JP4884808B2 - Polishing pad manufacturing method - Google Patents

Description

  The present invention stabilizes flattening processing of optical materials such as lenses and reflecting mirrors, silicon wafers, glass substrates for hard disks, aluminum substrates, and materials that require high surface flatness such as general metal polishing processing, In addition, the present invention relates to a polishing pad that can be performed with high polishing efficiency. The polishing pad of the present invention is particularly suitable for a step of planarizing a silicon wafer and a device having an oxide layer, a metal layer, etc. formed thereon, before further laminating and forming these oxide layers and metal layers. Used for.

  A typical material that requires high surface flatness is a single crystal silicon disk called a silicon wafer for manufacturing a semiconductor integrated circuit (IC, LSI). Silicon wafers have a highly accurate surface in each process of stacking and forming oxide layers and metal layers in order to form reliable semiconductor junctions of various thin films used for circuit formation in IC, LSI, and other manufacturing processes. It is required to finish flat. In such a polishing finishing process, a polishing pad is generally fixed to a rotatable support disk called a platen, and a workpiece such as a semiconductor wafer is fixed to a polishing head. A polishing operation is performed by generating a relative speed between the platen and the polishing head by both movements, and continuously supplying a polishing slurry containing abrasive grains onto the polishing pad.

  The polishing characteristics of the polishing pad are required to be excellent in the flatness (planarity) and in-plane uniformity of the object to be polished and to have a high polishing rate. The flatness and in-plane uniformity of the object to be polished can be improved to some extent by increasing the elastic modulus of the polishing layer. The polishing rate can be improved by using a foam containing bubbles and increasing the amount of slurry retained.

However, when the polishing layer is made to have a high elastic modulus (high hardness) in order to improve the planarization characteristics of the polishing pad, the specific gravity increases, and as a result, the number of bubbles per unit area decreases and the polishing rate decreases. There is a problem. Further, there is a problem that stress is not relieved at the contact portion between the polishing layer and the wafer edge, the wafer edge tends to be excessively shaved, and the in-plane uniformity of the wafer is lowered. In order to improve the above characteristics, a polishing pad made of a polymer matrix impregnated with a plurality of polymer microelements has been proposed (Patent Document 1). As the polymer microelement, a hollow microsphere having a shell having a thickness of about 0.1 μm is used. In addition, a polishing pad is proposed in which the number of closed cells in the polishing layer is 200 / mm ² or more and 600 / mm ² or less, and the average bubble diameter is 30 μm or more and 60 μm or less (Patent Document 2). .

  However, even with the above-described polishing pad, it is difficult to achieve both the required planarization characteristics and in-plane uniformity characteristics.

Japanese Patent No. 3013105 JP 2003-218074 A

  An object of this invention is to provide the polishing pad which is excellent in the planarization characteristic and in-plane uniform characteristic. Moreover, it aims at providing the manufacturing method of the semiconductor device using this polishing pad.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above object can be achieved by the polishing pad shown below, and have completed the present invention.

  That is, the present invention provides a polishing pad including a polishing layer having closed cells, wherein the closed cells include elliptical bubbles, and a ratio of an average major axis L to an average minor axis S (L / The polishing pad is characterized in that S) is 1.1-5.

  The present inventors changed the closed cells in the polishing layer from conventional spherical cells to elliptical cells (which are elliptical closed cells but may not be strictly balanced elliptical). The present inventors have found that the elastic modulus can be increased without increasing the specific gravity as compared with the conventional polishing layer. When the polishing pad of the present invention is used, since the center throw (a phenomenon in which the vicinity of the center of the object to be polished becomes difficult to be polished) can be effectively suppressed, the flatness of the object to be polished is improved. In addition, the stress applied to the edge portion of the object to be polished is relieved by the elliptical bubbles, and excessive cutting of the edge portion of the object to be polished can be suppressed. Thereby, the in-plane uniformity of the polishing object is improved.

  The major axis of the elliptical bubble is preferably parallel (substantially parallel) to the thickness direction of the polishing layer. By arranging the major axis of the elliptical bubble in parallel with the thickness direction of the polishing layer, the above effect is further improved.

  The closed cells in the polishing layer may contain spherical cells, but the number ratio of elliptical bubbles is preferably 50% or more of all closed cells in order to sufficiently achieve the intended effect.

  In the present invention, the polishing layer is preferably made of a polyurethane resin foam.

  Furthermore, the present invention relates to a semiconductor device manufacturing method including a step of polishing a surface of a semiconductor wafer using the polishing pad.

  The polishing pad of the present invention may be a polishing layer alone or a laminate of a polishing layer and another layer (for example, a cushion layer). The material for forming the polishing layer is not particularly limited. For example, halogen resins such as polyurethane resin, polyester resin, polyamide resin, acrylic resin, polycarbonate resin (polyvinyl chloride, polytetrafluoroethylene, polyvinylidene fluoride, etc.), polystyrene, olefin resin (polyethylene, polypropylene, etc.) 1 type, or 2 or more types of mixtures, such as an epoxy resin and a photosensitive resin. Polyurethane resin is a particularly preferable material for forming the polishing layer because it has excellent wear resistance and a polymer having desired physical properties can be easily obtained by variously changing the raw material composition. Hereinafter, a polyurethane resin will be described as a representative material for forming the polishing layer.

