Polishing layer, polishing pad, and method for manufacturing semiconductor device

Abstract

The present application relates to a kind of polishing layer, the closed-cell elastomer formed by the continuous polyurethane base material separated by 5-100 μm size pore comprises the reaction product of prepolymers via isocyanate end-capping and curing agent;The polishing layer includes polishing surface, at the distance h above polishing surface, the mass of the sphere of L diameter is m, when sphere contacts polishing surface, the height of the bottom of metal ball to polishing surface to the time when the upward rebound of metal ball to linear velocity is equal to 0 is h1, when h is between 490mm-520mm, the mass of sphere m is between 15g-19g, the diameter of sphere L is between 15mm-17mm, wherein, loss height h2=h-h1-L, the loss height h2 is between 280mm-440mm;Control polishing layer in above-mentioned range, the polishing pad prepared shows good polishing performance, including higher TEOS removal rate, lower polishing rate inhomogeneity and less Defect, and excellent comprehensive performance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of semiconductor chemical mechanical polishing, in particular to a polishing layer, a polishing pad and a manufacturing method of a semiconductor device. BACKGROUND

[0002] Chemical mechanical polishing is a conventional technique for planarizing or polishing a workpiece such as a semiconductor wafer, in conventional CMP, a wafer carrier or polishing head is mounted in a carrier assembly, the polishing head clamps the wafer and positions the wafer in contact with a polishing layer of a polishing pad, the polishing pad is mounted on a table or platen in a CMP device. The carrier assembly provides a controllable pressure between the wafer and the polishing pad. At the same time, a polishing medium such as a polishing slurry is dispensed onto the polishing pad and drawn into the interstices between the polishing pad and the wafer, for polishing, the polishing pad and the wafer are usually rotated relative to each other, as the polishing pad rotates beneath the wafer, the wafer sweeps out a generally annular polishing track or polishing area in which the wafer surface is directly against the polishing layer, through the polishing layer and the polishing medium on the surface and the chemical mechanical action, the wafer surface is polished and becomes planar.

[0003] Semiconductor devices are becoming more and more complex, with more fine structure units and more metallization layers, there is an urgent need to improve the performance of the polishing pad to maintain flatness and limit polishing defects; the resilience performance of the polishing pad affects the RR, the number of defects and other vital performances, the polishing pad is usually composed of polyurethane material, how to control the resilience performance of the polishing pad through formula design to obtain a polishing pad with more excellent performance is a problem to be solved in the prior art. SUMMARY

[0004] To solve the problems in the prior art, the present application provides a polishing layer, the polishing layer comprises a closed-cell elastomer formed by 5-100 μm size pores separating a continuous polyurethane substrate, the polyurethane substrate comprises a reaction product of a prepolymer terminated by isocyanate and a curing agent; the polishing layer comprises a polishing surface, at a distance h above the polishing surface, a sphere with a mass of m and a diameter of L is freely released, when the sphere contacts the polishing surface, the height from the bottom of the metal sphere to the polishing surface at the moment when the upward rebounding linear velocity of the metal sphere is equal to 0 is h1, when h is between 490 mm-520 mm, the mass m of the sphere is between 15 g-19 g, the diameter L of the sphere is between 15 mm-17 mm, wherein the loss height h2=h-h1-L, the loss height h2 is between 280 mm-440 mm;

[0005] Further, the thickness of the polishing layer is between 50 mil-120 mil;

[0006] Further, the density of the polishing layer is between 0.4 g / cm3 ~ 1.1 g / cm 3 ;

[0007] Preferably, the density of the polishing layer is between 0.5 g / cm 3 ~ 1.05 g / cm 3 ;

[0008] More preferably, the density of the polishing layer is between 0.6 g / cm 3 ~ 1.0 g / cm 3 ;

[0009] Further, the isocyanate-terminated prepolymer comprises a reaction product of a polyfunctional isocyanate and a polyol;

[0010] Further, the polyfunctional isocyanate comprises one or more of 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, ethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, norbornane diisocyanate;

[0011] Preferably, the polyfunctional isocyanate comprises one or more of 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate;

[0012] Further, the polyol comprises one or more of polytetramethylene ether glycol, polyethylene glycol, polypropylene glycol, ethylene glycol, butylene glycol, diethylene glycol, neopentyl glycol, 2-methyl-1,3-propanediol, hexanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanedimethanol, homopolymers and / or copolymers of ethylene oxide and propylene oxide;

[0013] Preferably, the polyol comprises one or more of polytetramethylene ether glycol, polypropylene glycol, diethylene glycol, homopolymers and / or copolymers of ethylene oxide and propylene oxide;

[0014] Further, the curing agent comprises a polyamine-based curing agent or a polyol curing agent;

[0015] Further, the polyamine curing agent comprises one or more of diethyltoluene diamine (DETDA), N,N'-dialkyl diamino diphenyl methane, 3,5-diethyl-2,4-toluene diamine and its isomers (e.g., 3,5-diethyl-2,6-toluene diamine), 3,5-dimethylthio-2,4-toluene diamine and its isomers, 4,4'-methylene-bis-(2-chloroaniline) (MOCA), 4,4'-bis-(sec-butylamino)-diphenyl methane, 1,4-bis-(sec-butylamino)-benzene, 4,4'-methylene-bis-(2-chloroaniline), 4,4'-methylene-bis-(3-chloro-2,6-diethyl aniline) (MCDEA), polyoxytetramethylene-di-p-aminobenzoate; p,p'-methylene bis aniline (MDA); m-phenylenediamine (MPDA); 4,4'-methylene-di-(2,6-diethyl aniline) (MDEA), 4,4'-methylene-di-(2,3-dichloro aniline) (MDCA), 4,4'-diamino-3,3'-diethyl-5,5'-dimethyl diphenyl methane, 2,2',3,3'-tetrachloro diamino diphenyl methane, propylene glycol-di-p-aminobenzoate;

[0016] Preferably, the polyamine curing agent is 4,4'-methylene-bis-(2-chloroaniline) (MOCA);

[0017] Further, the polyol curing agent has a number average molecular weight of 2000-100000, and the polyol curing agent has an average of 3-30 hydroxyl groups;

[0018] Preferably, the polyol curing agent comprises 4-8 hydroxyl groups;

[0019] Further, the unreacted NCO of the isocyanate-terminated prepolymer is between 8.0% and 9.5%, and the stoichiometric ratio of NH2 from the curing agent to NCO of the isocyanate-terminated prepolymer is between 80% and 105%;

[0020] The second aspect of the present application provides a polishing pad for chemical mechanical polishing of a substrate selected from at least one of a magnetic substrate, an optical substrate and a semiconductor substrate, the polishing pad comprising a polishing layer as described above.

[0021] The third aspect of the present application provides a polishing pad for chemical mechanical polishing of a substrate selected from at least one of a magnetic substrate, an optical substrate and a semiconductor substrate, the polishing pad having a resilience of between 5% and 40%.

[0022] Further, the polishing pad comprises a polishing layer, an intermediate adhesive layer, a buffer layer and a release film layer.

[0023] The fourth aspect of the present application provides a method for manufacturing a semiconductor device, a semiconductor device comprising a substrate selected from at least one of a magnetic substrate, an optical substrate or a semiconductor substrate, the polishing pad as described above, forming a dynamic contact between the polishing surface of the polishing layer and the substrate, thereby polishing the surface of the substrate, and trimming the polishing surface using an abrasive trimmer.

