt which is fixed on a table or cylinder in a CMP apparatus. The support assembly provides an adjustable pressure between the wafer and the polishing felt. A polishing medium (e.g. a suspension) is simultaneously dispensed onto the polishing felt and is drawn into the gap between the wafer and the polishing layer. The polishing felt and the wafer typically rotate relative to one another to effect polishing. When the polishing felt rotates below the wafer, the wafer scans a typically annular polishing path, or polishing region, in which the surface of the wafer is directly confronted with the polishing layer. The wafer surface is polished and made flat by the chemical and mechanical action of the polishing layer and the polishing medium on the surface. Felt surface "treatment" or "finishing" is critical to maintaining a consistent polishing surface for stable polishing performance. The polishing surface of the polishing felt wears over time, smoothing the microtexture of the polishing surface - a phenomenon called "glazing". The treatment of the polishing felt is typically accomplished by mechanical abrasion of the polishing surface with a treatment disk. The treatment disk has a rough treatment surface typically consisting of recessed diamond points. The treatment disk is brought into contact with the polishing surface either during intermittent interruptions in the CMP process when the polishing is quiescent ("ex situ"), or while the CMP process is in progress ("in situ" ). The treatment disk typically rotates in a position which is fixed relative to the axis of rotation of the polishing felt, and scans an annular treatment region as the polishing felt rotates. The treatment method, as described, cuts microscopic grooves into the polishing surface, abrading and planing both the felt material and renewing the polishing texture.
[0003] Semiconductor devices are becoming more complex with thinner aspects and more layers of metallization.
[0004] This trend requires improved performance for polishing consumables in order to maintain planarity and limit polishing defects. These can create breaks or short-circuits in the conductive lines that would render the semiconductor device non-functional. It is generally known that an approach to reduce polishing defects, such as micro-scratches or machining marks, is to use a softer polishing felt. A family of flexible polyurethane polishing layers is described by James et al. in U.S. Patent 7,074,115. James et al. Disclose a polishing felt comprising the reaction product of an isocyanate-terminated urethane prepolymer with an aromatic diamine or polyamine hardener, wherein the reaction product has a porosity of at least 0.1 volume percent , and a KEL energy loss factor at 40 ° C and 1 rad / s from 385 to 750 I / Pa, and an E 'module at 40 ° C and 1 rad / s from 100 to 400 MPa. As described above, it is necessary to diamond treat the surface of chemical-mechanical polishing felts to create an advantageous micro-texture for optimum polishing performance. However, it is difficult to create such a texture in conventional polishing layer materials, such as those described by James et al. since these materials have high ductility, as measured by tensile elongation values. As a result, when these materials are subjected to treatment with a diamond treatment disc, rather than cutting grooves in the surface of the felt, the diamonds in the processing disc simply push the felt material onto the side without cutting. A very small texture is thus created in the surface of these conventional materials as a result of treatment with a diamond treatment disk. Another problem with these conventional chemical mechanical polishing felts materials occurs during the machining process to form patterns of macro-grooves in the felt surface. Conventional chemical mechanical polishing felts are typically provided with groove pattern cutting in their polishing surfaces to promote slurry flow and to remove polishing debris from the felt-wafer interface. Such grooves are frequently cut into the polishing surface of the polishing felt either by using a lathe or by a CNC grinding machine. With soft felting materials, however, a problem similar to that of a diamond treatment appears, such that after the cutting end is passed, the felt material simply connects and the formed grooves are closed again. herself. The quality of the grooves is thus poor and it is more difficult to successfully manufacture commercially acceptable felts with such flexible materials. This problem becomes worse when the hardness of the felt material decreases.
[0005] Another challenge presented by chemical mechanical polishing is the determination of when the substrate has been polished to the desired extent. In situ processes for determining the polishing endpoints have been developed. In situ limiting point optical techniques can be classified into two basic categories: (1) control of the reflected optical signal at a single wavelength or (2) control of the reflected optical signal from lengths of d multiple waves. Typical wavelengths used for the optical determination of the limiting point include those of the visible spectrum (for example from 400 to 700 nm), the ultraviolet spectrum (315 to 400 nm), and the infrared spectrum (for example 700 at 1000 nm). In U.S. Patent 5,433,651, Lustig et al. have described a single-wavelength polymer end point detection method in which light from a laser source is transmitted on a wafer surface and the reflected signal is monitored. When the composition on the wafer surface changes from one metal to another, the reflection coefficient varies. This variation of the reflection coefficient is then used to detect the polishing end point. In U.S. Patent 6,106,662, Bibby et al. described the use of a spectrometer to obtain a spectrum of intensity of light reflected in the visible light range of the optical spectrum. In metal CMP applications, Bibby et al. cite the use of the entire spectrum to detect the polishing end point. Mechano-chemical polishing felts with windows have been developed to adapt these optical endpoint determination techniques. Roberts describes, for example, in U.S. Patent 5,605,760 a polishing felt in which at least a portion of the felt is transparent to laser light over a wavelength range. Roberts cites in some of the disclosed embodiments a polishing felt that includes a transparent window piece in an otherwise opaque felt. The window piece may be a bar or a clear polymer plug in a molded polishing felt. The bar or plug may be inserted in the molded state into the polishing felt (ie, an "integral window"), or may be installed in a blank in the polishing felt after the molding (ie a "plug-in-place window" or "plug10 in-place window"). Aliphatic isocyanate-based polyurethane materials, such as those disclosed in U.S. Patent 6,984,163, have provided improved light transmission over a broad spectrum of light. The necessary durability required for demanding polishing applications is unfortunately lacking in these aliphatic polyurethane windows, inter alla. Conventional polymer-based endpoint detection windows often have disadvantageous degradation when exposed to light having a length of 330 to 425 nm. However, increasing pressure is being used to utilize light with shorter wavelengths for endpoint detection purposes in semiconductor polishing applications to facilitate thinner material layers and sizes. smaller devices. In addition, semiconductor devices are becoming increasingly complex with finer aspects and more metallization layers. This trend requires improved performance for polishing consumables in order to maintain planarity and limit polishing defects. These may create breaks or short circuits in the conductive lines that would render the semiconductor device non-functional. It is generally known that one approach to reduce polishing defects, such as micro scratches or machining marks, is to use a softer polishing layer material. There is therefore a trend towards using softer polishing layer materials to facilitate improved defectivity performance. Nevertheless, conventional window formulations do not adapt well to such softer polishing layer materials, tending to increase polishing defectivity. There is therefore a continuing need for chemical mechanical polishing felts that provide a physical property profile that correlates well with that associated with low-defect formulations, but that also imparts improved processability to the polishing layer ( i.e., has a cutting speed of 25 to 150 pm / hr) and polymer formulations of end point detection windows for use in such chemical mechanical polishing felts. In particular, there is a continuing need for polymeric end point detection polymer formulations having a Shore D hardness of 50, coupled with an elongation at break of 5. 400%; wherein the window formulations have the durability required for demanding polishing applications.
[0006] The present invention provides a chemical-mechanical polishing cloth comprising a polishing layer having a polishing surface, a base surface and an average thickness, Tp-av, measured in a direction perpendicular to the polishing surface from the surface. polishing to the base surface; and a limit point detection window embedded in the polishing layer; wherein the polishing layer comprises an ingredient reaction product comprising a polishing layer prepolymer, wherein the polishing layer prepolymer is selected from the group consisting of isocyanate-terminated urethane prepolymers having from 2 to 12 % by weight of unreacted NCO groups; and a polishing layer hardener system comprising at least 5% by weight of an amine initiated polyol polishing layer hardener having at least one nitrogen atom per molecule and an average of at least three groups hydroxyl per molecule; from 25 to 95% by weight of a high molecular weight polyol polishing layer hardener having a number average molecular weight, MN, of 2,500 to 100,000 and an average of 3 to 10 hydroxyl groups per molecule; and from 0 to 70% by weight of a difunctional polishing layer hardener; wherein the endpoint detection window comprises an ingredient reaction product, comprising a window prepolymer, wherein the window prepolymer is selected from the group consisting of isocyanate-terminated urethane prepolymers having from 2 to 6, 5% by weight of unreacted NCO groups; and, a window hardener system comprising at least 5% by weight of a difunctional window hardener; at least 5% by weight of an amine initiated polyol window hardener having at least one nitrogen atom per molecule and an average of at least three hydroxyl groups per molecule; and from 25 to 90 by weight of a high molecular weight polyol window hardener having a number average molecular weight, MN, of 2,000 to 100,000 and an average of three to ten hydroxyl groups per molecule; Wherein the polishing layer has a density k 0.6 g / cm 3; a Shore D hardness of 5 to 40; an elongation at break of 100 to 450%; and, a cutting speed of 25 to 150 mph. In a particular embodiment, the polishing surface is adapted to polish a substrate selected from a magnetic substrate, an optical substrate and a semiconductor substrate. In a particular embodiment, the chemical mechanical polishing felt of the invention further comprises a rigid layer having a top surface and a bottom surface; and, a hot melt adhesive interposed between the base surface of the polishing layer and the upper surface of the rigid layer; wherein the hot melt adhesive bonds the polishing layer to the rigid layer. In a particular embodiment, the chemical mechanical polishing felt of the invention further comprises an adhesive responsive to the cylinder pressure; wherein the cylinder pressure sensitive adhesive is disposed on the bottom surface of the rigid layer; and, a detachable liner; wherein the cylinder pressure sensitive adhesive is interposed between the bottom surface of the rigid layer and the detachable liner. In a particular embodiment, the window hardener system has a reactive hydrogen group concentration and the window prepolymer has an unreacted NCO group concentration; and wherein the reactive hydrogen group concentration divided by the unreacted NCO group concentration is 0.7 to 1.2. In a particular embodiment, the limit point detection window has a density 1 g / cm3; porosity less than 0.1% in flight; a Shore D hardness of 10 to 50; elongation at break 5. 