  The polyurethane resin comprises an isocyanate component, a polyol component (high molecular weight polyol, low molecular weight polyol, etc.), and a chain extender.

  As the isocyanate component, a known compound in the field of polyurethane can be used without particular limitation. As the isocyanate component, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,2′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, aromatic diisocyanates such as p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, ethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1,6-hexamethylene diisocyanate, etc. Aliphatic diisocyanate, 1,4-cyclohexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate Isocyanate, alicyclic diisocyanates such as norbornane diisocyanate. These may be used alone or in combination of two or more.

  As the isocyanate component, a trifunctional or higher polyfunctional polyisocyanate compound can be used in addition to the diisocyanate compound. As a polyfunctional isocyanate compound, a series of diisocyanate adduct compounds are commercially available as Desmodur-N (manufactured by Bayer) or trade name Duranate (manufactured by Asahi Kasei Kogyo Co., Ltd.).

  Of the above isocyanate components, it is preferable to use an aromatic diisocyanate and an alicyclic diisocyanate in combination, and it is particularly preferable to use toluene diisocyanate and dicyclohexylmethane diisocyanate in combination.

  Examples of the high molecular weight polyol include polyether polyols typified by polytetramethylene ether glycol, polyester polyols typified by polybutylene adipate, polycaprolactone polyol, and a reaction product of a polyester glycol such as polycaprolactone and alkylene carbonate. Polyester polycarbonate polyol, polyester polycarbonate polyol obtained by reacting ethylene carbonate with polyhydric alcohol and then reacting the resulting reaction mixture with organic dicarboxylic acid, and polycarbonate polyol obtained by transesterification reaction between polyhydroxyl compound and aryl carbonate Etc. These may be used alone or in combination of two or more.

  The number average molecular weight of the high molecular weight polyol is not particularly limited, but is preferably 500 to 2000 from the viewpoint of the elastic properties of the resulting polyurethane resin. When the number average molecular weight is less than 500, a polyurethane resin using the number average molecular weight does not have sufficient elastic properties and becomes a brittle polymer. Therefore, the polishing pad manufactured from this polyurethane resin becomes too hard and causes scratches on the wafer surface. Moreover, since it becomes easy to wear, it is not preferable from the viewpoint of the pad life. On the other hand, when the number average molecular weight exceeds 2000, a polyurethane resin using the number average molecular weight becomes too soft, and a polishing pad produced from this polyurethane resin tends to have poor planarization characteristics.

  In addition to the high molecular weight polyols described above as the polyol component, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, diethylene glycol, triethylene glycol, 1,4-bis (2 -Hydroxyethoxy) benzene, trimethylolpropane, glycerin, 1,2,6-hexanetriol, pentaerythritol, tetramethylolcyclohexane, methylglucoside, sorbitol, mannitol, dulcitol, sucrose, 2,2,6,6-tetrakis (Hydroxymethyl) cyclohexanol, diethanolamine, N- methyldiethanolamine, and can be used in combination of low molecular weight polyols such as triethanolamine. Moreover, low molecular weight polyamines, such as ethylenediamine, tolylenediamine, diphenylmethanediamine, and diethylenetriamine, can also be used in combination. Also, alcohol amines such as monoethanolamine, 2- (2-aminoethylamino) ethanol, and monopropanolamine can be used in combination. These low molecular weight polyols and low molecular weight polyamines may be used alone or in combination of two or more. The blending amount of the low molecular weight polyol, the low molecular weight polyamine or the like is not particularly limited, and is appropriately determined depending on the properties required for the polishing pad (polishing layer) to be produced, and is 20 to 70 mol% of the total polyol component. Is preferred.

  The ratio of the high molecular weight polyol to the low molecular weight polyol in the polyol component is determined by the properties required for the polishing layer produced therefrom.

  When the polyurethane resin is produced by the prepolymer method, a chain extender is used for curing the prepolymer. The chain extender is an organic compound having at least two active hydrogen groups, and examples of the active hydrogen group include a hydroxyl group, a primary or secondary amino group, and a thiol group (SH). Specifically, 4,4′-methylenebis (o-chloroaniline) (MOCA), 2,6-dichloro-p-phenylenediamine, 4,4′-methylenebis (2,3-dichloroaniline), 3,5 -Bis (methylthio) -2,4-toluenediamine, 3,5-bis (methylthio) -2,6-toluenediamine, 3,5-diethyltoluene-2,4-diamine, 3,5-diethyltoluene-2 , 6-diamine, trimethylene glycol-di-p-aminobenzoate, polytetramethylene oxide-di-p-aminobenzoate, 4,4′-diamino-3,3 ′, 5,5′-tetraethyldiphenylmethane, 4, 4'-diamino-3,3'-diisopropyl-5,5'-dimethyldiphenylmethane, 4,4'-diamino-3,3 ', 5,5'-tetra Sopropyldiphenylmethane, 1,2-bis (2-aminophenylthio) ethane, 4,4′-diamino-3,3′-diethyl-5,5′-dimethyldiphenylmethane, N, N′-di-sec-butyl -4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, m-xylylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, m-phenylenediamine And polyamines exemplified by p-xylylenediamine and the like, or the low molecular weight polyols and low molecular weight polyamines mentioned above. These may be used alone or in combination of two or more.