[0024] Advantages

[0025] The present application adjusts the resilience of the polyurethane material by controlling the formulation of the polyurethane, so that the resilience of the polishing layer and the polishing pad prepared within a certain range, the polishing pad shows good polishing performance, including higher TEOS removal rate, lower polishing rate inhomogeneity and less defects, and excellent comprehensive performance. BRIEF DESCRIPTION OF DRAWINGS

[0026] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed in the embodiment description will be briefly introduced. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor.

[0027] Figure 1 A process diagram of the polishing operation of the polishing pad in the embodiments of the present application is provided.

[0028] Figure 2 A schematic diagram of the polishing pad provided in the embodiments of the present application is provided.

[0029] Figure 3 A schematic diagram of the original state of the device for measuring the loss height h2 and the resilience in the embodiments of the present application is provided.

[0030] Figure 4 A schematic diagram of the measuring state of the device for measuring the loss height h2 and the resilience in the embodiments of the present application is provided.

[0031] 1 - material to be polished; 2 - polishing pad; 3 - polishing machine; 4 - support; 5 - polishing liquid; 20 - polishing layer; 21 - adhesive layer; 22 - buffer layer; 23 - back adhesive layer. DETAILED DESCRIPTION

[0032] The polishing layer in the embodiment of the present application comprises a closed-cell elastomer formed by 5-100 μm size pores separating continuous polyurethane substrates, and the polyurethane substrate in the embodiment of the present application comprises a reaction product of a prepolymer terminated by isocyanate and a curing agent. Alternatively, the polyurethane substrate in the embodiment of the present application can also be synthesized by a one-step synthesis method, i.e. using a multifunctional isocyanate, a polyol and a curing agent to directly react to obtain; preferably, the prepolymer method of selecting the reaction of the prepolymer terminated by isocyanate and the curing agent is used for synthesis in the embodiment of the present application.

[0033] The polishing layer in the embodiment of the present application comprises a polishing surface, and a sphere with a mass of m and a diameter of L is freely released at a distance of h above the polishing surface, and when the sphere contacts the polishing surface, the height of the bottom of the metal sphere to the polishing surface at the moment when the upward rebounding speed of the metal sphere is equal to 0 is h1, when h is between 490 mm and 520 mm, the mass m of the sphere is between 15 g and 19 g, and the diameter L of the sphere is between 15 mm and 17 mm, wherein the loss height h2 = h - h1 - L, and the loss height h2 is between 280 mm and 440 mm.

[0034] The loss height h2 in the embodiment of the present application is a parameter for reflecting the rebound performance of the polishing layer, and the specific test equipment can be referred to, and the above test conditions are preferably: the release height h is 500 mm, the metal sphere is a steel ball, the mass m is 16.8 ± 1.5 g, and the diameter L is 16 mm.

[0035] The thickness of the polishing layer in the embodiment of the present application is between 50 mil and 120 mil, preferably between 50 mil and 100 mil, and particularly preferably between 50 mil and 80 mil.

[0036] The density of the polishing layer in the embodiment of the present application is between 0.4 g / cm 3 and 1.1 g / cm 3 , preferably between 0.5 g / cm 3 and 1.05 g / cm 3 , and particularly preferably between 0.6 g / cm 3 and 1.0 g / cm 3 .

[0037] The prepolymer terminated by isocyanate in the embodiment of the present application comprises a reaction product of a multifunctional isocyanate and a polyol.

[0038] The multifunctional isocyanate

[0039] The polyfunctional isocyanate in the embodiments of the present application includes, but is not limited to, one or more combinations of aromatic isocyanate or aliphatic isocyanate, preferably using 80 mol% or more of aromatic isocyanate, further preferably using 95 mol% or more of aromatic isocyanate, and particularly preferably using 100 mol% of aromatic isocyanate.

[0040] The aromatic isocyanate includes one or more combinations of toluene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylylene diisocyanate, and m-xylylene diisocyanate.

[0041] The aliphatic isocyanate includes one or more combinations of ethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, and norbornane diisocyanate.

[0042] In the embodiments of the present application, one or more combinations of toluene diisocyanate, diphenylmethane diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate are preferably used for the consideration of reactivity and physical properties of the polishing pad.

[0043] In the embodiments of the present application, one or a combination of toluene diisocyanate and 4,4-dicyclohexylmethane diisocyanate is particularly preferably used for the consideration of reactivity and physical properties of the polishing pad, wherein the toluene diisocyanate can include one or a combination of 2,4-toluene diisocyanate or 2,6-toluene diisocyanate.

[0044] Polyol

[0045] The polyol in the embodiments of the present application can include a polyether-based high molecular weight diol, wherein the polyether-based high molecular weight diol includes, but is not limited to, one or more combinations of polytetramethylene ether glycol (PTMEG), polyethylene glycol (PEG), polypropylene glycol (PPG), and polytetramethylene ether glycol-polyethylene glycol, polytetramethylene ether glycol-polypropylene glycol, polyethylene glycol-polypropylene glycol, homopolymers and / or copolymers of ethylene oxide and propylene oxide, or a high molecular polyol formed by homopolymerization or copolymerization of glycol, propylene glycol, butanediol, or an initiator having two hydroxyl groups with the above three small molecular diols, or a combination thereof.

[0046] The polyol in the embodiments of the present application can include a small molecular diol, wherein the small molecule includes, but is not limited to, one or more combinations of ethylene glycol, butanediol, diethylene glycol, neopentyl glycol, 2-methyl-1,3-propanediol, hexanediol, 3-methyl-1,5-pentanediol, and 1,4-cyclohexanedimethanol.

[0047] The polyol composition in the embodiments of the present application can also comprise a polyester-based polyol, wherein the polyester-based polyol is obtained by condensation reaction of a diol or diol / phenol with a diacid, wherein the diol comprises one or more of a combination of ethylene glycol, 1,3-butanediol, 1,4-butanediol, diethylene glycol, neopentyl glycol, 2-methyl-1,3-propanediol, hexanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanedimethanol, preferably the diol comprises one or a combination of 1,4-butanediol, hexanediol; the diol / phenol is one or more of a combination of hydroquinone, resorcinol, naphthalene diol, bisphenol A, bisphenol S, p-xylenol, m-xylenol, o-xylenol, 2,5-furandimethanol, p-xylenol, or diphenyl ether diol, preferably the diol / phenol is one or a combination of hydroquinone, p-xylenol; the diacid is one or more of a combination of succinic acid, adipic acid, azelaic acid, sebacic acid.

[0048] For reactivity and physical properties of the polishing pad, one or more of a combination of polytetramethylene ether glycol (PTMEG), diethylene glycol, butanediol, or homo- and / or co-polymers of ethylene oxide and propylene oxide are preferred in the embodiments of the present application.

[0049] For reactivity and physical properties of the polishing pad, one or more of a combination of polytetramethylene ether glycol (PTMEG), diethylene glycol, butanediol, or homo- and / or co-polymers of ethylene oxide and propylene oxide are preferred in the embodiments of the present application.

[0050] The isocyanate-terminated prepolymer described above can be obtained by reacting the polyol described above with the polyfunctional isocyanate, or can be obtained by purchasing a commercially available prepolymer product.