400%; and a 800-pass double pass transmission, DPT800, of 30 to 100 ° / 0. In a particular embodiment, the boundary point detection window also has a 400 nm double pass transmission, DPT400, of 25 to 100 ° h. In a particular embodiment, the polishing layer hardener system contains from 5 to 20% by weight of the amine initiated polyol polishing layer hardener, wherein the polyol polishing layer hardener initiated by amine has two nitrogen atoms per molecule, an average of four hydroxyl groups per molecule, and a number average molecular weight, MN, of 200 to 400; from 50 to 75% by weight of the high molecular weight polyol polishing layer hardener, wherein the high molecular weight polyol polishing layer hardener has a number average molecular weight, MN, of 10,000 to 12 000; and an average of six hydroxyl groups per molecule; from 10 to 30% by weight of the difunctional polishing layer hardener; wherein the difunctional polishing layer hardener is a diamine hardener selected from the group consisting of 4,4-methylene-bis- (2-chloroaniline) (MBOCA); 4,4'-methylene-bis- (3-chloro-2,6-diethylaniline) (MCDEA); and isomers thereof; wherein the polishing layer hardener system has a plurality of reactive hydrogen moieties and the polishing layer prepolymer has a plurality of unreacted NCO moieties; wherein the molar ratio of reactive hydrogen moieties in the polishing layer hardener system to unreacted isocyanate groups in the polishing layer prepolymer is from 0.95 to 1.05; and wherein the polishing layer has a density of 0.75 to 1.0 g / cm3; a Shore D hardness of 5 to 20; an elongation at break of 150 to 300%; and, a cutting speed of 30 to 60 pm / h. The invention also relates to a chemical mechanical polishing felt, comprising: a polishing layer having a polishing surface, a base surface and an average thickness, Tp-m oy, measured in a direction perpendicular to the polishing surface from the polishing surface to the base surface; and, a limit point detection window incorporated into the polishing layer; wherein the polishing layer comprises an ingredient reaction product, comprising: a polishing layer prepolymer, wherein the polishing layer prepolymer is selected from the group consisting of isocyanate-terminated urethane prepolymers having from 2 to 12% by weight of unreacted NCO groups; and, a polishing layer hardener system comprising: at least 5% by weight of an amine initiated polyol polishing layer hardener having at least one nitrogen atom per molecule and an average of at least one three hydroxyl groups per molecule; from 25 to 95% by weight of a high molecular weight polyol polishing layer hardener having a number average molecular weight, MN, of 2,500 to 100,000 and an average of three to ten hydroxyl groups per molecule; and from 0 to 70% by weight of a polishing layer difunctional hardener; wherein the endpoint detection window comprises an ingredient reaction product, comprising: a window prepolymer, wherein the window prepolymer is selected from the group consisting of isocyanate-terminated urethane prepolymers having from 2 to 6 5% by weight of unreacted NCO groups; and, a window hardener system comprising: at least 5% by weight of a difunctional window hardener; at least 5% by weight of an amine initiated polyol window hardener having at least one nitrogen atom per molecule and an average of at least three hydroxyl groups per molecule; and from 25 to 90% by weight of a high molecular weight polyol window hardener having a number average molecular weight, MN, of 2,000 to 100,000 and an average of three to ten hydroxyl groups per molecule; wherein the polishing layer has a density of 0.6 g / cm3; a Shore D hardness of 5 to 40; an elongation at break of 100 to 450%; and, a cutting speed of 25 to 150 pm / h. The present invention also relates to a chemical mechanical polishing felt, comprising: a polishing layer having a polishing surface, a base surface and an average thickness Tp-moy, measured in a direction perpendicular to the polishing surface from the polishing surface to the base surface; a limit point detection window incorporated in the polishing layer; a rigid layer having an upper surface and a bottom surface; and a hot melt adhesive interposed between the base surface of the polishing layer and the upper surface of the rigid layer; wherein the hot melt adhesive bonds the polishing layer to the rigid layer; wherein the polishing layer comprises an ingredient reaction product, comprising: a polishing layer prepolymer; wherein the polishing layer prepolymer is selected from the group consisting of isocyanate-terminated urethane prepolymers having from 2 to 12% by weight of unreacted NCO groups; and, a polishing layer hardener system comprising: at least 5% by weight of an amine initiated polyol polishing layer hardener having at least one nitrogen atom per molecule and an average of at least one three hydroxyl groups per molecule; from 25 to 95% by weight of a high molecular weight polyol polishing layer hardener having a number average molecular weight, MN, of 2,500 to 100,000 and an average of three to ten hydroxyl groups per molecule; and from 0 to 70% by weight of a difunctional polishing layer hardener; wherein the endpoint detection window comprises an ingredient reaction product, comprising: a window prepolymer, wherein the window prepolymer is selected from the group consisting of isocyanate-terminated urethane prepolymers having from 2 to 6 5% by weight of unreacted NCO groups; and, a window hardener system comprising: at least 5% by weight of a difunctional window hardener; at least 5% by weight of an amine initiated polyol window hardener having at least one nitrogen atom per molecule and an average of at least three hydroxyl groups per molecule; and from 25 to 90% by weight of a high molecular weight polyol window hardener having a number average molecular weight, MN, of 2,000 to 100,000 and an average of three to ten hydroxyl groups per molecule; wherein the polishing layer has a density of 0.6 g / cm3; a Shore D hardness of 5 to 40; an elongation at break of 100 to 450%; and, a cutting speed of 25 to 150 pm / h. The present invention also relates to a chemical-mechanical polishing felt, comprising: a polishing layer having a polishing surface, a base surface and an average thickness, Tp-moy, measured in a direction perpendicular to the polishing surface to from the polishing surface to the base surface; a peak limit detection window incorporated in the polishing layer; a rigid layer having an upper surface and a bottom surface; a hot melt adhesive interposed between the base surface of the polishing layer and the upper surface of the rigid layer; an adhesive sensitive to cylinder pressure; wherein the cylinder pressure sensitive adhesive is disposed on the bottom surface of the rigid layer; and, a detachable liner; wherein the hot melt adhesive bonds the polishing layer to the rigid layer; wherein the cylinder pressure sensitive adhesive is interposed between the bottom surface of the rigid layer and the detachable liner; wherein the polishing layer comprises an ingredient reaction product, comprising: a polishing layer prepolymer, wherein the polishing layer prepolymer is selected from the group consisting of isocyanate-terminated urethane prepolymers having from 2 to 12% by weight of unreacted NCO groups; and, a polishing layer hardener system comprising: at least 5% by weight of an amine initiated polyol polishing layer hardener having at least one nitrogen atom per molecule and an average of at least one three hydroxyl groups per molecule; from 25 to 95% by weight of a high molecular weight polyol polishing layer hardener having a number average molecular weight, MN, of 2,500 to 100,000 and an average of three to ten groups per molecule; and from 0 to 70% by weight of a difunctional polishing layer hardener; wherein the endpoint detection window comprises an ingredient reaction product, comprising: a window prepolymer, wherein the window prepolymer is selected from the group consisting of isocyanate-terminated urethane prepolymers having from 2 to 6 5% by weight of unreacted NCO groups; and, a window hardener system comprising: at least 5% by weight of a difunctional window hardener; at least 5% by weight of an amine initiated polyol window hardener having at least one nitrogen atom per molecule and an average of at least three hydroxyl groups per molecule; and from 25 to 90% by weight of a high molecular weight polyol window hardener having a number average molecular weight, MN, of 2,000 to 100,000 and an average of three to ten hydroxyl groups per molecule; wherein the polishing layer has a density 0.6 g / cm3; a Shore D hardness of 5 to 40; an elongation at break of 100 to 450%; and, a cutting speed of 25 to 150 mph.
[0007] The present invention also relates to a chemical-mechanical polishing felt, comprising: a polishing layer having a polishing surface, a base surface and an average thickness, Tp_moy, measured in a direction perpendicular to the polishing surface from the polishing surface towards the base surface; and, a peak limit detection window incorporated in the polishing layer; wherein the polishing layer comprises an ingredient reaction product, comprising: a polishing layer prepolymer, wherein the polishing layer prepolymer is selected from the group consisting of isocyanate-terminated urethane prepolymers having from 2 to 12% by weight of unreacted NCO groups; and, a polishing layer hardener system comprising: at least 5% by weight of an amine initiated polyol polishing layer hardener having at least one nitrogen atom per molecule and an average of at least one three hydroxyl groups per molecule; from 25 to 95 by weight of a high molecular weight polyol polishing layer hardener having a number average molecular weight, MN / from 2,500 to 100,000 and an average of from three to ten hydroxyl groups per molecule; and from 0 to 70% by weight of a difunctional polishing layer hardener; wherein the endpoint detection window comprises an ingredient reaction product, comprising: a window prepolymer, wherein the window prepolymer is selected from the group consisting of isocyanate-terminated urethane prepolymers having from 2 to 6 5% by weight of unreacted NCO groups; and, a window hardener system comprising: at least 5% by weight of a difunctional window hardener; at least 5% by weight of an amine initiated polyol window hardener having at least one nitrogen atom per molecule and an average of at least three hydroxyl groups per molecule; and from 25 to 90% by weight of a high molecular weight polyol window hardener having a number average molecular weight, MN, of 2,000 to 100,000 and an average of three to ten hydroxyl groups per molecule; wherein the polishing layer has a density of 0.6 g / cm3; a Shore D hardness of 5 to 40; an elongation at break of 100 to 450%; and, a cutting speed of 25 to 150 pm / hr; and wherein the limit point detection window has a density of 1 g / cm 3; porosity less than 0.1% in flight; a Shore D hardness of 10 to 50; elongation at break 400%; a double pass transmission at 800 nm, DPT800, of 50 to 100 ° / 0. The present invention also relates to a chemical-mechanical polishing felt, comprising: a polishing layer having a polishing surface, a base surface and an average thickness, Tp_moy, measured in a direction perpendicular to the polishing surface from the polishing surface towards the base surface; and, a peak limit detection window incorporated in the polishing layer; wherein the polishing layer comprises an ingredient reaction product, comprising: a polishing layer prepolymer, wherein the polishing layer prepolymer is selected from the group consisting of isocyanate-terminated urethane prepolymers having from 2 to 12% by weight of unreacted NCO groups; and, a polishing layer hardener system comprising: at least 5% by weight of an amine initiated polyol polishing layer hardener having at least one nitrogen atom per molecule and an average of at least one three hydroxyl groups per molecule; from 25 to 95 weight percent of a high molecular weight polyol polishing layer hardener having a number average molecular weight, MN, of 2,500 to 100,000 and an average of three to ten hydroxyl groups per molecule; and from 0 to 70% by weight of a difunctional polishing layer hardener; wherein the endpoint detection window comprises an ingredient reaction product, comprising: a window prepolymer, wherein the window prepolymer is selected from the group consisting of isocyanate-terminated urethane prepolymers having from 2 to 6 5% by weight of unreacted NCO groups; and, a window hardener system comprising: at least 5% by weight of a difunctional window hardener; at least 5% by weight of an amine initiated polyol window hardener having at least one nitrogen atom per molecule and an average of at least three hydroxyl groups per molecule; and from 25 to 90% by weight of a high molecular weight polyol window hardener having a number average molecular weight, MN, of 2,000 to 100,000 and an average of three to ten hydroxyl groups per molecule; wherein the polishing layer has a density k 0.6 g / cm 3; a Shore D hardness of 5 to 40; an elongation at break of 100 to 450%; and, a cutting speed of 25 to 150 pm / hr; and, wherein the limit point detection window has a density 1 g / cm3; porosity less than 0.1% in flight; a Shore D hardness of 10 to 50; an elongation at break of 400%; a double pass transmission at 10 800 nm, DPT800, of 50 to 100 ° h; and a 400 nm double pass transmission, DPT400, of 25 to 100%. The present invention provides a method of polishing a substrate, comprising: providing a chemical mechanical polishing apparatus having a cylinder, a light source and a photoelectric sensor or sensor; providing at least one substrate; providing a chemical mechanical polishing felt of the present invention; the installation on the cylinder of the chemical-mechanical polishing felt; optionally, providing a polishing medium at an interface between the polishing surface and the substrate; creating a dynamic contact between the polishing surface and the substrate, wherein at least a certain amount of material is removed from the substrate; and, determining a polishing boundary point by transmitting light from the light source through the boundary point detection window and analyzing light reflected from the surface of the substrate back through the limit point detection window incident on the photoelectric detector. In a particular embodiment of the invention, the at least one substrate is selected from the group consisting of at least one of a magnetic substrate, an optical substrate and a semiconductor substrate. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a representation of a perspective view of a chemical mechanical polishing felt of the present invention.