  The ratio of the isocyanate component, the polyol component, and the chain extender in the present invention can be variously changed depending on the molecular weight of each, the desired physical properties of the polishing pad, and the like. In order to obtain a polishing pad having desired polishing characteristics, the number of isocyanate groups of the isocyanate component relative to the total number of active hydrogen groups (hydroxyl group + amino group) of the polyol component and the chain extender is 0.80 to 1.20. Is more preferable, and 0.99 to 1.15 is more preferable. When the number of isocyanate groups is outside the above range, curing failure occurs and the required specific gravity and hardness cannot be obtained, and the polishing characteristics tend to be deteriorated.

  The polyurethane resin can be produced by applying a known urethanization technique such as a melting method or a solution method, but it is preferably produced by a melting method in consideration of cost, working environment, and the like.

  Polyurethane resin can be produced by either the prepolymer method or the one-shot method, but a prepolymer method in which an isocyanate-terminated prepolymer is synthesized in advance from an isocyanate component and a polyol component and then reacted with a chain extender. However, the obtained polyurethane resin has excellent physical properties and is suitable.

  As the isocyanate-terminated prepolymer, those having a molecular weight of about 800 to 5000 are preferable because of excellent processability and physical characteristics.

  In the production of the polyurethane resin, a first component containing an isocyanate group-containing compound and a second component containing an active hydrogen group-containing compound are mixed and cured. In the prepolymer method, the isocyanate-terminated prepolymer becomes an isocyanate group-containing compound, and the chain extender becomes an active hydrogen group-containing compound. In the one-shot method, the isocyanate component becomes an isocyanate group-containing compound, and the chain extender and the polyol component become active hydrogen group-containing compounds.

  The polyurethane resin foam, which is a material for forming the polishing layer of the present invention, can be produced by a mechanical foaming method, a chemical foaming method, or the like. In addition, you may use together the method of adding a hollow bead as needed.

  In particular, a mechanical foaming method using a silicon surfactant which is a copolymer of polyalkylsiloxane and polyether is preferable. Examples of suitable silicon surfactants include SH-192, SH-193, L5340 (manufactured by Toray Dow Corning Silicone), and the like.

  In addition, you may add stabilizers, such as antioxidant, a lubricant, a pigment, a filler, an antistatic agent, and another additive as needed.

An example of a method for producing a polyurethane resin foam containing closed cells (including elliptical cells) constituting the polishing layer of the present invention will be described below. The manufacturing method of this polyurethane resin foam has the following processes.
1) Foaming process for producing a cell dispersion of isocyanate-terminated prepolymer A silicon-based surfactant is added to the isocyanate-terminated prepolymer (first component), and the mixture is stirred in the presence of a non-reactive gas to remove the non-reactive gas. Disperse as fine bubbles to obtain a cell dispersion. When the prepolymer is solid at normal temperature, it is preheated to an appropriate temperature and melted before use.
2) Curing Agent (Chain Extender) Mixing Step A chain extender (second component) is added to the above cell dispersion, mixed and stirred to obtain a foaming reaction solution. 3) Casting process After pouring the foaming reaction liquid into the mold, the mold is clamped.
4) Curing process The inside of the mold is compressed or decompressed while heating and reacting the foaming reaction liquid poured into the mold, and the state is maintained until it does not flow.

  As the non-reactive gas used to form the fine bubbles, non-flammable gases are preferable, and specific examples include nitrogen, oxygen, carbon dioxide, rare gases such as helium and argon, and mixed gases thereof. In view of cost, it is most preferable to use air that has been dried to remove moisture.

  A known stirring device can be used without particular limitation as a stirring device for dispersing non-reactive gas in the form of fine bubbles and dispersed in the first component containing the silicon-based surfactant. Specifically, a homogenizer, a dissolver, 2 A shaft planetary mixer (planetary mixer) is exemplified. The shape of the stirring blade of the stirring device is not particularly limited, but it is preferable to use a whipper type stirring blade because fine bubbles can be obtained.

  In addition, it is also a preferable aspect to use a different stirring apparatus for the stirring which produces a cell dispersion in a foaming process, and the stirring which adds and mixes the chain extender in a mixing process. In particular, the stirring in the mixing step may not be stirring that forms bubbles, and it is preferable to use a stirring device that does not involve large bubbles. As such an agitator, a planetary mixer is suitable. There is no problem even if the same stirring device is used as the stirring device for the foaming step and the mixing step, and it is also preferable to adjust the stirring conditions such as adjusting the rotation speed of the stirring blade as necessary. .

  As described above, in order to produce a polyurethane resin foam containing elliptical cells, it is necessary to perform an operation different from the conventional mechanical foaming method in the casting process and the curing process. Specifically, the following operations are performed.

1) Case 1
In the casting step, after pouring the foaming reaction liquid in an amount of 50% by volume or more into a movable mold having one side face or the opposite side face, a mold is clamped with an upper lid on the upper face of the mold. The upper lid of the mold is preferably provided with a vent hole for discharging excess foaming reaction liquid when the mold is compressed. Thereafter, in the curing step, while the foaming reaction liquid is heated and reacted and cured, the side surface of the mold is moved to compress the mold, and the state is maintained until it does not flow. The degree of compression is preferably 50 to 95% of the original width, and more preferably 80 to 90%. Moreover, it is preferable to compress so that an excess foaming reaction liquid is fully discharged | emitted from a vent hole. In this case, the major axis of the elliptical bubble is substantially perpendicular to the moving direction of the mold side surface.