[0051] The commercially available isocyanate-terminated prepolymer includes, but is not limited to, any one or more of a combination of the series of prepolymers produced by Chemtura Corporation: LF800A, LF900A, LF910A, LF930A, LF931A, LF939A, LF950A, LF952A, LF600D, LF601D, LF650D, L42, L325, L100, L150, L167, L200, L275, L300, L310, L367, L480, L500, LF667, LF667D, LF700D, LF750D, LF751D, LF752D, LF753D, LFG963A, LFG964A, LFG740D.

[0052] Curing agent

[0053] The curing agent in the embodiments of the present application is selected from one or more of a combination of a polyamine curing agent or a polyol curing agent. The polyamine curing agent or the polyol curing agent is not particularly limited in the present application and can be any suitable aromatic difunctional curing agent or polyol curing agent in the art.

[0054] Examples of the polyamine curing agent that can be used in the embodiments of the present application include one or more of a combination of diethyltoluenediamine (DETDA), N,N'-dialkyldiaminodiphenylmethane, 3,5-diethyl-2,4-toluenediamine and its isomers (e.g., 3,5-diethyl-2,6-toluenediamine), 3,5-dimethylthio-2,4-toluenediamine and its isomers, 4,4'-methylene-bis-(2-chloroaniline) (MOCA), 4,4'-bis-(sec-butylamino)-diphenylmethane, 1,4-bis-(sec-butylamino)-benzene, 4,4'-methylene-bis-(2-chloroaniline), 4,4'-methylene-bis-(3-chloro-2,6-diethyl aniline) (M-CDEA), polyoxytetramethylene-di-p-aminobenzoate; p,p'- methylenedianiline (MDA); m-phenylenediamine (MPDA); 4,4'-methylene-bis-(2,6-diethyl aniline) (MDEA), 4,4'-methylene-bis-(2,3-dichloroaniline) (MDCA), 4,4'-diamino-3,3'- diethyl-5,5'-dimethyl diphenylmethane, 2,2',3,3'-tetrachlorodiaminodiphenylmethane, propylene glycol-di-p-aminobenzoate.

[0055] In view of the unique chemical structure of MOCA, to ensure that the polishing pad has a suitable workable time during the preparation of the polishing pad and the resulting polishing pad has good polishing performance, preferably, the polyamine curing agent comprises one or a combination of 4,4'-methylene-bis-(2-chloroaniline) (MOCA) and 4,4'-methylene-bis-(3-chloro-2,6-diethyl aniline) (M-CDEA); particularly preferably, the polyamine curing agent comprises 4,4'-methylene-bis-(2-chloroaniline) (MOCA).

[0056] Alternatively, the polyol curing agent in the embodiments of the present application can also be selected from a high molecular weight polyol curing agent. The high molecular weight polyol curing agent has a number average molecular weight of 2000 to 100000. The high molecular weight polyol curing agent has an average of 3 to 30 hydroxyl groups. Preferably, the high molecular weight polyol has 4 to 8 hydroxyl groups. Commercially available high molecular weight polyols can be selected from polyols, polyols and polyols in the polyol series (from Dow Chemical). Preferably, the embodiments of the present application comprise a combination of a polyamine curing agent and a high molecular weight polyol curing agent. Particularly preferably, the embodiments of the present application only comprise a polyamine curing agent.

[0057] Hollow microsphere polymer

[0058] In the polishing layer preparation process, the hollow microsphere polymer is usually uniformly dispersed in the polishing layer, so as to realize the adjustment of the polishing effect of the polishing layer.

[0059] The term "hollow microsphere polymer" in the embodiments of the present application refers to an expandable hollow polymer microsphere which can be moderately expanded by means of the temperature rise caused by reaction heat during the curing process. By adjusting the distribution mode (such as density) of the hollow microsphere polymer in the polyurethane polishing layer and combining with the adjustment of the particle size of the hollow microsphere polymer, the polishing performance of the polishing layer can be further adjusted. Preferably, the dispersion of the hollow microsphere polymer in the polishing layer can make the polishing layer finally have a porosity of 10% to 65%.

[0060] Preferably, the hollow microsphere polymer includes but is not limited to a capsule structure with a polyacrylonitrile and a polyacrylonitrile copolymer outer wall, and can be purchased from any one of the following companies: Nouryon, Matsumoto Yushi-Seiyu Co., Ltd. or Sekisui Chemical Co., Ltd. In particular, preferably, the hollow microspheres of Nouryon or the Matsumoto microbeads F series are selected in the embodiments of the present application.

[0061] The unreacted NCO of the isocyanate-terminated prepolymer in the embodiments of the present application is between 8.0% and 9.5%, and preferably, the unreacted NCO of the isocyanate-terminated prepolymer is between 8.5% and 9.5%.

[0062] The stoichiometric ratio of NH2 or / and OH in the curing agent to the NCO of the isocyanate-terminated prepolymer in the embodiments of the present application is between 80% and 105%, and preferably, the stoichiometric ratio of NH2 or / and OH in the curing agent to the NCO of the isocyanate-terminated prepolymer is between 80% and 100%.

[0063] The rebound performance of the polishing pad in the embodiments of the present application is between 5% and 40%, such as Figure 2 As shown in the figure, the polishing pad comprises a polishing layer 20, an intermediate adhesive layer 21, a buffer layer 22 and a release film layer 23.

[0064] In the present application, appropriate modifiers can also be added to the polyurethane base material in order to obtain more excellent comprehensive performance improvement. Preferably, these modifiers can improve at least one property of the polishing layer, and the above-mentioned properties include but are not limited to the following group consisting of porosity, rigidity, surface energy, wear resistance, conductivity, and chemical function. The modified materials include but are not limited to: antioxidants, lubricants, pigments, fillers, anti-static agents, etc.

[0065] In the present application, the polishing layer can be provided with grooves in accordance with the conventional practice in the art, the grooves being used to receive the polishing liquid during the polishing process. The grooves can be obtained by machining after the polishing layer is formed. The provision of the grooves can ensure smooth discharge and flow of the polishing liquid used in the polishing process. Preferably, the grooves are one or more of concentric circular grooves (e.g. annular or spiral grooves), curved grooves, grid line grooves, regular polygonal grooves (e.g. hexagonal, triangular), and tire tread pattern. Particularly preferably, the grooves are one or more of annular grooves, spiral grooves, X-Y grid grooves, hexagonal grooves, triangular grooves and fractal grooves. Particularly preferably, the cross-section of the grooves is one or more of straight-sided rectangular, "V"-shaped, "U"-shaped and zigzag.

[0066] Alternatively, the width of the grooves is 0.1-0.6 mm, the depth of the grooves is 0.5-0.9 mm, and the distance between adjacent grooves is 2-5 mm, and a center blank area or no center blank area can be provided, wherein the radius of the center blank area is 50-150 mm.

[0067] In CMP, a buffer layer is needed to balance the planarity and uniformity, which are in a trade-off relationship with each other. The planarity refers to the flatness of the pattern part when polishing a polished material having a slight concave-convex generated during pattern formation, and the uniformity refers to the uniformity of the entire polished material. The planarity is improved by the characteristics of the polishing layer, and the uniformity is improved by the characteristics of the buffer layer. In the polishing pad of the present application, the buffer layer preferably uses a material softer than the polishing layer.