[0008] Figure 2 is a representation of a cross-sectional view of a chemical mechanical polishing felt of the present invention. Figure 3 is a top view of a chemical-mechanical polishing felt of the present invention. Figure 4 is a side perspective view of a polishing layer of the present invention. Figure 5 is a side vertical projection of a cross section of a chemical mechanical polishing felt of the present invention with an integral end point detection window incorporated in the polishing felt. Figure 6 is a side vertical projection of a limit point detection window. DETAILED DESCRIPTION The chemical mechanical polishing felt of the present invention has a polishing layer which exhibits a unique combination of low hardness (i.e., Shore D 40) to provide low defect polishing performance and a low tensile elongation (i.e. elongation at break 5.50%) which provides both machinability to facilitate groove formation in the polishing layer and processability to facilitate the formation of a micro-texture using a diamond treatment disc. The balance of properties enabled by the polishing layer of the present invention further provides the ability to polish, for example, semiconductor wafers without damaging the wafer surface by creating micro scratch defects that would compromise the performance of the wafer. electrical integrity of the semiconductor device. The chemical mechanical polishing felt of the present invention also has a limit point detection window incorporated into the polishing layer which exhibits a unique combination of low hardness (i.e., Shore D.50) for provide low defect polishing performance and low tensile elongation (i.e. elongation at break 5. 400%) coupled with good optical properties to facilitate detection of the polishing end point; wherein the boundary detection window formulation does not exhibit undesirable window deformation (i.e., excessive swelling or indentation) and has the durability required for demanding polishing applications. The term "average total thickness, TT_moy" as used herein and in the appended claims with reference to a chemical mechanical polishing felt (10) having a polishing surface (14) indicates the average thickness, TT, of the chemical mechanical polishing measured in a direction perpendicular to the polishing surface (14) from the polishing surface (14) to the bottom surface (27) of the rigid layer (25). (Refer to Figures 1, 2 and 5). The term "substantially circular cross-section" as used herein and in the appended claims with reference to a chemical-mechanical polishing felt (10) indicates that the longest radius, r, of the cross-section from the axis center (12) to the outer perimeter (15) of the polishing surface (14) of the polishing layer (20) is 20% longer than the shortest radius, r, of the cross section of the central axis (12) to the outer perimeter (15) of the polishing surface (14). (Refer to Figure 1). The term "polishing medium" as used herein and in the appended claims includes polishing solutions containing particles and polishing solutions that do not contain particles, such as reactive and abrasive-free liquid polishing solutions. The term "double pass transmission" or "DPT" as used herein and in the appended claims with reference to a limit point detection window is determined using the following equation: DPT = (I 51-IIND) ÷ ( IA51-IAD) where IWsi, IWD, IAsi, and IAD are measured using a Verity SP2006 Spectral Interferometer comprising an SD1024F spectrograph, a xenon flash lamp, and a 3 mm optical fiber cable by placing a light emitting surface 3mm optical fiber cable against (and perpendicular to) a first face of the limit point detection window at a point of origin, directing light through the thickness, Tw, of the window (confer to Figures 5-6) and measuring at the point of origin the intensity of light reflected back through the window thickness, Tw, from a surface disposed against a second face of the detection window point limit p ratically parallel to the first face; where IWsi is a measure of the light intensity that passes through the window from the point of origin and is reflected from the surface of a silicon control wafer placed against a second face of the window back through the window to the point of origin; where IWD is a measure of the intensity of light that passes from the point of origin through the window and is reflected from the surface of a black body and back through the window to the point of origin; where IAsi is a measure of the intensity of light passing from the point of origin through an air thickness equivalent to the thickness, Tw, of the endpoint detection window, which is reflected from the surface of a silicon control wafer placed perpendicular to the light emitting surface of the 3 mm optical fiber cable and which is reflected back through the air thickness to the point of origin; and, where IAD is a measure of the intensity of light reflected from a black body on the light emitting surface of the 3 mm optical fiber cable. The term "DPT400" as used herein and in the appended claims is the DPT presented by a limit point detection window for light having a wavelength of 400 nm. The term "DPT800" as used herein and in the appended claims is TPD presented by a limit point detection window for light having a wavelength of 800 nm. The chemical-mechanical polishing felt (10) of the present invention is preferably adapted for rotation about a central axis (12) (see FIG. 1). The polishing surface (14) of the polishing layer (20) is preferably in a plane (28) perpendicular to the central axis (12). The electrochemical polishing felt (10) is optionally adapted for rotation in a plane (28) which is at an angle, 7, of 85 to 95 ° with respect to the central axis (12), preferably at 90 ° to the central axis (12). The polishing layer (20) preferably has a polishing surface (14) which has a substantially circular cross-section perpendicular to the central axis (12). The radius, r, of the cross-section of the polishing surface (14) perpendicular to the central axis (12) preferably varies by 5% for the cross section, more preferably by 10% for the cross-section. The chemical-mechanical polishing felt (10) of the present invention is preferably developed to facilitate the polishing of a substrate selected from at least one of a magnetic substrate, an optical substrate and a semi-substrate. -driver. The chemical mechanical polishing felt (10) has a polishing layer (20) which has a unique combination of low hardness (i.e., Shore D 40) to provide low defect polishing performance and a low tensile elongation (i.e. 450% elongation at break) which provides both machinability to facilitate groove formation in the polishing layer and processability to facilitate forming a micro-texture using a diamond treatment disc. In addition, the balance of properties enabled by the polishing layer of the present invention provides the ability to polish, for example, semiconductor wafers without damaging the wafer surface by creating micro-scratch defects that would compromise the performance of the wafer. electrical integrity of the semiconductor device.
[0009] The chemical-mechanical polishing felt (10) of the present invention comprises (preferably consists of): a polishing layer (20) having a polishing surface (14), a base surface (17) and an average thickness, Tp-moy, measured in a direction perpendicular to the polishing surface (14) from the polishing surface (14) to the base surface (17); a limit point detection window (30) incorporated in the polishing layer (preferably in which the limit point detection window facilitates detection of the in situ polishing boundary point; optionally, a rigid layer (25) having a upper surface (26) and a bottom surface (27), optionally a hot melt adhesive (23) interposed between the base surface (17) of the polishing layer (20) and the upper surface (26) of the rigid layer (25), wherein the hot melt adhesive (23) bonds the polishing layer (20) to the rigid layer (25), optionally a cylinder pressure sensitive adhesive (70); the cylinder pressure (70) is disposed on the bottom surface (27) of the rigid layer (25) (where preferably the cylinder pressure sensitive adhesive facilitates the attachment of the chemical mechanical polishing felt to a machine polishing) and possibly detachable seal (75), wherein the cylinder pressure sensitive adhesive (70) is interposed between the bottom surface (27) of the rigid layer (25) and the detachable liner (75); wherein the polishing layer (20) comprises the ingredient reaction product, comprising: a polishing layer prepolymer, wherein the polishing layer prepolymer is selected from the group consisting of isocyanate-terminated urethane prepolymers having from 2 to 12% by weight (preferably from 2 to 10% by weight, more preferably from 4 to 8% by weight, most preferably from 5 to 7% by weight) of unreacted NCO groups; and, a polishing layer hardener system comprising: at least 5% by weight (preferably 5 to 30% by weight, more preferably 5 to 25% by weight, more preferably 5 to 20% by weight ) an amine-initiated polyol polishing layer hardener having at least one nitrogen atom (preferably one to four nitrogen atoms, more preferably two to four nitrogen atoms, more preferably two nitrogen atoms) 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; from 25 to 95% by weight (preferably from 35 to 90% by weight, more preferably from 50 to 75% by weight, particularly preferably from 60 to 75% by weight) of a polyol polishing layer hardener of high molecular weight having a number average molecular weight, MN, of 2500 to 100,000 (preferably 5,000 to 50,000, more preferably 7,500 to 25,000, more preferably 10,000 to 15,000) and an average of from three to ten (preferably from four to eight, more preferably from five to seven, most preferably six) hydroxyl groups per molecule; and 0 to 70% by weight (preferably 5 to 60% by weight, more preferably 10 to 50% by weight, more preferably 10 to 30% by weight, particularly preferably 10 to 20% by weight ) a difunctional polishing layer hardener; wherein the limit point detection window (30) comprises an ingredient reaction product, comprising: a window prepolymer, wherein the window prepolymer is selected from a group consisting of isocyanate-terminated urethane prepolymers having From 2 to 6.5% by weight (preferably from 3 to 6% by weight, more preferably from 5 to 6% by weight, most preferably from 5.5 to 6% by weight) of NCO groups which do not have reacted; and, a window hardener system comprising: at least 5% by weight, preferably 5 to 70% by weight; still more preferably from 10 to 60% by weight; more preferably 20 to 40% by weight) of a bifunctional window hardener; at least 5% by weight (preferably 5 to 25% by weight, more preferably 5 to 20% by weight, more preferably 5 to 15% by weight) of an amine initiated polyol window hardener having at least one nitrogen atom (preferably one to four nitrogen atoms, more preferably two to four nitrogen atoms, more preferably two nitrogen atoms) per molecule and an average of at least three (preferably from three to six, more preferably from three to five, more preferably four) hydroxyl groups per molecule; and 25 to 90% by weight (preferably 35 to 90% by weight, more preferably 40 to 75% by weight, more preferably 50 to 65% by weight) of a mass polyol window hardener high molecular weight having a number average molecular weight, MN, of 2,000 to 100,000 (preferably 2,500 to 100,000, more preferably 5,000 to 50,000, more preferably 7,500 to 15,000) and an average from three to ten (preferably from four to eight, more preferably from five to seven, most preferably six) hydroxyl groups per molecule; wherein the polishing layer has a density 0.6 g / cm 3 (preferably 0.6 to 1.2 g / cm 3, more preferably 0.7 to 1.1 g / cm 3, most preferably 0.75 to 1.0 cm 3); a Shore D hardness of 5 to 40 (more preferably 5 to 30, more preferably 5 to 20, most preferably 5 to 15); an elongation at break of 100 to 450% (preferably 125 to 425%, more preferably 150 to 300%, more preferably 150 to 200%); and a cutting speed of 25 to 150 μm / h (preferably 30 to 125 μm / h, more preferably 30 to 100 μm / h, more preferably 30 to 60 μm / h); and, wherein the polishing layer has a density 0.6 g / cm 3 (preferably 0.6 to 1.2 g / cm 3, more preferably 0.7 to 1.1 g / cm 3, most preferably 0.75 to 1.0 g / cm 3) ; a Shore D hardness of 5 to 40 (more preferably 5 to 30, more preferably 5 to 20, most preferably 5 to 15); an elongation at break of 100 to 450% (preferably 125 to 425%, more preferably 150 to 300%, more preferably 150 to 200%); and a cutting speed of 25 to 150 μm / h (preferably 30 to 125 μm / h, more preferably 30 to 100 μm / h, more preferably 30 to 60 μm / h). (Refer to Figures 1-6). The isocyanate-terminated urethane prepolymers for use as the polishing prepolymer and the window prepolymer preferably include: an ingredient reaction product comprising: a polyfunctional isocyanate and a prepolymer polyol. The polyfunctional isocyanate used in the preparation of the isocyanate-terminated urethane prepolymers is preferably selected from the group consisting of aliphatic polyfunctional isocyanates, polyfunctional aromatic isocyanates, and mixtures thereof. The polyfunctional isocyanate is even better a diisocyanate selected from the group consisting of 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; 4,4'-diphenylmethane diisocyanate; naphthalene-1,5-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 is still more preferably a diisocyanate selected from the group consisting of 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; and mixtures thereof. The prepolymer polyol used in the preparation of the isocyanate-terminated urethane prepolymers is preferably selected from the group consisting of diols, polyols, polyol diols, copolymers thereof, and mixtures thereof. The prepolymer polyol is even more preferably selected from the group consisting of polyether polyols (for example poly (oxytetramethylene) glycol, poly (oxypropylene) glycol, poly (oxyethylene) glycol); polycarbonate polyols; polyesters polyols; polycaprolactones polyols; mixtures thereof; and mixtures thereof with one or more low molecular weight polyols selected from the group consisting of ethylene glycol; 1,2-propylene glycol; 1,3-propylene glycol; 1,2-butanediol; 1,3-butanediol; 2-methyl-1,3-propanediol; 1,4-butanediol; neopentyl glycol; 1,5-pentanediol; 3-trimethyl-1,5-pentanediol; 1,6-hexanediol; diethylene glycol; dipropylene glycol; and, tripropylene glycol. The prepolymer polyol is more preferably selected from the group consisting of at least one of 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; 1,2-propylene glycol; 1,3-propylene glycol; 1,2-butanediol; 1,3-butanediol; 2-methyl-1,3-propanediol; 1,4-butanediol; 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 PPG mixed with at least one of ethylene glycol; 1,2-propylene glycol; 1,3-propylene glycol; 1,2-butanediol; 1,3-butanediol; 2-methyl-1,3-propanediol; 1,4-butanediol; neopentyl glycol; 1,5-pentanediol; 3-methyl-1,5-pentanediol; 1,6-hexanediol; diethylene glycol; dipropylene glycol; and, tripropylene glycol. Examples of commercially available PTMEG-based isocyanate-terminated urethane prepolymers include Imuthane® prepolymers (available from COIM USA, Inc., such as PET-80A, PET-85A, PET-90A, PET-93A, PET-95A, PET-60D, PET-70D, PET-75D); Adiprene® prepolymers (available from Chemtura, such as LF 800A, LF 900A, LF 910A, LF 930A, LF 931A, LF 939A, LF 950A, LF 952A, LF 600D, LF 601D, LF 650D, LF 667, LF 700D, LF 750D, LF751D, LF752D, LF753D and L325); Andur® prepolymers (available from Anderson Development Company, such as 70APLF, 80APLF, 85APLF, 90APLF, 95APLF, 60DPLF, 70APLF, 75APLF). Examples of commercially available PPG-based isocyanate-terminated urethane prepolymers include Imuthane® prepolymers (available from COIM USA, Inc., such as PPT-80A, PPT-90A, PTT-95A, PPT-65D, PPT-75D); Adiprene® prepolymers (available from Chemtura, such as LFG 963A, LFG 964A, LFG 740D); and, Andur® prepolymers (available from Anderson Development Company, such as 8000APLF, 9500APLF, 650DPLF, 7501DPLF).