2) Case 2
In the casting step, the foaming reaction solution is poured into the mold in an amount of 50% by volume or more, and then the upper surface of the mold is covered with a top cover to perform clamping. It is preferable that at least one side surface of the mold is provided with a vent hole for discharging excess foaming reaction liquid when the mold is compressed. Thereafter, in the curing step, while the foaming reaction liquid is heated and reacted and cured, the upper lid and / or the lower surface of the mold is moved to compress the mold, and the state is maintained until it does not flow. The degree of compression is preferably 50 to 98% of the original height, and more preferably 85 to 95%. Moreover, it is preferable to compress so that an excess foaming reaction liquid is fully discharged | emitted from a vent hole. In this case, the major axis of the elliptical bubble is substantially perpendicular to the moving direction of the upper lid or lower surface of the mold.

3) Case 3
In the casting step, after pouring an amount of foaming reaction liquid into the mold so as to create a space, an upper lid is placed on the upper surface of the mold and the mold is clamped. The upper lid is provided with a hole for decompressing the inside of the mold. Thereafter, in the curing step, the inside of the mold is decompressed while heating and reacting the foaming reaction liquid, and the decompressed state is maintained until it does not flow. The degree of decompression is preferably 90 to 30 kPa, and more preferably 90 to 70 kPa. In this case, the major axis of the elliptical bubble is substantially parallel to the height direction of the mold.

4) Case 4
A predetermined amount of water and a curing agent are added to an isocyanate-terminated prepolymer cell dispersion and stirred to obtain a foaming reaction solution. After pouring the foaming reaction liquid in an amount of 50% by volume or more into a heated mold, an upper lid is placed on the upper surface of the mold and the mold is clamped. The upper lid is provided with a vent hole for discharging excess foaming reaction liquid. Thereafter, in the curing step, the foaming reaction liquid is heated and reacted and cured. At this time, the carbon dioxide gas generated by the reaction increases the pressure in the mold, and excess foaming reaction liquid is discharged from the vent hole. In this case, the major axis of the elliptical bubble is substantially parallel to the height direction of the mold.

  In the case of a mold having a vent hole size of about φ1 to 5 mm and a venthole number of about □ 1000 mm, about 6 to 20 vent holes are preferably provided. When it is outside the above range, the loss of the raw material tends to be large, or the target elliptical bubble tends to be difficult to obtain. In the cases 1 and 2, it is preferable that the timing at which compression starts to be applied is when the viscosity of the foaming reaction liquid exceeds 10 Pa · s. The viscosity of the foaming reaction liquid can be measured, for example, using a rotor H5 (rotation speed: 4 rpm) of a TV-10H viscometer (Toki Sangyo). In case 3 as well, the timing for starting depressurization is the same as described above. In case 4, the compression or decompression step may be used in combination.

  In the method for producing a polyurethane resin foam, heating and post-curing the foam block that has reacted until it no longer flows is effective in improving the physical properties of the foam, which is extremely suitable.

  In the polyurethane resin foam, a known catalyst that promotes a polyurethane reaction such as tertiary amine may be used. The type and addition amount of the catalyst are selected in consideration of the flow time for pouring into a mold having a predetermined shape after the mixing step.

  Thereafter, the obtained polyurethane resin foam block is sliced by using a bowl-like or band saw-like slicer to produce a polishing layer. In that case, it may be sliced so that the major axis of the elliptical bubble is parallel to the thickness direction of the polishing layer, or may be sliced so as to be perpendicular.

  The polishing layer obtained by the manufacturing method has elliptical bubbles, and the ratio (L / S) of the average major axis L to the average minor axis S of the elliptical bubbles at the cut surface of the polishing layer is 1.1-5. And preferably 1.2 to 3, particularly preferably 1.5 to 3. When L / S is less than 1.1, it is difficult to increase the elastic modulus without increasing the specific gravity, and it is not possible to suppress center throw or excessive cutting of the edge portion of the object to be polished. On the other hand, when L / S exceeds 5, it becomes difficult to orient the long axis of the elliptical bubble in a certain direction, and the polishing rate tends to decrease.

  The average major axis of the elliptical bubbles is preferably 30 to 200 μm, and the average minor axis is preferably 25 to 65 μm. When deviating from this range, the polishing rate tends to decrease or the flatness of the polished object (wafer) after polishing tends to decrease.

  In addition, the closed cells in the polishing layer may contain spherical cells, but in order to sufficiently achieve the intended effect, the number ratio of elliptical bubbles is preferably 50% or more of all closed cells. More preferably, it is 60% or more, particularly preferably 80% or more. The number ratio of the elliptical bubbles can be adjusted to the target range by adjusting the degree of compression of the mold or the pressure reduction inside the mold and the amount of water added.

  The specific gravity of the polyurethane resin foam is preferably 0.3 to 0.88. When the specific gravity is less than 0.3, the surface strength of the polishing pad (polishing layer) decreases, and the planarity of the wafer tends to decrease. On the other hand, when the value is larger than 0.88, the number of bubbles on the surface of the polishing pad is reduced and the planarity is good, but the polishing rate tends to decrease.