[0068] As the buffer layer, the following can be listed: fibrous nonwoven fabrics such as polyester nonwoven fabric, nylon nonwoven fabric, acrylonitrile-based nonwoven fabric, resin-impregnated nonwoven fabric such as polyester nonwoven fabric impregnated with polyurethane, polyurethane foam, polyethylene foam, rubbery resin such as butadiene rubber and isoprene rubber, and photosensitive resin.

[0069] As the method of bonding the polishing layer and the buffer layer, an intermediate adhesive is used, and the intermediate adhesive can alternatively use a double-sided adhesive tape, and the polishing layer and the buffer layer are placed on both sides of the intermediate adhesive and pressed.

[0070] The polishing pad of the present application further comprises a back adhesive layer, and the back adhesive layer can also alternatively use a double-sided adhesive tape, and as the composition of the back adhesive layer, the following can be listed: rubber-based adhesives, acrylic adhesives, and the like. The content of metal ions is considered, and the content of metal ions in the acrylic adhesive is less, so it is preferred.

[0071] In the present application, the back adhesive layer further comprises a release film or a release paper, and the release film or the release paper can be torn off before use to achieve the adhesion of the polishing pad to the polishing machine.

[0072] The polishing layer in the embodiment of the present application can be provided with an end point detection window according to actual needs. Optionally, at least one end point detection area is formed in the polishing layer. When polishing is performed, the end point detection area of the polishing layer can perform high-precision optical end point detection. The detection method can be optical detection. The end point detection area is made of a suitable material and has a suitable light transmittance so as to observe the polished object (such as a silicon wafer). As a preferred solution, the light transmittance of the material forming the end point detection area is not less than 20% in the entire range of 300-800 nm. Further preferably, the light transmittance of the high-transmittance material is not less than 60%.

[0073] As a preferred solution, the material of the end point detection area includes but is not limited to one or more combinations of thermosetting resins such as polyurethane resin, polyester resin, phenol resin, urea resin, melamine resin, epoxy resin and acrylic resin; and thermoplastic resins such as polyurethane resin, polyester resin, polyamide resin, cellulose resin, acrylic resin, polycarbonate resin, halogen-containing resin (polyvinyl chloride, polytetrafluoroethylene and polyvinylidene fluoride), polystyrene and olefin resin (polyethylene and polypropylene).

[0074] <Polishing process>

[0075] The polishing pad involved in the present application can be applied to semiconductor processes. As common processes, examples include but are not limited to STI process, Oxide process, W process, Al process, Copper process and Poly process.

[0076] Polishing process: performed using a polishing device such as shown in Figure 1 The polishing pad 2 is attached to the polishing table 3 by a backing layer, for example. The polishing table 3 and the holder 4 are arranged to face each other with the polishing pad 2 and the semiconductor wafer 1 supported thereon, respectively, and each has a rotation shaft. In addition, a pressing mechanism for pressing the semiconductor wafer 1 against the polishing pad 2 is provided on the side of the holder 4. When polishing is performed, the polishing table 3 and the holder 4 are rotated, and the semiconductor wafer 1 is pressed against the polishing pad 2, and polishing is performed while slurry is supplied. The flow rate of the slurry, the polishing load, the rotation speed of the polishing table and the rotation speed of the wafer are not particularly limited and can be appropriately adjusted.

[0077] Embodiment

[0078] Embodiments of the present application will be described in detail below with reference to Examples, but those skilled in the art will appreciate that the following Examples are intended to be illustrative only and should not be viewed as limiting the scope of the present application. Where specific conditions are not noted in the Examples, they were carried out under conventional conditions or under conditions recommended by the manufacturer. Where the manufacturer of the reagent or instrument used is not noted, it is a conventional product that can be obtained by purchase on the market.

[0079] Explanation of reference numerals in Examples:

[0080] L325, LF750D, LFG963A, LF667: represent, respectively, L325 isocyanate-terminated prepolymer; LF750D isocyanate-terminated prepolymer; LFG963A isocyanate-terminated prepolymer; LF667 isocyanate-terminated prepolymer;

[0081] MOCA: 4,4'-methylene-bis-(2-chloroaniline);

[0082] DEG: diethylene glycol;

[0083] TDI: toluene diisocyanate;

[0084] HMDI: 4,4'-dicyclohexylmethane diisocyanate;

[0085] PTMEG: polytetramethylene ether glycol;

[0086] 800: polyol available from Dow Chemical Company, functionality 4, molecular weight 280;

[0087] HF505: polyol available from Dow Chemical Company, functionality 6, molecular weight 11400;

[0088] 920DE 40d30: Nouryon 920DE 40d30, average particle diameter 40 pm, density 0.03 g / cm 3 ;

[0089] 920DET 40d25: Nouryon 920DET 40d25, average particle diameter 40 pm, density 0.025 g / cm 3 ;

[0090] 920DE 80d30: Nouryon 920DE 80d30, average particle size 80 pm, density 0.03 g / cm 3 ;

[0091] 043DET 80d20: Nouryon 043DET 80d20, average particle size 80 pm, density 0.02 g / cm 3 ;

[0092] The above raw materials without marked sources of trademarks are all from commercially available bulk industrial products, manufacturers including BASF, Covestro, Wanhua Chemical, Suzhou Xiangyuan, Chizhou Tianci, Mitsui Chemical, Mitsubishi Chemical, etc.

[0093] Example 1

[0094] This example provides a polishing pad, the preparation method is as follows:

[0095] Step one: take 37.79 parts by mass of TDI and 1.22 parts by mass of HMDI and 55.08 parts by mass of PTMEG1000 and 5.92 parts by mass of DEG to react to obtain an isocyanate-terminated prepolymer, heat to 25-65°C, degas under vacuum (-0.095 MPa) for 2 h, so as to remove the gas and small molecular compounds in the prepolymer; then add 1.34 parts by mass of hollow microsphere polymer 920DE 40d30, uniformly disperse the hollow microsphere polymer in the prepolymer under stirring, and degas again under vacuum (-0.095 MPa) for 2 h, and wait for use. The unreacted NCO in the isocyanate-terminated prepolymer is 9.31%.

[0096] Step two: warm 25.75 parts by mass of MOCA to 115°C, and wait for use. The stoichiometric ratio of NH2 in MOCA to NCO in the isocyanate-terminated prepolymer is 87%.

[0097] Step three: mix the prepolymer and the curing agent under high-speed shearing, then cast into a circular mold to form a cast block with a thickness of 12 cm, stand still at room temperature for 10 min, then place in a 100°C oven for curing for 16 hours. After curing, automatically cool it in the oven to room temperature, then cut into slices with thicknesses of 80 mil, 50 mil and 120 mil.

[0098] Step four: select the slice with a thickness of 80 mil, select the groove shape of concentric circle groove with a blank (no groove) area in the center, and the groove parameters are: groove depth 30 mil, groove width 20 mil, groove pitch 120 mil, center blank area diameter 5 inch, and the polishing layer after grooving.

[0099] Step five: the intermediate glue and back glue layer select to use double-sided tape (purchased from the chemical company and 3M company of the water), using the intermediate glue to bond the above polishing layer and the buffer layer, and bonding the back glue layer on the other side of the buffer layer (the side not bonded with the polishing layer), so as to obtain the polishing pad P1, wherein the buffer layer uses the polyurethane impregnated non-woven material Z70 (purchased from the shares of the dragon).