[0010] It is also possible to use isocyanate-terminated urethane prepolymers which are not based on TDI. Isocyanate-terminated urethane prepolymers comprising, for example, those formed by the reaction of 4,4'-diphenylmethane diisocyanate (MDI) and polyols, such as polytetramethylene glycol (PTMEG) with optional diols, such as 1,4 -butanediol (BDO), are acceptable. When using such isocyanate-terminated urethane prepolymers, the concentration of unreacted isocyanate groups (NCO) is preferably from 4 to 10% by weight (more preferably from 4 to 8% by weight, although more preferably 5 to 7% by weight). Examples of commercially available isocyanate-terminated urethane prepolymers in this class include Imuthane® prepolymers (available from COIM USA, Inc., such as 27-85A, 27-90A, 27-95A); Andur® prepolymers (available from Anderson Development Company, such as IE75AP, IE80AP, IE85AP, IE90AP, IE95AP, IE98AP); and, Vibratane® prepolymers (available from Chemtura, such as B625, B635, B821). The polishing layer prepolymer and the window prepolymer are preferably selected from isocyanate-terminated urethane prepolymers having a free toluene diisocyanate (TDI) monomer content of less than 0.1% by weight.
[0011] The polishing layer prepolymer and the window prepolymer are preferably selected from isocyanate-terminated urethane prepolymers having an average of two reactive isocyanate groups (i.e., NCO) per molecule. The difunctional polishing layer hardener and the difunctional window hardener are each preferably independently selected from the group consisting of difunctional diol hardeners and difunctional diamine hardeners. The difunctional polishing layer hardener and the difunctional window hardener are each more preferably each independently 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 (sec-butylamino) benzene; 4,4'35 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'-methylenebis (2,6-diethylaniline) (M DEA); 4,4'-methylene-bis- (2,3-dichloroanil) (MDCA); 4,4'-diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane; 2,2 ', 3,3'-tetrachlorodiaminodiphenylmethane; trimethylene glycol di-p-aminobenzoate; and mixtures thereof. . The difunctional polishing layer hardener and the difunctional window hardener are all further preferably each independently selected from the group consisting of 4,4'-methylene-bis- (2-chloroaniline) (MBOCA); 4,4'-methylene-bis- (3-chloro-2,6-diethylaniline) (MCDEA); and isomers thereof. The difunctional polishing layer hardener and the difunctional window hardener are particularly preferably each 4,4'-methylene-bis- (2-chloroaniline) (MBOCA).
[0012] The amine initiated polishing hardener and the amine initiated window hardener are preferably each independently selected from the group consisting of amine initiated polyol hardeners having at least one nitrogen atom (preferably one to four nitrogen atoms, still more preferably two to four nitrogen atoms, still more preferably two nitrogen atoms) per molecule and an average of at least three (preferably three to six, more preferably three to six). five, and most preferably four) hydroxyl groups per molecule. The amine initiated polyol hardeners, of which the amine initiated polishing hardener and the amine initiated window hardener are selected, preferably have a number average molecular weight, MN, 5.700 (again preferably from 150 to 650, more preferably from 200 to 500, particularly preferably from 250 to 300). The amine initiated polyol hardeners, of which the amine initiated polishing hardener and the amine initiated window hardener are selected, preferably have a hydroxyl number (as determined by the ASTM D4274 test method). 11) from 350 to 1200 mg KOH / g (more preferably 400 to 1000 mg KOH / g, more preferably 600 to 850 mg KOH / g).
[0013] Examples of commercially available amine-initiated polyol hardeners 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); Plucarol® 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.
[0014] TABLE 1 Initiated polyol hardener Number of MN hydroxyl number (mg KOH / g) per amine OH groups per 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 The high molecular weight polyol polishing layer hardener and the high molecular weight polyol window hardener are preferably each independently selected from the group consisting of polyol, polyvinyl alcohol, polyvinyl alcohol and polyol. high molecular weight polyol hardeners having an average of from three to ten (more preferably from four to eight, more preferably from five to seven, particularly preferably six) hydroxyl groups per molecule.
[0015] The high molecular weight polyol hardeners, among which the high molecular weight polyol polishing layer hardener is selected, preferably have a number average molecular weight, MN, which is greater than the number average molecular weight, MN, an amine initiated polyol polishing layer hardener used in the polishing layer hardener system; and preferably has a hydroxyl number which is less than the hydroxyl number of the amine initiated polishing hardener used in the polishing layer hardener system. The high molecular weight polyol polishing layer hardener used in the formation of the polishing layer (20) preferably has a number average molecular weight, MN, of 2,500 to 100,000 (even more preferably 5,000 to 50%). More preferably from 7,500 to 25,000, particularly preferably from 10,000 to 15,000). The high molecular weight polyol hardeners, of which the high molecular weight polyol window hardener is selected, preferably have a number average molecular weight, MN, which is greater than the number average molecular weight, MN, an amine initiated polyol window hardener used in the window hardener system; and preferably has a hydroxyl number which is less than the hydroxyl number of the amine initiated window hardener used in the window hardener system. The high molecular weight polyol window hardener used in the formation of the window (30) preferably has a number average molecular weight, MN, of 2,000 to 100,000 (more preferably 2,500 to 100,000; more preferably from 5,000 to 50,000, particularly preferably from 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 curatives are listed in TABLE 2.
[0016] TABLE 2 Polyol Hardener Number of MN Number High Molecular Weight OH Groups by Hydroxyl Molecule (mg KOH / g) 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 7,000 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 30 Polyol MULTRANOL The sum of the reactive hydrogen groups (i.e. the sum of the amine (NH 2) and hydroxyl (OH) groups) contained in the reactive hydrogen groups (ie, the sum of the amine (NH 2) and hydroxyl (OH) groups) contained in the components of the polishing layer hardener system divided by the unreacted isocyanate groups (NCO) in the polishing layer prepolymer (i.e., the stoichiometric ratio) used in the formation of the polishing (20) of the chemical mechanical polishing felt (10) of the present invention is preferably from 0.85 to 1.15 (even better from 0.90 to 1.10; much better still from 0.95 to 1.05). The sum of the reactive hydrogen groups (i.e. the sum of the amine (NH 2) and hydroxyl (OH) groups) contained in the constituents of the window hardener system divided by the isocyanate (NCO) groups which have not reacted in the window prepolymer (i.e., the stoichiometric ratio) used in the formation of the end point detection window (30) of the chemical mechanical polishing felt (10) of the present invention The invention is preferably 0.7 to 1.2 (more preferably 0.8 to 1.10, more preferably 0.95 to 1.05, particularly preferably 0.98 to 1.02). The polishing layer (20) optionally further comprises a plurality of microelements. The plurality of microelements are preferably uniformly dispersed throughout the polishing layer (20). The plurality of microelements are preferably selected from entrapped gas bubbles, hollow core polymer materials, liquid filled hollow core polymeric materials, water soluble materials, and insoluble phase material (eg, oil). mineral). The multiple microelements are even more preferably selected from entrapped gas bubbles and hollow core polymer materials uniformly distributed throughout the polishing layer (20). 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). The several microelements are preferably incorporated in the polishing layer (20) to a porosity of 0 to 35% in flight (more preferably a porosity of 10 to 25% in flight). The polishing layer (20) can be provided in both porous and non-porous (i.e., unfilled) configurations. The polishing layer (20) preferably has a density of 0.6 g / cm3 measured according to ASTM D1622. The polishing layer (20) even more preferably has a density of 0.6 to 1.2 g / cm 3 (more preferably 0.7 to 1.1 g / cm 3, most preferably 0.75 to 1.0 g / cm3) measured according to ASTM D 1622.
[0017] The polishing layer (20) preferably has a Shore D hardness of 5 to 40 measured according to ASTM D2240. The polishing layer (20) even more preferably has a Shore D hardness of 5 to 30 (more preferably 5 to 20, more preferably 5 to 15) measured according to ASTM D2240.
[0018] Polishing layers having a Shore D hardness of less than 40 typically have very high ultimate elongation values (i.e.,> 600 ° h). Materials having such high values of elongation at break become reversibly deformed when subjected to machining operations, resulting in unacceptably poor groove formation and texture creation during processing. diamond treatment that is insufficient.
[0019] The unique polishing layer hardener system used in forming the polishing layer (20) of the chemical mechanical polishing felt (10) of the present invention provides a low hardness coupled with an elongation at break of 100 to 450% measured according to ASTM D412. The polishing layer (20) preferably has an elongation at break of 125 to 425% (more preferably 150 to 300%, most preferably 150 to 200%) measured according to ASTM D412. The polishing layer (20) preferably has a cutting speed of 25 to 150 lm / h measured using the method described herein in the Examples. The polishing layer (20) even more preferably has a cutting speed of 30 to 125 μm / h (more preferably 30 to 100 μm / h, most preferably 30 to 60 μm / h) measured using the method described herein. in the Examples. Those skilled in the art will be able to choose a polishing layer (20) having a thickness, Tp, which can be used in a chemical-mechanical polishing felt (10) for a given polishing operation. The polishing layer (20) preferably has an average thickness, Tp_moy, along an axis (A) perpendicular to a plane (28) of the polishing surface (14). The average thickness, Tp_moy, is preferably 20 to 150 thousandths of an inch (more preferably 30 to 125 thousandths of an inch, more preferably 40 to 120 thousandths of an inch). (Refer to Figures 2 and 5). The polishing surface (14) of the polishing layer (20) is preferably adapted to polish a substrate. The polishing surface (14) is preferably adapted to polish a substrate selected from at least one of a magnetic substrate, an optical substrate and a semiconductor substrate (more preferably a semiconductor substrate; semi-conductive slab). The polishing surface (14) of the polishing layer (20) preferably has at least one of a macro-texture and a micro-texture to facilitate the polishing of the substrate. The polishing surface (14) preferably has a macrotexture, wherein the macro-texture is developed to achieve at least one action of (i) avoiding at least hydroplaning; (ii) influencing the flow of the polishing medium; (iii) modifying the stiffness of the polishing layer; (iv) reduce edge effects; and, (v) facilitating the transfer of polishing debris out of the surface between the polishing surface (14) and the substrate to be polished. The polishing surface (14) preferably has a macro-texture selected from at least one of perforations and grooves.