  The hardness of the polyurethane resin foam is preferably 45 to 65 degrees as measured by an Asker D hardness meter. When the Asker D hardness is less than 45 degrees, the planarity of the wafer is lowered. On the other hand, when it is larger than 65 degrees, the planarity is good, but the uniformity of the wafer tends to be lowered.

  The storage elastic modulus at 40 ° C. and 1 Hz of the polyurethane resin foam is preferably 230 to 650 MPa. When the storage elastic modulus is less than 230 MPa, the surface strength of the polishing layer decreases, and the planarity of the object to be polished tends to decrease. On the other hand, when it exceeds 650 MPa, the surface strength of the polishing layer becomes too high, and the edge portion of the polishing object tends to be excessively cut. The storage elastic modulus is an elastic modulus measured by applying a sinusoidal vibration to a fine foam using a dynamic viscoelasticity measuring device and using a tensile test jig.

  The polishing surface in contact with the object to be polished of the polishing layer may have a concavo-convex structure for holding and renewing the slurry. The polishing layer made of foam has many openings on the polishing surface and has the function of holding and updating the slurry. By forming a concavo-convex structure on the polishing surface, the slurry can be held and updated more efficiently. It can be performed well, and destruction of the polishing object due to adsorption with the polishing object can be prevented. The concavo-convex structure is not particularly limited as long as it is a shape that holds and renews the slurry. For example, an XY lattice groove, a concentric circular groove, a through hole, a non-penetrating hole, a polygonal column, a cylinder, a spiral groove, Examples include eccentric circular grooves, radial grooves, and combinations of these grooves. In addition, these uneven structures are generally regular, but in order to make the slurry retention and renewability desirable, the groove pitch, groove width, groove depth, etc. should be changed for each range. Is also possible.

  The method for producing the concavo-convex structure is not particularly limited. For example, a method of machine cutting using a jig such as a tool of a predetermined size, pouring a resin into a mold having a predetermined surface shape, and curing. Using a press plate having a predetermined surface shape, a method of producing a resin by pressing, a method of producing using photolithography, a method of producing using a printing technique, a carbon dioxide laser, etc. Examples include a manufacturing method using laser light.

  The thickness of the polishing layer is not particularly limited, but is usually about 0.8 to 4 mm, and preferably 1.0 to 2.5 mm.

  The thickness variation of the polishing layer is preferably 100 μm or less. When the thickness variation exceeds 100 μm, the polishing layer has a large undulation, and there are portions where the contact state with the object to be polished is different, which adversely affects the polishing characteristics. In order to eliminate the thickness variation of the polishing layer, in general, the surface of the polishing layer is dressed with a dresser in which diamond abrasive grains are electrodeposited and fused in the initial stage of polishing. As a result, the dressing time becomes longer and the production efficiency is lowered.

  Examples of a method for suppressing the variation in the thickness of the polishing layer include a method of buffing the surface of the polishing layer sliced to a predetermined thickness. Moreover, when buffing, it is preferable to carry out stepwise with abrasives having different particle sizes.

  The polishing pad of the present invention may be a laminate of the polishing layer and a cushion sheet.

  The cushion sheet (cushion layer) supplements the characteristics of the polishing layer. The cushion sheet is necessary for achieving both planarity and uniformity in a trade-off relationship in CMP. Planarity refers to the flatness of a pattern portion when a polishing object having minute irregularities generated during pattern formation is polished, and uniformity refers to the uniformity of the entire polishing object. The planarity is improved by the characteristics of the polishing layer, and the uniformity is improved by the characteristics of the cushion sheet. In the polishing pad of the present invention, it is preferable to use a cushion sheet that is softer than the polishing layer.

  Examples of the cushion sheet include a fiber nonwoven fabric such as a polyester nonwoven fabric, a nylon nonwoven fabric, and an acrylic nonwoven fabric, a resin-impregnated nonwoven fabric such as a polyester nonwoven fabric impregnated with polyurethane, a polymer resin foam such as polyurethane foam and polyethylene foam, a butadiene rubber, Examples thereof include rubber resins such as isoprene rubber and photosensitive resins.

  Examples of means for attaching the polishing layer and the cushion sheet include a method of pressing the polishing layer and the cushion sheet with a double-sided tape.

  The double-sided tape has a general configuration in which adhesive layers are provided on both sides of a substrate such as a nonwoven fabric or a film. In consideration of preventing the penetration of the slurry into the cushion sheet, it is preferable to use a film for the substrate. Examples of the composition of the adhesive layer include rubber adhesives and acrylic adhesives. Considering the content of metal ions, an acrylic adhesive is preferable because the metal ion content is low. In addition, since the composition of the polishing layer and the cushion sheet may be different, the composition of each adhesive layer of the double-sided tape can be made different so that the adhesive force of each layer can be optimized.

  The polishing pad of the present invention may be provided with a double-sided tape on the surface to be bonded to the platen. As the double-sided tape, a tape having a general configuration in which an adhesive layer is provided on both surfaces of a base material can be used as described above. As a base material, a nonwoven fabric, a film, etc. are mentioned, for example. In consideration of peeling from the platen after use of the polishing pad, it is preferable to use a film for the substrate. Examples of the composition of the adhesive layer include rubber adhesives and acrylic adhesives. Considering the content of metal ions, an acrylic adhesive is preferable because the metal ion content is low.