[0100] Example 2

[0101] The present embodiment provides a polishing pad, and the preparation method is as follows:

[0102] Step one: 32.65 parts by mass of TDI and 8 parts by mass of HMDI and 57.25 parts by mass of PTMEG650 and 2.10 parts by mass of DEG are reacted to obtain an isocyanate-terminated prepolymer, heated to 25-65℃, and degassed under vacuum (-0.095 MPa) for 2h, so as to remove the gas and small molecular compounds in the prepolymer; then 1.96 parts by mass of hollow microsphere polymer 920DE 40d30 is added, and the hollow microsphere polymer is uniformly dispersed in the prepolymer under stirring, and degassed again under vacuum (-0.095 MPa) for 2h, and then used. The unreacted NCO in the isocyanate-terminated prepolymer is 9.25%.

[0103] Step two: 25.58 parts by mass of MOCA is warmed to 115℃, and then used. The stoichiometric ratio of NH2 in MOCA to NCO in the isocyanate-terminated prepolymer is 87%.

[0104] Step three: the prepolymer is mixed with the curing agent under high-speed shearing, and then cast into a circular mold to form a cast block with a thickness of 12 cm, and then placed in a 100℃ oven for curing for 16 hours. After curing, it is automatically cooled to room temperature in the oven, and then cut into thin slices with a thickness of 80 mil, 50 mil and 120 mil.

[0105] Step four: select the thin slice with a thickness of 80 mil, and select the groove shape of concentric circle groove with a blank (no groove) area in the center, and the groove parameters are: groove depth 30 mil, groove width 20 mil, groove pitch 120 mil, and the center blank area diameter is 5 inch. After grooving, it is the polishing layer.

[0106] Step five: the intermediate glue and back glue layer select to use double-sided tape (purchased from the chemical company and 3M company of the water), using the intermediate glue to bond the above polishing layer and the buffer layer, and bonding the back glue layer on the other side of the buffer layer (the side not bonded with the polishing layer), so as to obtain the polishing pad P1, wherein the buffer layer uses the polyurethane impregnated non-woven material Z70 (purchased from the shares of the dragon).

[0107] Example 3

[0108] The present example provides a polishing pad, which is prepared by the following method:

[0109] Step one: 32.65 parts by mass of TDI and 8 parts by mass of HMDI and 57.25 parts by mass of PTMEG650 and 2.10 parts by mass of DEG are reacted to obtain an isocyanate-terminated prepolymer, heated to 25-65°C, degassed under vacuum (-0.095 MPa) for 2 h, so as to remove the gas and small molecule compounds in the prepolymer; then 3.61 parts by mass of hollow microsphere polymer 920DET 40d25 is added, and the hollow microsphere polymer is uniformly dispersed in the prepolymer under stirring, and degassed again under vacuum (-0.095 MPa) for 2 h, and then used. The unreacted NCO in the isocyanate-terminated prepolymer is 9.25%.

[0110] Step two: 25.58 parts by mass of MOCA is warmed to 115°C, and then used. The stoichiometric ratio of NH2 in MOCA to NCO in the isocyanate-terminated prepolymer is 87%.

[0111] Step three: the prepolymer and the curing agent are mixed under high-speed shearing, and then cast into a circular mold to form a cast block with a thickness of 12 cm, and then placed at room temperature for 10 min, and then placed in a 100°C oven for curing for 16 hours. After curing, it is automatically cooled to room temperature in the oven, and then cut into a thickness of 80 mil, 50 mil, and 120 mil.

[0112] Step four: select the thickness of 80 mil, the groove selects the groove shape of concentric circle groove with white space (no groove) area in the center, and the groove parameters are: groove depth 30 mil, groove width 20 mil, groove spacing 120 mil, center white space area diameter 5 inch, and the groove is the polishing layer.

[0113] Step five: the intermediate glue and the back glue layer select to use double-sided adhesive tape (purchased from Jushi Chemical Co., Ltd. and 3M Co.), the above polishing layer is bonded with the buffer layer using the intermediate glue, and the back glue layer is bonded on the other side of the buffer layer (the side not bonded with the polishing layer), to obtain a polishing pad P3, wherein the buffer layer uses polyurethane impregnated non-woven fabric material Z70 (purchased from Dinglong Shares).

[0114] Example 4

[0115] The present example provides a polishing pad, which is prepared by the following method:

[0116] Step one: 37.79 parts by mass of TDI and 1.22 parts by mass of HMDI and 55.08 parts by mass of PTMEG1000 and 5.92 parts by mass of DEG were reacted to obtain an isocyanate-terminated prepolymer, heated to 25-65°C, and degassed under vacuum (-0.095 MPa) for 2 h in order to remove gas and small molecular compounds in the prepolymer; then 1.28 parts by mass of hollow microsphere polymer 920DE 80d30 was added and the hollow microsphere polymer was uniformly dispersed in the prepolymer under stirring, and degassed again under vacuum (-0.095 MPa) for 2 h, and was ready for use. The unreacted NCO in the isocyanate-terminated prepolymer was 9.31%.

[0117] Step two: 25.75 parts by mass of MOCA was warmed to 115°C and was ready for use. The stoichiometric ratio of NH2 in MOCA to NCO in the isocyanate-terminated prepolymer was 87%.

[0118] Step three: the prepolymer and the curing agent were mixed under high-speed shearing, and then cast into a circular mold to form a cast block with a thickness of 12 cm, and then placed at room temperature for 10 min, and then placed in an oven at 100°C for curing for 16 hours. After curing, it was automatically cooled to room temperature in the oven, and then cut into a thickness of 80 mil, 50 mil, and 120 mil.

[0119] Step four: select the thickness of 80 mil, the groove selects the groove shape of concentric circle groove with blank (no groove) area in the center, and the groove parameters are: groove depth 30 mil, groove width 20 mil, groove spacing 120 mil, center blank area diameter 5 inch, and the groove is polished after the groove.

[0120] Step five: the intermediate glue and the back glue layer select to use double-sided adhesive tape (purchased from Jushi Chemical Co., Ltd. and 3M Co.), use the intermediate glue to bond the above-mentioned polishing layer and the buffer layer, and bond the back glue layer on the other side of the buffer layer (the side not bonded with the polishing layer), and the polishing pad P4 is obtained, wherein the buffer layer uses polyurethane impregnated non-woven fabric material Z70 (purchased from Dinglong Co., Ltd.).

[0121] Example 5

[0122] This example provides a polishing pad, and the preparation method is as follows:

[0123] Step one: 32.65 parts by mass of TDI and 8 parts by mass of HMDI and 57.25 parts by mass of PTMEG650 and 2.10 parts by mass of DEG were reacted to obtain an isocyanate-terminated prepolymer, heated to 25-65°C, and degassed under vacuum (-0.095 MPa) for 2 h in order to remove gas and small molecular compounds in the prepolymer; then 0.83 parts by mass of hollow microsphere polymer 043DET 80d20 was added and the hollow microsphere polymer was uniformly dispersed in the prepolymer under stirring, and degassed again under vacuum (-0.095 MPa) for 2 h, and was ready for use. The unreacted NCO in the isocyanate-terminated prepolymer was 9.25%.

[0124] Step two: 30.87 parts by mass of MOCA was warmed to 115°C and was ready for use. The stoichiometric ratio of NH2 in MOCA to NCO in the isocyanate-terminated prepolymer was 105%.