[0020] The perforations may preferably extend from the polishing surface (14) over part or all through the thickness of the polishing layer (20). The grooves are preferably disposed on the polishing surface (14) so that, upon rotation of the felt (10) during polishing, at least one groove sweeps the substrate. The grooves are preferably selected from curved grooves, linear grooves and combinations thereof. The grooves have a depth 10 thousandths of an inch (preferably 10 to 150 thousandths of an inch). The grooves preferably form a pattern of grooves which comprises at least two grooves having a combination of a depth selected from. 10 thousandths of an inch, 15 thousandths of an inch and 15 to 150 thousandths of an inch; a width selected from 10 thousandths of an inch and 10 to 100 thousandths of an inch; and a step selected from _ . 30 thousandths of an inch, 50 thousandths of an inch, 50 to 200 thousandths of an inch, 70 to 200 thousandths of an inch, and 90 to 200 thousandths of an inch. The polishing layer (20) preferably contains <1 ppm of abrasive particles incorporated therein. The limit point detection window (30) of the chemical mechanical polishing felt (10) of the present invention preferably has a density of 1 g / cm 3 (preferably 1.05 to 1.2 g / cm 3; 1.1 to 1.2 g / cm 3, most preferably 1.1 to 1.15 g / cm 3); porosity less than 0.1% in flight; a Shore D hardness of 10 to 50 (preferably 15 to 45, more preferably 20 to 40, most preferably 25 to 35); and elongation at break 5. 400% (preferably 150-400%, more preferably 200-400%, most preferably 250-400%). The limit point detection window (30) of the chemical mechanical polishing felt (10) of the present invention preferably has a double pass transmission at 800 nm, DPT800, of 30 to 100% (preferably 30 to 85%). more preferably 50 to 85%, more preferably 60 to 80%) measured under the conditions given here in the Examples. The limit point detection window (30) of the chemical mechanical polishing felt (10) of the present invention preferably has a DPT800 of 30 to 100% (preferably 30 to 85%, more preferably 50 to 85% much better still 60 to 85%) measured under the conditions given here in the Examples; and a 400 nm double pass transmission, DPT400, of 25 to 100% (preferably 25 to 85%, more preferably 40 to 85%, most preferably 45 to 85%) measured under the conditions given herein. in the Examples. The boundary detection window (30) incorporated into the polishing layer in the chemical mechanical polishing felt (10) of the present invention is preferably an integral window. (Refer to Figure 5). Methods for incorporating integral windows into polishing layers are well known. The limit point detection window (30) preferably has a planarity + 2.0 mil (even better + 1.5 mil) with the polishing surface (14) of the polishing layer (20) after four hours of simulated substrate polishing at a polishing temperature of 40 ° C (as described in the Examples). That is, the limit point detection window (30) preferably has a swelling, or maximum indentation <2.0 mils (more preferably 1.5 mils) from the surface polishing (14) in a direction parallel to the B-axis after four hours of simulated substrate polishing at a polishing temperature of 40 ° C (as described in the Examples). The limit point detection window (30) has a thickness, Tw, along an axis B perpendicular to a plane (28) of the polishing surface (14). The limit point detection window (30) has an average thickness, Tw_moy, which satisfies the following expression: (Tp_moy - 1 mil) 5_ Tw_moy 5. (Tp_moy + 1 mil). The boundary point detection window (30) is even more preferably of an average thickness, Tw_moy, which satisfies the following expression: (Tp-moy- 0.5 mil) 5, Tw-moy5 (Tp-moy + 0.5 thousandth) inch). The limit point detection window (30) is even more preferably an average thickness, Tw_moy, which is equal to the average thickness of the polishing layer, Tp_moy- The rigid layer (25) preferably consists of a material selected from the group consisting of a polymer, a metal, a reinforced polymer and combinations thereof. The rigid layer (25) is even better made of a polymer. The rigid layer (25) is more preferably comprised of a polymer selected from the group consisting of a polyester, a nylon, an epoxy, a glass fiber reinforced epoxy; and polycarbonate (more preferably polyester, more preferably polyethylene terephthalate polyester, particularly preferably biaxially oriented polyester polyethylene terephthalate).
[0021] The rigid layer (25) preferably has an average thickness of> 5 to 60 mils (more preferably 6 to 30 mils, more preferably 6 to 15 mils, particularly preferably 6 to 10 mils). thumb). The upper surface (26) and the bottom surface (27) of the rigid layer (25) are preferably both non-grooved. The upper surface (26) and the bottom surface (27) are both even better smooth. The upper surface (26) and the bottom surface (27) even more preferably have a roughness, Ra, of 1 to 500 nm (preferably 1 to 100 nm, more preferably 10 to 50 nm, most preferably 20 to 40 nm) determined using an optical profilometer. The rigid layer (25) preferably has a Young's modulus measured according to ASTM D882-12 100 MPa (more preferably from 1000 to 10,000 MPa, still more preferably from 2,500 to 7,500 MPa, particularly preferably from 3,000 to 10,000 MPa). 7,000 MPa).
[0022] The rigid layer (25) preferably has a void fraction <0.1% by volume (more preferably <0.01% by volume). The rigid layer (25) is preferably a biaxially oriented polyethylene terephthalate having an average thickness of> 5 to 60 mils (preferably 6 to 30 mils), more preferably 6 to 15 mils, although more preferably 6 to 10 thousandths of an inch); and, a Young's modulus, measured according to ASTM D882-12, at 100 MPa (preferably 1000 to 10,000 MPa, more preferably 2500 to 7500 MPa, most preferably 3000 to 7000 MPa).
[0023] To facilitate the detection of the polishing boundary point, the rigid layer (25) is preferably transparent to light at the wavelength (or wavelengths) of light detection for which the mechanical polishing felt is chemical (10) of the present invention is developed; has a through passage (35) in optical communication with the limit point detection window (30). (Refer to Figure 5). The cross-section of the through-passage (35) in the rigid layer (25) perpendicular to the B-axis may correspond in size to or be greater than, or smaller than, the cross section of the boundary-point detection window (30) parallel to the axis B. The cross section of the through passage (35) in the rigid layer (25) parallel to the B axis is even better for the chemical mechanical polishing felt (10) of the present invention smaller in dimension than the cross section of the limit point detection window (30). (Refer to Figure 5). Those skilled in the art will be able to choose a suitable hot melt adhesive (23) for use in the chemical mechanical polishing cloth (10). The hot melt adhesive (23) is preferably a cured reactive hot melt adhesive. The hot-melt adhesive (23) is even more preferably a cured reactive hot melt adhesive which has a melt temperature in its uncured state of from 50 to 150 ° C, preferably from 115 to 135 ° C and has a life-time of 5 90 minutes after melting. The hot melt adhesive (23) in its uncured state further includes a polyurethane resin (eg, Mor-Melt-Rm R5003 available from Rohm and Haas Company). The chemical-mechanical polishing felt (10) is preferably adapted to be connected to a cylinder of a polishing machine. The chemical-mechanical polishing felt (10) is preferably adapted to be attached to the cylinder of a polishing machine. The chemical mechanical polishing felt (10) can be attached to the cylinder using at least one of a pressure sensitive adhesive and vacuum.
[0024] The chemical mechanical polishing felt (10) preferably comprises a cylinder pressure sensitive adhesive (70) applied to the bottom surface (27) of the rigid layer (25). Those skilled in the art will be able to choose a pressure sensitive adhesive suitable for use as a cylinder pressure sensitive adhesive (70). The chemical mechanical polishing felt (10) will also preferably include a detachable liner (75) applied to the cylinder pressure sensitive adhesive (70), wherein the cylinder pressure sensitive adhesive (70) is interposed between the bottom surface (27) of the rigid layer (25) and the detachable liner (75). (Refer to Figure 2). The chemical-mechanical polishing felt (10) of the present invention optionally further comprises: at least one additional layer connected to and interposed between the polishing layer (20) and the cylinder pressure-sensitive adhesive layer ( 70). The at least one additional layer (not shown) may be incorporated into the polishing felt (10) using an additional layer adhesive (not shown). The additional layer adhesive may be selected from pressure sensitive adhesives, hot melt adhesives, contact adhesives, and combinations thereof. The additional layer adhesive is preferably a hot melt adhesive or a pressure sensitive adhesive. The additional layer adhesive is even better a hot melt adhesive. The method of the present invention for mechano-chemical polishing of a substrate preferably comprises: providing a chemical mechanical polishing apparatus having a cylinder, a light source and a photoelectric detector (preferably a multi-spectrograph) detector); providing at least one substrate to be polished (wherein the substrate is preferably selected from the group consisting of at least one of a magnetic substrate, an optical substrate and a semiconductor substrate; wherein the substrate is even better a substrate semiconductor, where the substrate is still more preferably a semi-conductive slab); providing a chemical mechanical polishing felt of the present invention; the installation on the cylinder of the chemical-mechanical polishing felt; optionally, providing a polishing medium at an interface between a polishing surface of the chemical mechanical polishing felt and the substrate (wherein the polishing medium is preferably selected from the group consisting of a polishing slurry and a reactive liquid formulation containing no abrasive); creating a dynamic contact between the polishing surface and the substrate, wherein at least a certain amount of material is removed from the substrate; and, determining a polishing boundary point by transmitting light from the light source through the boundary point detection window and analyzing light reflected from the substrate surface back through the limit point detection window incident on the photoelectric detector. The polishing boundary point is preferably determined based on an analysis of a wavelength of light reflected from the surface of the substrate and transmitted through the boundary point detection window, where the wavelength of light has a wavelength> 370 nm at 800 nm. The polishing limit point is further best determined on the basis of multiple wavelength analysis of light reflected from the surface of the substrate and transmitted through the boundary point detection window, where one of the lengths of analyzed wave has a wavelength> 370 nm at 800 nm. The method of polishing a substrate of the present invention optionally further comprises: periodically treating the polishing surface (14) with an abrasive treating agent.
[0025] Some embodiments of the present invention will now be described in detail in the following Examples. Polishing Layer: Comparative Examples AB and Examples 1-19 Polishing layers were prepared according to the details of the formulations provided in TABLE 3. Polyurethane cakes were specifically prepared by the controlled mixture of the polishing prepolymer at 50.degree. ° C (ie, Adiprene® LF667 for Comparative Example A and Examples 1-9, and Adiprene® LFG963A for Comparative Example B and Examples 10-19, both available from Chemtura Corporation) with the constituents of the polishing layer hardener system. The amine-initiated polyol curing agent (i.e., Voranol® 800 available from The Dow Chemical Company) and the high molecular weight polyol curing agent (i.e., Voralux® HF505 available from The Dow Chemical Company) were premixed before combination in the other raw materials. All raw materials, except MBOCA, were maintained at a pre-mix temperature of 51 ° C. MBOCA was maintained at a pre-mixing temperature of 116 ° C.
[0026] The ratio of the polishing layer hardener system to the polishing layer prepolymer has been set so that stoichiometry, defined by the ratio of reactive hydrogen groups (i.e., the sum of -OH groups and -NH2) in the unreacted isocyanate group (NCO) hardener system in the polishing layer prepolymer, was that shown in TABLE 3. Porosity was introduced into the polishing layers by adding microspheres Expancel® to the polishing layer prepolymer prior to combination with the polishing layer hardener system to achieve the desired porosity and density.
[0027] The polishing layer prepolymer with the incorporated Expancel® microspheres and the polishing layer hardener system were mixed together using a high shear mixing head. After the release of the mixing head, the combination was dispensed over a period of 5 minutes in a circular mold with a diameter of 86.4 cm (34 inches) to provide a total pouring thickness of approximately 10 cm (4 inches). . The dispensed combination was allowed to gel for 15 minutes before placing the mold in a curing oven. The mold was then cured in the curing oven using the following cycle: ramp 30 minutes from room temperature to a set point of 104 ° C, then hold for 15.5 hours at 104 ° C, and then 2 hour ramp from 104 ° C to 21 ° C. The cured polyurethane cakes were then removed from the mold and sliced (cut using a moving blade) at a temperature of 30 to 80 ° C in approximately forty separate sheets of thickness 2.0 mm (80 thousandths of an inch). Slicing was initiated from the top of each cake. Incomplete leaves were discarded. It is noted that Adiprene® LF667 used in the Examples is a PTMEG-based isocyanate-terminated urethane prepolymer comprising a 50/50 weight percent combination of Adiprene® LF950A and Adiprene® LF600D available from Chemtura. Adiprene® LFG963A is also a PPG-based isocyanate-terminated urethane prepolymer available from Chemtura. TABLE 3 Ex No. Prepolymer Prepolymer (Active H / NCO) Hardener System Porosity Agent Agent polishing layer (% NCO) stoichiometric polishing layer formation formation of (% by weight (%) pore pore volume) Expancel® (% by weight) MBOCA Voranol® Voralux® 800 HF 505 A Adiprene® LF667 6.7 100 0 0 0.85 551DE40d42 1.8 35 B Adiprene® LFG963A 5.8 100 0 0 0.9 551DE40d42 1.3 23 1 Adiprene® LF667 6.7 0 25 75 0.97 920DE40d30 1.3 34 2 Adiprene® LF667 6.7 67 8 25 0.97 920DE40d30 1.3 34 3 Adiprene® LF667 6.7 0 14 86 1.0 551DE40d42 1,4 29 4 Adiprene® LF667 6.7 14 12 74 1.0 551DE40d42 1.4 29 5 Adiprene® LF667 6.7 25 11 64 1.0 551DE40d42 1.4 28 6 Adiprene® LF667 6.7 25 11 64 1.0 551DE40d42 0.6 15 7 Adiprene® LF667 6.7 40 9 51 1.0 551DE40d42 1.4 28 8 Adiprene® LF667 6.7 50 7 43 1.0 551DE40d42 1.6 32 9 Adiprene® LF667 6 , 7 50 7 43 1.0 551DE40d42 0.7 18 10 Adiprene® LFG963A 5.8 14 12 74 1.0 551DE20d60 2.0 28 11 Adiprene® LFG963A 5.8 33 10 57 1.0 551DE20d60 2.0 28 12 Adiprene® LFG963A 5.8 14 12 74 1.0 551DE20d60 1.4 22 13 Adiprene® LFG963A 5.8 33 10 57 1.0 551DE20d60 1.5 23 14 Adiprene® LFG963A 5.8 41 8 51 1.0 551DE20d60 1.4 22 15 Adiprene® LFG963A 5.8 33 10 57 1.0 - - - 16 Adiprene® LFG963A 5.8 0 25 75 1.0 551DE20d60 2.0 28 17 Adiprene® LFG963A 5 , 8 0 14 86 1.0 551DE20d60 1.8 26 18 Adiprene® LFG963A 5.8 25 19 56 1.0 551DE20d42 1.6 32 19 Adiprene® LFG963A 5.8 25 19 56 1.0 551DE20d42 0.7 17 On analyzed the materials of the non-grooved polishing layers for each of Comparative Examples AB and Examples 1-19 to determine their physical properties as listed in TABLE 4. It is noted that the density data cited were determined according to ASTM D1622; quoted Shore D hardness data were determined according to ASTM D2240; the quoted Shore A hardness data were determined according to ASTM D2240; and, the cited elongation data were determined according to ASTM D412. The cutting speed data cited in TABLE 4 was measured using a Mirra® 200 mm polishing tool from Applied Materials. This polishing tool is developed to house a circular chemical mechanical polishing felt having a nominal diameter of 51 cm (20 inches). The polishing layers having a circular cross section were prepared as described herein in the