  The semiconductor device is manufactured through a step of polishing the surface of the semiconductor wafer using the polishing pad. A semiconductor wafer is generally a laminate of a wiring metal and an oxide film on a silicon wafer. The method and apparatus for polishing the semiconductor wafer are not particularly limited. For example, as shown in FIG. 1, a polishing surface plate 2 that supports a polishing pad (polishing layer) 1 and a support table (polishing head) that supports the semiconductor wafer 4. 5 and a polishing apparatus equipped with a backing material for uniformly pressing the wafer and a supply mechanism of the abrasive 3. The polishing pad 1 is attached to the polishing surface plate 2 by attaching it with a double-sided tape, for example. The polishing surface plate 2 and the support base 5 are disposed so that the polishing pad 1 and the semiconductor wafer 4 supported on each of the polishing surface plate 2 and the support table 5 face each other, and are provided with rotating shafts 6 and 7 respectively. Further, a pressurizing mechanism for pressing the semiconductor wafer 4 against the polishing pad 1 is provided on the support base 5 side. In polishing, the semiconductor wafer 4 is pressed against the polishing pad 1 while rotating the polishing surface plate 2 and the support base 5, and polishing is performed while supplying slurry. The flow rate of the slurry, the polishing load, the polishing platen rotation speed, and the wafer rotation speed are not particularly limited and are appropriately adjusted.

  As a result, the protruding portion of the surface of the semiconductor wafer 4 is removed and polished flat. Thereafter, a semiconductor device is manufactured by dicing, bonding, packaging, or the like. The semiconductor device is used for an arithmetic processing device, a memory, and the like.

  Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

[Measurement and evaluation methods]
(Measurement of average major axis and average minor axis of elliptical bubbles, ratio of elliptical bubbles)
A sample for measurement was obtained by cutting the produced polyurethane resin foam sheet in the thickness direction with a microtome cutter. The cut surface of the measurement sample was photographed at 100 times with a scanning electron microscope (S-3500N, manufactured by Hitachi Science Systems, Ltd.). And the major axis and minor axis of all elliptical bubbles in an arbitrary range are measured using image analysis software (manufactured by MITANI Corporation, WIN-ROOF), and the average major axis L, average minor axis S, and L / S was calculated. In addition, the number ratio (%) of elliptical bubbles to all closed cells was calculated.

(Specific gravity measurement)
This was performed according to JIS Z8807-1976. The produced polyurethane resin foam was cut into a 4 cm × 8.5 cm strip (thickness: arbitrary) and used as a sample for measuring specific gravity, and allowed to stand for 16 hours in an environment of temperature 23 ° C. ± 2 ° C. and humidity 50% ± 5%. I put it. The specific gravity was measured using a hydrometer (manufactured by Sartorius).

(Measurement of compression rate)
A polyurethane resin foam cut into a circle (thickness: arbitrary) having a diameter of 7 mm was used as a sample for measuring the compressibility, and allowed to stand for 40 hours in an environment of a temperature of 23 ° C. ± 2 ° C. and a humidity of 50% ± 5%. For the measurement, a compression ratio was measured using a thermal analysis measuring instrument TMA (manufactured by SEIKO INSTRUMENTS, SS6000). The calculation formula of the compression rate is shown below.
Compression rate (%) = {(T1-T2) / T1} × 100
T1: Foam thickness when a stress load of 30 kPa (300 g / cm ² ) is maintained for 60 seconds from an unloaded state on the foam.
T2: Foam thickness when a stress load of 180 kPa (1800 g / cm ² ) is maintained for 60 seconds from the state of T1.

(Measurement of storage modulus)
This was performed in accordance with JIS K7198-1991. A polyurethane resin foam cut into a strip shape (thickness: arbitrary) of 3 mm × 40 mm was used as a sample for dynamic viscoelasticity measurement, and was allowed to stand for 4 days in a container containing silica gel under an environmental condition of 23 ° C. The accurate width and thickness of the foam after cutting was measured with a micrometer. For measurement, a storage elastic modulus E ′ was measured using a dynamic viscoelastic spectrometer (manufactured by Iwamoto Seisakusho, present IS Engineering Co., Ltd.). The measurement conditions at that time are shown below.
<Measurement conditions>
Measurement temperature: 40 ° C
Applied strain: 0.03%
Initial load: 20g
Frequency: 1Hz

(Evaluation of polishing characteristics)
Using SPP600S (manufactured by Okamoto Machine Tool Co., Ltd.) as a polishing apparatus, polishing characteristics were evaluated using the prepared polishing pad. An interference type film thickness measuring device (manufactured by Otsuka Electronics Co., Ltd.) was used for measuring the thickness of the oxide film. As polishing conditions, silica slurry (SS12, manufactured by Cabot Corporation) was added as a slurry at a flow rate of 150 ml / min. The polishing load was 350 g / cm ² , the polishing platen rotation number was 35 rpm, and the wafer rotation number was 30 rpm.