[0125] Step three: the prepolymer and the curing agent were mixed under high shear, then cast into a circular mold to form a cast block with a thickness of 12 cm, and then placed in a 100°C oven for curing for 16 hours. After curing, it was automatically cooled to room temperature in the oven, and then cut into sheets with a thickness of 80 mil, 50 mil, and 120 mil.

[0126] Step four: select the sheet with a thickness of 80 mil, and select the groove shape with concentric circular grooves and a blank (no grooves) area in the center. The groove parameters are: groove depth 30 mil, groove width 20 mil, groove pitch 120 mil, and center blank area diameter 5 inch. After grooving, it is a polishing layer.

[0127] Step five: the intermediate glue and the back glue layer were selected to use double-sided adhesive tape (purchased from Shenzhen Jishui Chemical Co., Ltd. and 3M Company). The intermediate glue was used to bond the above polishing layer and the buffer layer, and the back glue layer was bonded on the other side of the buffer layer (the side not bonded with the polishing layer), and a polishing pad P5 was obtained, wherein the buffer layer used polyurethane impregnated non-woven fabric material Z70 (purchased from Dinglong Shares).

[0128] Example 6

[0129] This example provides a polishing pad, and the preparation method is as follows:

[0130] Step one: 39.01 parts by mass of TDI and 55.08 parts by mass of PTMEG1000 and 5.91 parts by mass of DEG were reacted to obtain an isocyanate-terminated prepolymer, heated to 25-65°C, and degassed under vacuum (-0.095 MPa) for 2 h in order to remove gas and small molecular compounds in the prepolymer; then 0.32 parts by mass of hollow microsphere polymer 920DE40d30 was added and stirred to uniformly disperse the hollow microsphere polymer in the prepolymer, and degassed again under vacuum (-0.095 MPa) for 2 h, and then used. The unreacted NCO in the isocyanate-terminated prepolymer was 8.90%.

[0131] Step two: 29.72 parts by mass of MOCA was warmed to 115°C and used. The stoichiometric ratio of NH2 in MOCA to NCO in the isocyanate-terminated prepolymer was 105%.

[0132] Step three: the prepolymer and the curing agent were mixed under high shear, then cast into a circular mold to form a cast block with a thickness of 12 cm, and then placed in a 100°C oven for 16 hours. After curing, it was automatically cooled to room temperature in the oven, and then cut into sheets with a thickness of 80 mil, 50 mil, and 120 mil.

[0133] Step four: select a sheet with a thickness of 80 mil, and select a groove shape with concentric circular grooves and a blank (no grooves) area in the center. The groove parameters are: groove depth 30 mil, groove width 20 mil, groove pitch 120 mil, center blank area diameter 5 inch, and after grooving, it is a polishing layer.

[0134] Step five: the intermediate glue and the back glue layer were selected to use double-sided adhesive tape (purchased from Shizu Chemical Co., Ltd. and 3M Co.), the above polishing layer and the buffer layer were bonded using the intermediate glue, and the back glue layer was bonded on the other side of the buffer layer (the side not bonded with the polishing layer), to obtain a polishing pad P6, wherein the buffer layer used polyurethane impregnated non-woven material Z70 (purchased from Dinglong Co., Ltd.).

[0135] Example 7

[0136] This example provides a polishing pad, and the preparation method is as follows:

[0137] Step one: take 100 parts by mass of L325 isocyanate-terminated prepolymer, heat to 25-65°C, degas under vacuum (-0.095 MPa) for 2 h, then add 1.07 parts by mass of hollow microsphere polymer 920 DE 40 d30, stir to disperse the hollow microspheres uniformly in the prepolymer, degas again under vacuum (-0.095 MPa) for 2 h, and let stand. The unreacted NCO in the isocyanate-terminated prepolymer is 9.25%.

[0138] Step two: keep the curing agent composition: MOCA 28.6 parts by mass at a temperature of 115°C and the polyether polyol HF505 (molecular weight 11400) 31.7 parts by mass at 25-65°C. The stoichiometric ratio of the sum of NH2 in MOCA and OH in the polyether polyol to the NCO in the isocyanate-terminated prepolymer is 105%.

[0139] Step three: mix the prepolymer and the curing agent composition under high shear, then cast into a circular mold to form a cast block with a thickness of 12 cm, let stand at room temperature for 10 min, then place in a 100°C oven to cure for 16 hours. After curing, let it cool to room temperature automatically in the oven, then cut into sheets with a thickness of 80 mil, 50 mil, and 120 mil.

[0140] Step four: select the sheet with a thickness of 80 mil, select a groove shape that uses a concentric circle groove with a blank (no groove) area in the center, and the groove parameters are: groove depth 30 mil, groove width 20 mil, groove pitch 120 mil, center blank area diameter 5 inches, and the groove is followed by a polishing layer.

[0141] Step five: select a double-sided adhesive tape (purchased from Shenzhen Jushui Chemical Co., Ltd. and 3M Company) for the intermediate adhesive and the back adhesive layer, use the intermediate adhesive to bond the above polishing layer and the buffer layer, and bond the back adhesive layer on the other side of the buffer layer (the side not bonded to the polishing layer), to obtain a polishing pad P7, wherein the buffer layer uses a polyurethane-impregnated non-woven fabric material Z70 (purchased from Diling Shares).

[0142] Example 8

[0143] This example provides a polishing pad, and the preparation method is as follows:

[0144] Step one: take 78 parts by mass of L325 isocyanate-terminated prepolymer, heat to 25-65°C, degas under vacuum (-0.095 MPa) for 2 h, then add 1.07 parts by mass of hollow microsphere polymer 920 DE 40 d30, stir to disperse the hollow microspheres uniformly in the prepolymer, degas again under vacuum (-0.095 MPa) for 2 h, and let stand. The unreacted NCO in the isocyanate-terminated prepolymer is 9.25%. LF750D isocyanate-terminated prepolymer and 22 parts by mass of LFG963A isocyanate-terminated prepolymer was mixed, heated to 25-65°C, degassed under vacuum (-0.095 MPa) for 2 h, then 0.55 parts by mass of hollow microsphere polymer 920 DE 40 d30 was added, and the hollow microsphere polymer was uniformly dispersed in the prepolymer under stirring, and degassed again under vacuum (-0.095 MPa) for 2 h, and then used. The unreacted NCO in the isocyanate-terminated prepolymer was 8.3%.

[0145] Step two: the curing agent composition: MOCA 23.49 parts by mass was kept at a temperature of 115°C, and then used. The stoichiometric ratio of NH2 in MOCA to NCO in the isocyanate-terminated prepolymer was 89%.

[0146] Step three: the prepolymer and the curing agent composition were mixed under high shear, then cast into a circular mold to form a cast block with a thickness of 12 cm, and then placed in a 100°C oven for curing for 16 hours. After curing, it was automatically cooled to room temperature in the oven, and then cut into sheets with a thickness of 80 mil, 50 mil, and 120 mil.

[0147] Step four: select the sheet with a thickness of 80 mil, and select the groove shape of the concentric circle groove with a blank (no groove) area in the center. The groove parameters are: groove depth 30 mil, groove width 20 mil, groove spacing 120 mil, and center blank area diameter 5 inch. After grooving, it is a polishing layer.

[0148] Step five: the intermediate adhesive and the back adhesive layer are selected to use double-sided adhesive tape (purchased from Jushi Chemical Co., Ltd. and 3M Co.). The intermediate adhesive is used to bond the above polishing layer and the buffer layer, and the back adhesive layer is bonded on the other side of the buffer layer (the side not bonded with the polishing layer), and a polishing pad P8 is obtained, wherein the buffer layer uses polyurethane impregnated non-woven material Z70 (purchased from Dinglong Shares).