Examples. These polishing layers were then grooved by machining to provide a pattern of grooves in the polishing surface comprising a plurality of concentric circular grooves having pitch dimensions of 120 mils (3.05 mm), width of 20 mils (0.51 mm) and 30 mil (0.76 mm) deep. The polishing layers were then laminated to form an expanded underlayment layer (SP2310 available from Rohm and Haas Electronic Materials CMP Inc.). A diamond treatment disc (DiaGrid® AD3CL-150840-3 felt treatment agent manufactured by Kinik Company) was used to abrade the polishing surface of the grooved polishing layers using the following processing conditions: the polishing surface polishing layers were continuously abraded from the diamond treatment disc over a period of 2 hours, with a cylinder speed of 100 rpm, a deionized water flow rate of 150 cm 3 / min and a downward force of the 48.3 kPa (7 psi) treatment disk. The cutting speed was determined by measuring the change in the average groove depth over time. The groove depth was measured (in pm / hour) using a Microtrack II Laser Triangulation Sensor MTI attached to a Zaber Technologies Motorized Slide to profile the polishing surface of each polishing layer from the center to the outer edge. The scanning speed of the sensor on the slide was 0.732 mm / s and the sampling rate (measurements / mm scan) for the sensor was 6.34 dots / mm. The cutting speed quoted in TABLE 4 is the average arithmetic reduction of the groove depth over time, based on the collected thickness measurements taken for> 2,000 points across the polishing surface of the polishing layer. . TABLE 4 Ex No. Density Hardness G 'to G' to G "to G 'to 30 ° C / G' to 90 ° C (MPa) Resistance Elongation Modulus Toughness (MPa) Speed (g / cm3) Shore 30 ° C 40 ° C 40 ° C Tensile tensile strength (MPa) (MPa) (MPa) (MPa) (%) (MPa) (MPH) ADA 0.78 93 43 - 44.0 2 , 6 1.4 17 191 65 24 34 B 0.88 91 41 - 49.0 3.2 1.9 15 293 95 62 26 1 0.76 56 10 3.2 3.1 0.1 1.0 3 161 4 3 - 2 0.76 83 35 27.8 24.2 2.7 1.4 16 250 46 23 - 3 0.81 48 7 2.2 2.2 0.1 1.1 2 160 3 2 72 4 0.81 57 11 4.6 3.8 0.5 1.5 5 294 5 9 41 5 0.82 62 18 9.0 8.2 0.9 1.3 7 360 13 15 - 6 0.98 61 17 5.0 4.6 0.5 1.1 8 414 7 16 - 7 0.82 75 23 16.8 15.6 1.4 1.3 11 346 26 22 30 8 0, 79 79 27 21.4 19.7 1.6 1.4 12 332 36 26 29 9 0.95 83 31 23.2 21.5 1.9 1.2 16 351 40 34 - 0.83 56 10 6 , 0 4.5 0.9 2.8 4 189 6 5 46 11 0.82 75 23 18.6 13.4 3.0 6.0 7 256 31 13 - 12 0.90 61 14 8.2 6 , 4 1,2 3,1 4,164 8 4 - 13 0,88 72 21 18,1 13,8 3,1 5,1 7 288 24 15 - 14 0,89 77 25 23,6 18,7 3.8 5.2 9 291 33 18 43 1.14 78 27 21.2 1 5.6 3.7 4.7 10 293 23 18 - 16 0.83 55 10 5.6 4.5 0.7 2.0 3 162 4 3 - 17 0.85 57 11 4.6 4, 0 0.4 1.7 3 143 4 2 - 18 0.78 70 19 18.0 13.3 2.6 4.7 5 173 23 7 - 19 0.96 73 20 17.9 12.5 2 Window: Comparative Examples C1-C24 and Examples 20-31 End point detection windows were prepared according to the details of the formulations provided in TABLE 5. Specifically, the window prepolymer with constituents of the hardener system using a vortex mixer at 1000 rpm for 30 seconds. All of the raw materials with the exception of the difunctional aromatic hardener (i.e., MBOCA and MCDEA) were maintained at a pre-mixing temperature of 60 ° C. MBOCA and MCDEA were maintained, when used, at a premix temperature of 120 ° C. The stoichiometric ratio between the window prepolymer and the window hardener system used for the endpoint detection windows is provided in TABLE 5 as the ratio of the reactive hydrogen groups (i.e., the sum of the groups). OH and -NH2 groups) in the window hardener system relative to the unreacted isocyanate groups (NCO) in the window prepolymer. In each of Comparative Examples C1-C24 and Examples 20-31, the window prepolymer and the window hardener system were mixed together using a high shear mixing head. After the release of the mixing head, the combination was dispensed into a 2 mm x 125 mm x 185 mm pocket mold. The pocket mold with the dispensed combination was then cured in an oven for eighteen (18) hours. The setting point temperature for the oven was initially set at 93 ° C for the first twenty (20) minutes; at 104 ° C for the next fifteen (15) hours and forty (40) minutes; and was then lowered to 21 ° C during the final two (2) hours. The pocket mold and its contents were then removed from the oven and the produced end-point detection window was then removed from the pocket mold. TABLE 5 Ex No. Pre- (% Window Hardener System (Active H / NCO Polymer) NCO) Stoichiometric Window Hardener Pl Hardener P2 Hardener P3 Hardener P4 Aromatic (% MW% (% in% non-amine (% in (P1) weight) high (P2) weight) amine weight (P4) weight (P3) Cl A 6.67 MbOCA 14.20 H 73.41 J 12.39 - - 1.0 C2 A 6.67 MBOCA 12.39 H 75.22 J 12.39 - - 1.0 C3 A 6.70 MbOCA 14.16 H 73.49 J 12.35 - - 1 0 C4 A 6.70 MbOCA 33.33 H 57.25 J 9.42 - - 1.0 C5 C 8.88 MbOCA - H 85.62 J 14.38 - - 1.0 C6 C 8.88 MbOCA - I 85.78 J 14.22 - - 1.0 C7 B 5.72 MbOCA - H 85.84 J 14.16 - - 1.0 C8 D 8.94 MbOCA - H 85.68 3 14.32 - - 1.0 C9 D 8.94 MbOCA - I 85.82 J 14.18 - - 1.0 C10 A 6.67 MCDEA - I 85 , 59 J 14.41 - - 1.0 C11 A 6.70 MbOCA - H 85.68 J 14.32 - - 1.0 C12 G 4.15 MbOCA 100 - - - - - - - 1.0 C13 B 5.83 MbOCA 100 - - - - - - 1.0 C14 E 2.86 MbOCA 100 - - - - - - 1 , 0 C15 F 3.80 MbOCA 100 - - - - - - 1.0 C16 B 5.83 MbOCA 14.26 H 85.74 - - - - 1.0 C17 B 5.83 MbOCA 14.25 I 85.75 - - - - 1.0 C18 B 5.72 MbOCA 14 , 38 H 73.44 - - K 12.18 1.0 C19 B 5.72 MbOCA 33.33 H 56.98 - - K 9.69 1.0 C20 A 6.67 MbOCA 14.29 H 85.71 - - - - 1.0 C21 A 6.67 MbOCA 14.29 I 85.71 - - - - 1.0 C22 A 6.70 MbOCA 14.37 H 73 , 52 - - K 12.11 1.0 C23 A 6.70 MbOCA 33.22 H 57.09 - - K 9.69 1.0 C24 L 8.95-9.25 MbOCA 100 - - - - - - 1.05 20 B 5.83 MbOCA 14.24 H 73.51 J 12.25 1.0 21 B 5.83 MbOCA 14.15 H 73.54 J 12.31 - - 1,0 TABLE 5 (CONTINUED) Ex No. Prepolymer (% Window Hardener System (Active H / NCO Window) NCO) Stoichiometric Hardener P1 Hardener P2 Hardener P3 Hardener P4 Aromatic (% MW) (% insider by (% non-amine (% by (P1) weight) high (P2) weight) amine weight (P4) weight (P3) 22 B 5.72 MbOCA 14.38 H 73.24 3 12.38 - - 1.0 23 B 5.72 MbOCA 33.33 H 57.32 3 9.35 - 1.0 24 B 5.83 MbOCA 14.24 H 73.51 3 12.25 - - 1.0 25 B 5.83 MbOCA 14.24 H 77.15 3 8.6 1 - - 0.84 26 B 5.83 MCDEA 14.29 H 79.12 3 6.59 - - 1.0 27 B 5.83 MbOCA 21.94 H 66.91 3 11.15 - - - 1.0 28 B 5.83 MbOCA 31.76 H 58.43 3 9.81 - - 1.0 29 B 5.83 MbOCA 43.67 H 48.47 3 7.86 - - - 1.0 30 B 5.83 MbOCA 58.33 H 35.78 3 5.89 - - 1.0 31 B 5.83 MbOCA 14.24 H 79.14 3 6.62 - - 0 , 76A is the Adiprene LF667 isocyanate-terminated urethane prepolymer comprising a combination of 50/50 weight percent Adiprene® LF950A and Adiprene® LF600D available from Chemtura. B is the Adiprene® LFG963A isocyanate-terminated urethane prepolymer available from Chemtura Corporation. This is the Adiprene® LFG740D isocyanate-terminated urethane prepolymer available from Chemtura Corporation. D is the Adiprene® LFG750D isocyanate-terminated urethane prepolymer available from Chemtura Corporation. E is the Adiprene® LF800A isocyanate-terminated urethane prepolymer available from Chemtura Corporation. F is the Adiprene® LF900A isocyanate-terminated urethane prepolymer available from Chemtura Corporation. G is the TDI-terminated prepolymer based on Polyether Vibrathane® 8628 available from Chemtura Corporation. H is the high molecular weight polyol hardener Voralux® HF505 having a number average molecular weight, MN, of 11,400 and an average of six hydroxyl groups per molecule available from The Dow Chemical Company. I is polytetramethylene ether glycol having a number average molecular weight, MN, of 2,000 and an average of two hydroxyl groups per molecule available from Sigma-Aldrich. 3 is the Voranol® 800 amine-initiated polyol curing agent having a number average molecular weight, MN, of 280 and an average of four hydroxyl groups per molecule available from The Dow Chemical Company. K is the non-Voranol 230-660 amine-containing polyol hardener having a number average molecular weight, MN, of 255 and an average of three hydroxyl groups per molecule available from The Dow Chemical Company. L is the Adiprene® L 325 isocyanate-terminated urethane prepolymer available from Chemtura Corporation.
[0028] The endpoint detection windows prepared according to each of Comparative Examples C1-C23 and Examples 20-31 were analyzed to determine the physical properties as set forth in TABLE 6.
[0029] The DPT400 and DPTsoo transmission data cited for the endpoint detection windows were determined using the following equation: DPT = (IWsi - IWD) ÷, (IAsi - IAD) where IWSi, IWD, IAsi, and IAD are measured using a Verity SP2006 Spectral Interferometer comprising an SD1024F spectrograph, a xenon flash lamp, and a 3mm optical fiber cable by placing a light emitting surface of the 3mm optical fiber cable against (and perpendicular to) a first face of the boundary point detection window at a point of origin, directing light at a given wavelength (i.e. at 400 nm and 800 nm respectively) through the thickness , Tw, of the window and measuring at the point of origin the light intensity of the given wavelength reflected back through the thickness of the window, Tw, from a surface disposed against a second face of the point detection window limit practically parallel to the first face; where IWsi is a measure of the light intensity at the given wavelength that passes through the window from the point of origin and is reflected from the surface of a silicon control wafer placed against a second face of the window back through the window to the point of origin; where IWD is a measure of the intensity of light at the given wavelength that passes from the point of origin through the window and is reflected from the surface of a black body and back through the window to the point of origin; where 'As; is a measure of the light intensity at the given length that passes from the point of origin through an air thickness equivalent to the thickness, Tw, of the endpoint detection window, which is reflected at from the surface of a silicon control wafer placed perpendicular to the light emitting surface of the 3 mm optical fiber cable and which is reflected back through the air thickness to the point of origin; and, where IAD is a measure of the intensity of light at the given wavelength reflected from a black body on the light emitting surface of the 3 mm optical fiber cable. The density data cited for the endpoint detection windows were determined according to ASTM D1622.
[0030] The Shore D hardness data cited for the endpoint detection windows were determined according to ASTM D2240. The tensile properties of the endpoint detection windows (i.e. tensile strength and elongation at break) were measured according to ASTM D1708-10 using an Alliance RT / 5 mechanical testing device available from MTS Systems Corporation as a crosshead speed of 2.54 cm / min. The entire test of tensile properties was carried out in a temperature and humidity controlled laboratory set at 23 ° C and a relative humidity of 50%. All test samples were packaged under the laboratory conditions cited for 5 days prior to testing. The tensile strength (MPa) and elongation at break (%) quoted for each end point detection window material were determined from tension-strain curves of four duplicate samples. TABLE 6 Ex. No. Properties DPT Density Hardness Resistance Elongation (in%) at (g / cm3) Shore D tensile strength at break (15s) (MPa) (%) 400 nm 800 nm Cl 0 0 1,11 17 8,38 426 C2 0 0 1,10 24 8,56 279 C3 2 1 1,09 6 3,55 287 C4 0 18 1,08 22 9,78 306 C5 0 0 1,07 10 2,81 131 C6 0 0 1,08 14 6,70 223 C7 16 41 1,08 14 2,48 160 C8 0 0 1,11 12 6,02 199 C9 0 0 1,07 10 8,18 345 C10 0 9 1,06 17 2,17 146 C11 1 0 1.07 6 2.91 262 C12 38 68 1.13 32 18.68 807 C13 8 64 1.13 55 24.94 492 C14 48 70 1.06 28 12.22 768 C15 26 53 1.08 38 27.32 860 C16 0 0 1.10 24 7.58 362 C17 0 1.07 9 1.82 145 C18 0 4 1.10 23 6.30 284 C19 0 31 1.11 32 12.22 404 C20 0 0 1,08 29 8,96 337 C21 0 0 1,07 14 2,89 517 C22 0 10 1,09 28 7,08 247 C23 0 8 1,09 36 15.08 353 20 55 70 1.12 21 6.30 242 21 38 61 1.07 26 6.63 196 22 44 70 1.10 15 5.19 281 23 37 66 1.10 25 11.05 390 24 42 59 1.11 7.21 248 25 25 68 1.12 29 6.98 152 26 50 61 1.13 23 6.88 243 27 51 70 1.11 6.30 255 28 50 75 1.12 34 9.77 328 29 47 74 1.13 38 12.98 379 30 32 68 1.13 42 14.50 356 31 22 54 1.12 28 5.79 1465 Evaluation of end point detection window swelling / indentation Window blocks were prepared according to the formulation and method described for each of Comparative Example C24 and Examples 8-11 except that the pocket mold was replaced by a window block mold having a cavity with the dimensions of 5.7 cm x 1 , 9 cm x 10.2 cm. The window blocks obtained were incorporated into polishing felt cakes of identical composition by conventional means and polishing layers having integral end point detection windows and an 80 mils Tp_moy were cut from the polishing layers. resultant felt cakes to provide a control polishing layer with a conventional window formulation (Comparative Example C24) and polishing layers with the window formulations of the invention (Examples 8-11). All of the polishing layers were 80-thousandths of an inch thick and had circular grooves that were 30-thousandths of an inch deep and 20-thousandths of an inch wide with a pitch of 120 thousandths of an inch. All polishing layers were laminated to Suba IVTM underfelt material. All polishing layers were subjected to simulated substrate polishing for four hours using a 200 mm Applied Materials Mirra polishing device with complete treatment (i.e., treatment alone). The felts were specifically installed in the polishing device and treated with a Saesol AK45 CMP processing disc (available from Saesol Diamond Ind. Co., Ltd.) with a downward force for treating 48.3 kPa; deionized water at a flow rate> 300 ml / min; a table rotation speed of 99 rpm; a treatment agent speed of 90 rpm. After the four (4) hours of simulated substrate polishing under the conditions cited, the integral window profiles were measured at the polishing surface to determine the measurement of outward swelling of the window from the surface polishing or recessing the window from the polishing surface. The maximum swelling or recess observed for each window is given in TABLE 7.35 TABLE 7 Window of the Example Maximum Swelling / Recess (in thousandths of an inch) C24 29.2 8 <1 9 1.3 10 1.5 11 1 , 0