  The flatness is evaluated by depositing a thermal oxide film of 0.5 μm on an 8-inch silicon wafer, and then patterning with L / S (line and space) = 25 μm / 5 μm and L / S = 5 μm / 25 μm. Then, an oxide film (TEOS) was further deposited by 1 μm to produce a patterned wafer having an initial step of 0.5 μm. This wafer was polished under the above-mentioned polishing conditions and evaluated by measuring the amount of scraping of the bottom portion of the 25 μm space when the global level difference was 2000 mm or less. It can be said that the flatness is better as the amount of scraping is smaller.

The center throw was evaluated by measuring the in-plane uniformity. In-plane uniformity is obtained by polishing for 2 minutes under the above-mentioned polishing conditions using a 1-μm thick thermal oxide film deposited on an 8-inch silicon wafer. As shown in FIG. The maximum polishing rate and the minimum polishing rate were obtained from the film thickness measurement values, and the values were calculated by substituting them into the following formula. Table 1 shows the in-plane uniformity of the tenth wafer. Note that the smaller the in-plane uniformity value, the higher the uniformity of the wafer surface.
In-plane uniformity (%) = {(maximum polishing rate−minimum polishing rate) / (maximum polishing rate + minimum polishing rate)} × 100

Grinding characteristics of the edge part Polishing is performed for 2 minutes under the above-mentioned polishing conditions using a 1-μm thick thermal oxide film deposited on an 8-inch silicon wafer, and then the film thickness is measured at intervals of 1 mm from the outer peripheral edge of the wafer to 15 mm inward. did. The film thickness ratio between the film thickness A at the position of 15 mm and the film thickness B at the position of 3 mm was calculated. If the film thickness ratio is less than 10%, the shaving characteristics are good.
Film thickness ratio (%) = (film thickness B / film thickness A) × 100

Example 1
In a reaction vessel, 100 parts by weight of a polyether-based isocyanate-terminated prepolymer (Uniroy Corporation, Adiprene L-325, NCO concentration: 2.22 meq / g) and a silicon-based surfactant (Toray Dow Corning Silicone, SH -192) 3 parts by weight was added and mixed, adjusted to 80 ° C. and degassed under reduced pressure. Then, it stirred vigorously for about 4 minutes so that a bubble might be taken in in a reaction system with the rotation speed of 900 rpm using the stirring blade. Thereto was added 26.2 parts by weight of 4,4′-methylenebis (o-chloroaniline) (Ihara Chemical Amine, Iharacamine MT) previously melted at 120 ° C. The mixed solution was stirred for about 1 minute, and then poured into a mold (width 800 mm, height 1300 mm, height 35 mm) until the liquid level reached 35 mm. Thereafter, the upper surface of the mold was covered with an upper lid provided with 10 φ3 mm vent holes, and the mold was clamped. Then, while the mixture is heated at 60 ° C. and cured by reaction, when the viscosity of the mixture exceeds 10 Pa · s, the side surface of the mold is moved to compress the width of the mold from 800 mm to 700 mm. The state was maintained until it stopped flowing. In addition, the excess liquid mixture was discharged | emitted from the vent hole. Thereafter, post cure was performed at 110 ° C. for 6 hours to obtain a polyurethane resin foam block.

  The polyurethane resin foam block was sliced using a band saw type slicer (manufactured by Fecken) so that the major axis of the elliptical cell was parallel to the thickness direction, to obtain a polyurethane resin foam sheet. Next, using a buffing machine (Amitech Co., Ltd.), the surface of the sheet was buffed to a thickness of 1.27 mm to obtain a sheet with an adjusted thickness accuracy. The buffed sheet was punched out with a diameter of 61 cm, and the surface was punched with a diameter of 1.6 mm to obtain an abrasive sheet. A double-sided tape (manufactured by Sekisui Chemical Co., Ltd., double tack tape) was affixed to the surface opposite to the punching surface of this polishing sheet using a laminator. Further, the surface of the corona-treated cushion sheet (manufactured by Toray Industries, Inc., polyethylene foam, Torepef, thickness 0.8 mm) was buffed and bonded to the double-sided tape using a laminator. Further, a double-sided tape was attached to the other surface of the cushion sheet using a laminator to prepare a polishing pad.

Example 2
Adiprene L-325 (100 parts by weight) and 3 parts by weight of a silicon-based surfactant (SH-192) were added to the reaction vessel and mixed, adjusted to 80 ° C. and degassed under reduced pressure. Then, it stirred vigorously for about 4 minutes so that a bubble might be taken in in a reaction system with the rotation speed of 900 rpm using the stirring blade. Iharacuamine MT (22 parts by weight) and water (0.3 parts by weight) previously melted at 120 ° C. were added thereto. The mixed solution was stirred for about 1 minute, and then poured into a mold (width 800 mm, height 1300 mm, height 35 mm) until the liquid level became 33 mm. Thereafter, a polishing pad was produced in the same manner as in Example 1.

Comparative Example 1
Adiprene L-325 (100 parts by weight) and 3 parts by weight of a silicon-based surfactant (SH-192) were added to the reaction vessel and mixed, adjusted to 80 ° C. and degassed under reduced pressure. Then, it stirred vigorously for about 4 minutes so that a bubble might be taken in in a reaction system with the rotation speed of 900 rpm using the stirring blade. Iharacuamine MT (26.2 parts by weight) previously melted at 120 ° C. was added thereto. The mixed solution was stirred for about 1 minute and then poured into a pan-shaped open mold (casting container). When the fluidity of the mixed solution disappeared, it was placed in an oven and post-cured at 100 ° C. for 16 hours to obtain a polyurethane resin foam block. The closed cells of the polyurethane resin foam were all spherical, and the average cell diameter was 53 μm.