[0149] Comparative Example 1

[0150] This comparative example provides a polishing pad, and the preparation method is as follows:

[0151] Step one: take 100 parts by mass of LFG963A isocyanate-terminated prepolymer was mixed, heated to 25-65°C, degassed under vacuum (-0.095 MPa) for 2 h, then 0.55 parts by mass of hollow microsphere polymer 920 DE 40 d30 was added, and the hollow microsphere polymer was uniformly dispersed in the prepolymer under stirring, and degassed again under vacuum (-0.095 MPa) for 2 h, and then used. The unreacted NCO in the isocyanate-terminated prepolymer was 8.3%.

[0152] Step two: keep the temperature of curing agent composition: MOCA 7.07 parts by mass at 115℃ and polyether polyol HF505 (molecular weight 11400) 15.92 parts by mass and 800 (molecular weight 280) 5.31 parts by mass at 25-65℃ ready for use. The sum of NH2 in MOCA and 800 and OH in HF505 and the stoichiometric ratio of NCO in isocyanate-terminated prepolymer is 100%.

[0153] Step three: mix the prepolymer and curing agent composition under high shear, then cast into a round mold to form a cast block with a thickness of 12 cm, stand at room temperature for 10 min, then place in a 100℃ oven for 16 hours to cure. After curing, let it cool down to room temperature in the oven automatically, then cut into sheets with a thickness of 80 mil, 50 mil, 120 mil.

[0154] Step four: select the sheet with a thickness of 80 mil, select the groove shape with concentric circle grooves and a blank (no grooves) area in the center, the groove parameters are: groove depth 30 mil, groove width 20 mil, groove pitch 120 mil, the diameter of the center blank area is 5 inches, and the grooves are polished after grooving.

[0155] Step five: select double-sided adhesive tape (purchased from Shenzhen Jushi Chemical Co., Ltd. and 3M Company) for the intermediate adhesive and back adhesive layer. Use the intermediate adhesive to bond the above polishing layer and the buffer layer, and bond the back adhesive layer on the other side of the buffer layer (the side not bonded with the polishing layer), to obtain a polishing pad PD1, wherein the buffer layer uses polyurethane impregnated non-woven material Z70 (purchased from Dinglong Shares).

[0156] Comparative Example 2

[0157] This comparative example provides a polishing pad, the preparation method is as follows:

[0158] Step one: take 100 parts by mass of LF667 isocyanate-terminated prepolymer, heat to 25-65℃, vacuum (-0.095 MPa) degassing for 2h, then add 1.40 parts by mass of hollow microsphere polymer 920DE 40d30, stir to make the hollow microsphere polymer uniformly dispersed in the prepolymer, vacuum (-0.095 MPa) degassing for 2h, ready for use. The unreacted NCO in the isocyanate-terminated prepolymer is 6.7%.

[0159] Step two: keep the temperature of curing agent composition: polyether polyol HF505 (molecular weight 11400) 55.93 parts by mass and 800 (molecular weight 280) 9.11 parts by mass and kept at 25-65°C until use. Among them, the NH2 in MOCA and 800 and The stoichiometric ratio of the sum of OH of HF505 to the NCO of the isocyanate-terminated prepolymer is 100%.

[0160] Step three: the prepolymer and the curing agent composition are mixed under high shear, and then cast into a circular mold to form a cast block with a thickness of 12 cm, and then placed in a 100°C oven for 16 hours. After curing, it is automatically cooled to room temperature in the oven, and then cut into 80 mil, 50 mil, and 120 mil thick slices.

[0161] Step four: select the 80 mil thick slice, and select the groove shape with concentric circle grooves and a blank (no grooving) area in the center. The grooving parameters are: groove depth 30 mil, groove width 20 mil, groove spacing 120 mil, center blank area diameter 5 inch, and the grooving layer is polished after grooving.

[0162] Step five: the intermediate adhesive and the back adhesive layer are selected to use double-sided adhesive tape (purchased from Jushi Chemical Co., Ltd. and 3M Co.), the above-mentioned polishing layer and the buffer layer are bonded using the intermediate adhesive, and the back adhesive layer is bonded on the other side of the buffer layer (the side not bonded with the polishing layer), and a polishing pad PD2 is obtained, wherein the buffer layer uses polyurethane impregnated non-woven fabric material Z70 (purchased from Dinglong Shares).

[0163] Shore hardness of the polishing layer

[0164] The REX digital Shore D type automatic hardness tester and the Bareiss digital Shore D type automatic hardness tester are used for measurement. The sample to be tested is punched into a 3" x 3" square sample, the thickness of the sample to be tested is not less than 5 mm, the measurement point is at least 9 mm away from any edge of the sample, the hardness value is measured at least 6 mm apart on the same sample, the maximum value is taken, and the sample needs to be tested in a standard environment of 23±2℃, humidity 50%±10%.

[0165] Density of the polishing layer

[0166] The S.G is calculated according to the following formula: S.G = m / v = m / (π(d / 2)^2*h), wherein m is the weight of the polishing layer, d is the diameter of the polishing layer, and h is the thickness of the polishing layer.

[0167] Loss height h2 of the polishing layer

[0168] As described above, the polishing pad PD2 is obtained. Figure 3The apparatus shown includes a transparent tube with an inner diameter of 35 mm, a steel ball with a diameter of 16 mm and a mass of 16.8 ± 1.5 g, and a drop height h of 500 mm. The steel ball must not touch the transparent tube during its fall. The steel ball is released by a magnet or other device. The height h1 is recorded when the ball rebounds to zero after contacting the object being measured. For the polished layer, h2 = hL - h1. The object being measured is a 100 mm * 100 mm polished layer sample, which may or may not contain grooves.

[0169] Polishing pad rebound performance test

[0170] Use such as Figure 3 The apparatus shown includes a transparent tube with an inner diameter of 35 mm, a steel ball with a diameter of 16 mm and a mass of 16.8 ± 1.5 g, and a drop height h of 500 mm. The steel ball must not touch the transparent tube during its fall. The ball is released by a magnet or other device, and the height h1 is recorded when it rebounds to zero after contacting the object being measured. The rebound energy is calculated as h1 / h * 100%. The object being measured is a 100 mm * 100 mm polishing pad sample, which may or may not contain grooves. The test results are shown in Table 1.