权利要求:
Claims (10)
[0001]
REVENDICATIONS1. A chemical mechanical polishing felt (10), characterized in that it comprises: a polishing layer (20) having a polishing surface (14), a base surface (17) and a mean thickness, Tpni oy, measured in a direction perpendicular to the polishing surface (14) from the polishing surface (14) to the base surface (17); and, a limit point detection window (30) incorporated in the polishing layer (20); wherein the polishing layer (20) comprises an ingredient reaction product, comprising: a polishing layer prepolymer, wherein the polishing layer prepolymer is selected from the group consisting of isocyanate-terminated urethane prepolymers having from 2 to 12% by weight of unreacted NCO groups; and, a polishing layer hardener system comprising: at least 5% by weight of an amine initiated polyol polishing layer hardener having at least one nitrogen atom per molecule and an average of at least one three hydroxyl groups per molecule; from 25 to 95% by weight of a high molecular weight polyol polishing layer hardener having a number average molecular weight, MN, of 2,500 to 100,000 and an average of 3 to 10 hydroxyl groups per molecule; and from 0 to 70% by weight of a difunctional polishing layer hardener; wherein the limit point detection window (30) comprises an ingredient reaction product, comprising: a window prepolymer, wherein the window prepolymer is selected from the group consisting of isocyanate-terminated urethane prepolymers having 2 6.5% by weight of unreacted NCO groups; and, a window hardener system comprising: at least 5% by weight of a difunctional window hardener; at least 5% by weight of an amine initiated polyol window hardener having at least one nitrogen atom per molecule and an average of at least three hydroxyl groups per molecule; and from 25 to 90% by weight of a high molecular weight polyol window hardener having a number average molecular weight, MN, of 2,000 to 100,000 and an average of three to ten hydroxyl groups per molecule; wherein the polishing layer has a density 0.6 g / cm3; a Shore D hardness of 5 to 40; an elongation at break of 100 to 450%; and, a cutting speed of 25 to 150 pm / h.
[0002]
2. Chemical mechanical polishing felt according to claim 1, characterized in that the polishing surface is adapted to polish a substrate selected from a magnetic substrate, an optical substrate and a semiconductor substrate.
[0003]
3. The chemical mechanical polishing felt according to claim 1, characterized in that it further comprises: a rigid layer (25) having an upper surface (26) and a bottom surface (27); and, a hot melt adhesive (23) interposed between the base surface (17) of the polishing layer (20) and the upper surface (26) of the rigid layer (25); wherein the hot melt adhesive (23) binds the polishing layer (20) to the rigid layer (25).
[0004]
The chemical mechanical polishing mat according to claim 3, characterized in that it further comprises: a cylinder pressure sensitive adhesive (70); wherein the cylinder pressure sensitive adhesive (70) is disposed on the bottom surface (27) of the rigid layer (25); and, a detachable liner (75); wherein the cylinder pressure sensitive adhesive (70) is interposed between the bottom surface (27) of the rigid layer (25) and the detachable liner (75).
[0005]
A chemical mechanical polishing felt according to claim 1, characterized in that the window hardener system has a reactive hydrogen concentration and the window prepolymer has an unreacted NCO group concentration; and wherein the reactive hydrogen group concentration divided by the unreacted NCO group concentration is 0.7 to 1.2.
[0006]
The chemical mechanical polishing felt according to claim 1, characterized in that the limit point detection window has a density of 1 g / cm3; porosity less than 0.1% in flight; a Shore D hardness of 10 to 50; elongation at break 5. 400%; and, a double pass transmission at 800 nm, DPT800, of 30 to 100%.
[0007]
The chemical mechanical polishing pad according to claim 6, characterized in that the limit point detection window also has a 25-100% 400-pass double-pass transmission, DPT400.
[0008]
The chemical mechanical polishing pad according to claim 1, characterized in that the polishing layer hardener system contains: 5 to 20% by weight of the amine initiated polyol polishing layer hardener, wherein the amine-initiated polyol polishing layer hardener has two nitrogen atoms per molecule, an average of four hydroxyl groups per molecule, and a number average molecular weight, MN, of 200 to 400; From 50 to 75% by weight of the high molecular weight polyol polishing layer hardener, wherein the high molecular weight polyol polishing layer hardener has a number average molecular weight, MN, of 10,000 to 12 000; and an average of six hydroxyl groups per molecule; From 10 to 30% by weight of the difunctional polishing layer hardener; wherein the difunctional polishing layer hardener is a diamine hardener selected from the group consisting of 4,4-methylene-bis- (2-chloroaniline) (MBOCA); 4,4'-methylenebis- (3-chloro-2,6-diethylaniline) (MCDEA); and isomers thereof; Wherein the polishing layer hardener system has a plurality of reactive hydrogen moieties and the polishing layer prepolymer has a plurality of unreacted NCO moieties; wherein the molar ratio of reactive hydrogen moieties in the polishing layer hardener system to unreacted isocyanate groups in the polishing layer prepolymer is from 0.95 to 1.05; and, wherein the polishing layer has a density of 0.75 to 1.0 g / cm3; a Shore D hardness of 5 to 20; an elongation at break of 150 to 300%; and, a cutting speed of 30 to 60 pm / h. 10
[0009]
9. A method of polishing a substrate, characterized in that it comprises: providing a chemical-mechanical polishing apparatus having a cylinder, a light source and a photoelectric sensor; Providing at least one substrate; providing a chemical mechanical polishing felt according to claim 1; the installation on the cylinder of the chemical-mechanical polishing felt; Optionally, providing a polishing medium at an interface between the polishing surface and the substrate; creating a dynamic contact between the polishing surface and the substrate, wherein at least a certain amount of material is removed from the substrate; and, determining a polishing boundary point by transmitting light from the light source through the boundary point detection window and analyzing light reflected from the surface of the substrate back through the limit point detection window incident on the photoelectric sensor. 30
[0010]
10. The method of claim 9, characterized in that the at least one substrate is selected from the group consisting of at least one of a magnetic substrate, an optical substrate and a semiconductor substrate.