[0171] Table 1

[0172] Number Density (g / cm 3 )]]> Hardness (D) H (mm) L (mm) Thickness (mil) h2 (80 mil) Thickness (mil) h2(50 mil) Thickness (mil) h2(120 mil) Example 1 0.80 61.0 500 16 80.0 365.8 50.0 409.1 120.0 326.7 Example 2 0.71 59.6 500 16 80.0 376.2 50.0 415.7 120.1 340.4 Example 3 0.50 46.1 500 16 80.0 406.5 50.0 439.8 120.0 380.8 Example 4 0.81 62.2 500 16 80.0 364.8 50.0 408.4 120.0 325.2 Example 5 0.82 66.3 500 16 80.0 363.7 50.0 407.8 120.2 323.8 Example 6 1.01 72.4 500 16 80.0 345.7 50.0 396.3 120.0 280.4 Example 7 0.89 58.3 500 16 80.0 356.6 50.0 403.3 120.0 314.4 Example 8 0.95 64.2 500 16 80.0 351.0 50.0 399.7 120.1 306.9 Comparative Example 1 0.78 19.2 500 16 80.0 447.8 50.0 461.1 120.0 442.2 Comparative Example 2 0.81 7.1 500 16 80.0 454.7 50.0 465.4 120.0 445.0

[0173] Polishing performance evaluation of polishing pads

[0174] The polishing pads used in the prepared examples and comparative examples were tested on a machine to evaluate their polishing performance. The test conditions are as follows:

[0175] The test equipment was an AMAT Refelxion (Modify 5Zone);

[0176] The polished wafers were 300 mm 3S20K TENTEOS (oxide) blanket wafers from Novellus Systems, Inc.; the slurry used for polishing was CES333F polish from Asahi Glass Company, the polishing conditions used included a platen speed of 92 rpm, a carrier speed of 93 rpm, a slurry flow rate of 250 ml / min, and a down pressure of 20.7 kPa, the I-PDA 31G-3N diamond conditioning puck from Kinik Company was used to condition the chemical mechanical polishing pad, the chemical mechanical polishing pad was broken in each for 40 min using a conditioner off-site with a down force of 7.51 bs (3.40 kg), the polishing pad was further conditioned off-site, then polished for 18 seconds using a down force of 7.51 bs (3.40 kg), the removal rate was measured by KLA-Tencor, the removal rate (TEOS RR) is shown in the table below:

[0177] Defect Evaluation

[0178] The defects on the material after polishing of the polished substrate were inspected using a KLA-Tencor available SP2 defect inspection system, the size of the defects was measured: 0.16 μm, on the 10th wafer. The results of the evaluation are shown in Table 2.

[0179] Table 2

[0180]

[0181] It should be noted that the above-mentioned embodiments can be changed and modified by those skilled in the art according to the explanation and elaboration of the above description. Therefore, the present application is not limited to the specific embodiments disclosed and described above, and some equivalent modifications and changes of the present application should be within the scope of protection of the claims of the present application. In addition, although specific terms are used in the present description, these terms are only for convenience of description and do not constitute any limitation on the application.

Claims

1. A polishing layer comprising a closed cell elastomer formed by 5-100 μm size pores separating a continuous polyurethane substrate, the polyurethane substrate comprising a reaction product of a pre-polymer terminated with isocyanate and a curative; the polishing layer comprising a polishing surface, a sphere having a mass of m, a diameter of L, freely released at a distance of h above the polishing surface, the height of the bottom of the metal sphere to the polishing surface at the time when the sphere contacts the polishing surface and the metal sphere bounces upward to a linear velocity equal to 0 is hi, when h is between 490 mm and 520 mm, the mass of the sphere m is between 15 g and 19 g, and the diameter of the sphere L is between 15 mm and 17 mm, wherein, The loss height h2 = h - h1 - L is between 280 mm and 440 mm.

2. The polishing layer of claim 1, wherein The thickness of the polishing layer is between 50 mil and 120 mil.

3. The polishing layer of claim 1, wherein The polishing layer has a density of 0.4 g / cm 3 1.1 g / cm 3 .

4. The polishing layer of claim 1, wherein The polishing layer has a density of 0.5 g / cm 3 1.05 g / cm 3 .

5. The polishing layer of claim 1, wherein The polishing layer has a density of 0.6 g / cm 3 1.0 g / cm 3 .

6. The polishing layer of claim 1, wherein The isocyanate-terminated prepolymer comprises a reaction product of a polyfunctional isocyanate and a polyol.

7. The polishing layer of claim 6, wherein The polyfunctional isocyanate comprises one or more of 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, ethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, norbornane diisocyanate.

8. The polishing layer of claim 6, wherein The polyfunctional isocyanate comprises one or more of 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate.

9. The polishing layer of claim 6, wherein The polyol comprises one or more of polytetramethylene ether glycol, polyethylene glycol, polypropylene glycol, ethylene glycol, butylene glycol, diethylene glycol, neopentyl glycol, 2-methyl-1,3-propanediol, hexanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanedimethanol, homopolymers and / or copolymers of ethylene oxide and propylene oxide.

10. The polishing layer of claim 6, wherein The polyol comprises one or more of polytetramethylene ether glycol, polypropylene glycol, diethylene glycol, homopolymers and / or copolymers of ethylene oxide and propylene oxide.

11. The polishing layer of claim 1, wherein The curing agent comprises a polyamine-based curing agent or a polyol curing agent.

12. The polishing layer of claim 11, wherein, The polyamine-based curing agent comprises one or more of diethyltoluene diamine (DETDA), N,N'-dialkyldiaminodiphenylmethane, 3,5-diethyl-2,4-toluene diamine and its isomers, 3,5-dimethylthio-2,4-toluene diamine and its isomers, 4,4'-methylene-bis-(2-chloroaniline) (MOCA), 4,4'-bis-(sec-butylamino)-diphenylmethane, 1,4-bis-(sec-butylamino)-benzene, 4,4'-methylene-bis-(2-chloroaniline), 4,4'-methylene-bis-(3-chloro-2,6-diethyl aniline) (MCDEA), polyoxytetramethylene-di-p-aminobenzoate, p,p'-methylenedianiline (MDA), m-phenylenediamine (MPDA), 4,4'-methylene-bis-(2,6-diethyl aniline) (MDEA), 4,4'-methylene-bis-(2,3-dichloroaniline) (MDCA), 4,4'-diamino-3,3'-diethyl-5,5'-dimethyl diphenylmethane, 2,2',3,3'-tetrachlorodiaminodiphenylmethane, propylene glycol-di-p-aminobenzoate.

13. The polishing layer of claim 11, wherein The polyamine-based curing agent is 4,4'-methylene-bis-(2-chloroaniline) (MOCA).

14. The polishing layer of claim 11, wherein, The polyol curing agent has a number average molecular weight of 2000 to 100000, and has an average of 3 to 30 hydroxyl groups.

15. The polishing layer of claim 11, wherein, The polyol curing agent contains 4 to 8 hydroxyl groups.

16. The polishing layer of claim 1, wherein The unreacted NCO of the isocyanate-terminated prepolymer is between 8.0% and 9.5%, and the stoichiometric ratio of NH2 or / and OH from the curing agent to NCO of the isocyanate-terminated prepolymer is between 80% and 105%.

17. A polishing pad for use in chemical mechanical polishing of a substrate selected from at least one of a magnetic substrate, an optical substrate, and a semiconductor substrate, the polishing pad comprising: The polishing pad comprises the polishing layer as claimed in any one of claims 1 to 16.

18. The polishing pad of claim 17, wherein the substrate is selected from at least one of a magnetic substrate, an optical substrate, and a semiconductor substrate. The polishing pad has a resilience of 5% to 40%.

19. The polishing pad of claim 18, wherein, The polishing pad comprises a polishing layer, an intermediate adhesive layer, a cushion layer and a release film layer.

20. A method of manufacturing a semiconductor device, characterized by A semiconductor device is provided, the semiconductor device comprising a substrate selected from at least one of a magnetic substrate, an optical substrate or a semiconductor substrate, a polishing pad as claimed in claim 17 or 18, forming a dynamic contact between a polishing surface of the polishing layer and the substrate, thereby polishing a surface of the substrate, and a truing tool for truing the polishing surface.

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