类似技术:

---

公开号 | 公开日 | 专利标题

---

FR3019076B1|2019-06-14|MECANO-CHEMICAL POLISHING FELT WITH POLISHING LAYER AND WINDOW

---

FR3019077A1|2015-10-02|MECANO-CHEMICAL POLISHING FELT WITH FLEXIBLE WINDOW AND TREATMENT-FRIENDLY

---

FR3020296A1|2015-10-30|MECANO-CHEMICAL POLISHING FELT

---

FR3020298A1|2015-10-30|MECHANICAL CHEMICAL POLISHING FELT WITH TRANSPARENT LIMIT POINT DETECTION WINDOW

---

FR3020297A1|2015-10-30|MECHANICAL CHEMICAL POLISHING FELT WITH LIMITED STITCH DETECTION WINDOW

---

KR102195526B1|2020-12-28|Soft and conditionable chemical mechanical window polishing pad

---

FR3022814A1|2016-01-01|FORMULATION OF MECHANICAL CHEMICAL POLISHING LAYER WITH TREATMENT TOLERANCE

---

US9238296B2|2016-01-19|Multilayer chemical mechanical polishing pad stack with soft and conditionable polishing layer

---

FR2997331A1|2014-05-02|MECANO-CHEMICAL POLISHING SKIN FLEXIBLE AND PUTABLE

---

FR3022815A1|2016-01-01|METHOD FOR MECHANICAL CHEMICAL POLISHING

---

KR102191947B1|2020-12-17|Soft and conditionable chemical mechanical polishing pad stack

---

FR3037835A1|2016-12-30|FORMULATION OF MECANO-CHEMICAL POLISHING PILL POLISHING LAYER COMPOSITION

---

FR3043001A1|2017-05-05|METHOD FOR MECANO-CHEMICAL POLISHING, CORRESPONDING POLISHING PAD AND METHOD OF PRODUCING THE SAME

---

FR3037836A1|2016-12-30|

---

TWI590919B|2017-07-11|Soft and conditionable chemical mechanical polishing pad with window and method of polishing substrate

---

FR3019075A1|2015-10-02|MECHANICAL CHEMICAL POLISHING FELT WITH LIMITED STITCH DETECTION WINDOW

---

TWI510526B|2015-12-01|A chemical mechanical polishing pad having a low defect integral window

同族专利:

---

公开号 | 公开日

---

JP6538397B2|2019-07-03|

---

CN104942700A|2015-09-30|

---

FR3019077B1|2018-08-17|

---

US9064806B1|2015-06-23|

---

CN104942700B|2017-09-12|

---

JP2015189003A|2015-11-02|

---

KR20150112853A|2015-10-07|

---

DE102015003200A1|2015-10-01|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

US5433651A|1993-12-22|1995-07-18|International Business Machines Corporation|In-situ endpoint detection and process monitoring method and apparatus for chemical-mechanical polishing|

---

US5605760A|1995-08-21|1997-02-25|Rodel, Inc.|Polishing pads|

---

US6106662A|1998-06-08|2000-08-22|Speedfam-Ipec Corporation|Method and apparatus for endpoint detection for chemical mechanical polishing|

---

US6171181B1|1999-08-17|2001-01-09|Rodel Holdings, Inc.|Molded polishing pad having integral window|

---

JP2002001647A|2000-06-19|2002-01-08|Rodel Nitta Co|Polishing pad|

---

JP2004259728A|2003-02-24|2004-09-16|Toray Ind Inc|Polishing pad|

---

US8864859B2|2003-03-25|2014-10-21|Nexplanar Corporation|Customized polishing pads for CMP and methods of fabrication and use thereof|

---

US7195539B2|2003-09-19|2007-03-27|Cabot Microelectronics Coporation|Polishing pad with recessed window|

---

US7101275B2|2003-09-26|2006-09-05|Rohm And Haas Electronic Materials Cmp Holdings, Inc.|Resilient polishing pad for chemical mechanical polishing|

---

US7074115B2|2003-10-09|2006-07-11|Rohm And Haas Electronic Materials Cmp Holdings, Inc.|Polishing pad|

---

US7258602B2|2003-10-22|2007-08-21|Iv Technologies Co., Ltd.|Polishing pad having grooved window therein and method of forming the same|

---

US6984163B2|2003-11-25|2006-01-10|Rohm And Haas Electronic Materials Cmp Holdings, Inc.|Polishing pad with high optical transmission window|

---

US7204742B2|2004-03-25|2007-04-17|Cabot Microelectronics Corporation|Polishing pad comprising hydrophobic region and endpoint detection port|

---

US7018581B2|2004-06-10|2006-03-28|Rohm And Haas Electronic Materials Cmp Holdings, Inc.|Method of forming a polishing pad with reduced stress window|

---

US8075372B2|2004-09-01|2011-12-13|Cabot Microelectronics Corporation|Polishing pad with microporous regions|

---

JP2007307639A|2006-05-17|2007-11-29|Toyo Tire & Rubber Co Ltd|Polishing pad|

---

JP5110677B2|2006-05-17|2012-12-26|東洋ゴム工業株式会社|Polishing pad|

---

JP5145683B2|2006-07-20|2013-02-20|東レ株式会社|Polishing method, polishing pad, and manufacturing method of polishing pad|

---

US8083570B2|2008-10-17|2011-12-27|Rohm And Haas Electronic Materials Cmp Holdings, Inc.|Chemical mechanical polishing pad having sealed window|

---

US8118641B2|2009-03-04|2012-02-21|Rohm And Haas Electronic Materials Cmp Holdings, Inc.|Chemical mechanical polishing pad having window with integral identification feature|

---

US8257544B2|2009-06-10|2012-09-04|Rohm And Haas Electronic Materials Cmp Holdings, Inc.|Chemical mechanical polishing pad having a low defect integral window|

---

JP5715770B2|2010-06-17|2015-05-13|ローム アンド ハース エレクトロニック マテリアルズ シーエムピー ホウルディングス インコーポレイテッド|Chemical mechanical polishing pad having a low defect integral window and method of chemical mechanical polishing a substrate using the chemical mechanical polishing pad|

---

US8257545B2|2010-09-29|2012-09-04|Rohm And Haas Electronic Materials Cmp Holdings, Inc.|Chemical mechanical polishing pad with light stable polymeric endpoint detection window and method of polishing therewith|

---

US8512427B2|2011-09-29|2013-08-20|Rohm And Haas Electronic Materials Cmp Holdings, Inc.|Acrylate polyurethane chemical mechanical polishing layer|US9259820B2|2014-03-28|2016-02-16|Rohm And Haas Electronic Materials Cmp Holdings, Inc.|Chemical mechanical polishing pad with polishing layer and window|

---

US9216489B2|2014-03-28|2015-12-22|Rohm And Haas Electronic Materials Cmp Holdings, Inc.|Chemical mechanical polishing pad with endpoint detection window|

---

USD785339S1|2014-10-23|2017-05-02|Griot's Garage, Inc.|Hand applicator buffing pad|

---

US20160144477A1|2014-11-21|2016-05-26|Diane Scott|Coated compressive subpad for chemical mechanical polishing|

---

US9484212B1|2015-10-30|2016-11-01|Rohm And Haas Electronic Materials Cmp Holdings, Inc.|Chemical mechanical polishing method|

---

TW201807142A|2016-05-10|2018-03-01|陶氏全球科技有限責任公司|Two-component solventless adhesive compositions comprising an amine-initiated polyol|

---

US20180281149A1|2017-03-31|2018-10-04|Rohm And Haas Electronic Materials Cmp Holdings, Inc.|Chemical mechanical polishing pad|

---

KR101945878B1|2017-07-11|2019-02-11|에스케이씨 주식회사|Polishing pad comprising window having similar hardness with polishing layer|

---

CN112720282A|2020-12-31|2021-04-30|湖北鼎汇微电子材料有限公司|Polishing pad|

法律状态:
2016-02-08| PLFP| Fee payment|Year of fee payment: 2 |

---

2017-02-13| PLFP| Fee payment|Year of fee payment: 3 |

---

2018-01-26| PLSC| Publication of the preliminary search report|Effective date: 20180126 |

---

2018-02-23| PLFP| Fee payment|Year of fee payment: 4 |

---

2020-02-14| PLFP| Fee payment|Year of fee payment: 6 |

---

2021-02-10| PLFP| Fee payment|Year of fee payment: 7 |

---

2022-02-09| PLFP| Fee payment|Year of fee payment: 8 |

优先权:

---

申请号 | 申请日 | 专利标题

---

US14228744|2014-03-28|

---

US14/228,744|US9064806B1|2014-03-28|2014-03-28|Soft and conditionable chemical mechanical polishing pad with window|

---