  The polyurethane resin foam block was sliced using a band saw type slicer (manufactured by Fecken) to obtain a polyurethane resin foam sheet. Thereafter, a polishing pad was produced in the same manner as in Example 1.

Comparative Example 2
Adiprene L-325 (100 parts by weight) and 3 parts by weight of a silicon-based surfactant (SH-192) were added to the reaction vessel and mixed, adjusted to 80 ° C. and degassed under reduced pressure. Then, it stirred violently for about 3 minutes so that a bubble might be taken in in a reaction system with the rotation speed of 900 rpm using the stirring blade. Iharacuamine MT (26.2 parts by weight) previously melted at 120 ° C. was added thereto. The mixed solution was stirred for about 1 minute and then poured into a pan-shaped open mold (casting container). When the fluidity of the mixed solution disappeared, it was placed in an oven and post-cured at 100 ° C. for 16 hours to obtain a polyurethane resin foam block. The closed cells of the polyurethane resin foam were all spherical, and the average cell diameter was 53 μm. Thereafter, a polishing pad was produced in the same manner as in Comparative Example 1.

表１の結果より、楕円気泡を有する本発明の研磨パッドは、球状気泡を有する研磨パッド（比較例１及び２）に比べて平坦化特性に優れ、センタースロー及びエッジ部の削り過ぎを効果的に抑制することができることがわかる。

From the results shown in Table 1, the polishing pad of the present invention having elliptical bubbles has excellent flattening characteristics as compared with the polishing pad having spherical bubbles (Comparative Examples 1 and 2), and effectively cuts the center throw and the edge part excessively. It can be seen that it can be suppressed.

Schematic configuration diagram showing an example of a polishing apparatus used in CMP polishing Schematic showing 25 film thickness measurement positions on wafer

Explanation of symbols

1: Polishing pad (polishing layer)
2: Polishing surface plate 3: Abrasive (slurry)
4: Polishing object (semiconductor wafer)
5: Support base (polishing head)
6, 7: Rotating shaft

Claims (5)

In a method for producing a polishing pad comprising a polishing layer comprising a polyurethane resin foam having closed cells,
A step of preparing a foaming reaction liquid by dispersing non-reactive gas as fine bubbles in a polyurethane resin raw material composition by a mechanical stirring method, 50 volumes of the foaming reaction liquid in a mold in which one side or the opposite side is movable Casting process in which an upper lid is placed on the upper surface of the mold and then the mold is clamped, and the side surface of the mold is 50 to 95% of the original width while heating and reacting the foaming reaction liquid. A curing step of compressing the mold by moving it to a width of 5 mm and maintaining the state until it does not flow, and a step of slicing the polyurethane resin foam block obtained in the curing step to produce a polishing layer See
The closed cells contain 50% or more of elliptical bubbles, the polishing layer has elliptical bubbles in the entire thickness direction, and the ratio of the average major axis L to the average minor axis S of the elliptical bubbles on the cut surface of the polishing layer ( L / S) is 1.5-3, The manufacturing method of the polishing pad characterized by the above-mentioned . In a method for producing a polishing pad comprising a polishing layer comprising a polyurethane resin foam having closed cells,
A step of preparing a foaming reaction liquid by dispersing non-reactive gas as fine bubbles in a polyurethane resin raw material composition by a mechanical stirring method, and after pouring 50% by volume or more of the foaming reaction liquid into the mold, A casting process in which the upper lid is installed and the mold is clamped, and the upper lid and / or the lower surface of the mold is 50 to 98% higher than the original height while heating and reacting the foaming reaction liquid. as roll it to mold to compress, it viewed including the step of preparing a curing step to retain that state until it does not flow, and by slicing the obtained polyurethane foam blocks curing step polishing layer,
The closed cells contain 50% or more of elliptical bubbles, the polishing layer has elliptical bubbles in the entire thickness direction, and the ratio of the average major axis L to the average minor axis S of the elliptical bubbles on the cut surface of the polishing layer ( L / S) is 1.5-3, The manufacturing method of the polishing pad characterized by the above-mentioned . In a method for producing a polishing pad comprising a polishing layer comprising a polyurethane resin foam having closed cells,
A step of preparing a foaming reaction liquid by dispersing non-reactive gas as fine bubbles in a polyurethane resin raw material composition by a mechanical stirring method, and after pouring the foaming reaction liquid leaving a space in the mold, on the upper surface of the mold Obtained in a casting process in which an upper lid is placed and the mold is clamped, while the foaming reaction liquid is heated and reaction-cured, the inside of the mold is decompressed, and the decompressed state is maintained until it no longer flows, and the curing process. slicing a polyurethane resin foam block was observed including the step of preparing a polishing layer,
The closed cells contain 50% or more of elliptical bubbles, the polishing layer has elliptical bubbles in the entire thickness direction, and the ratio of the average major axis L to the average minor axis S of the elliptical bubbles on the cut surface of the polishing layer ( L / S) is 1.5-3, The manufacturing method of the polishing pad characterized by the above-mentioned . In a method for producing a polishing pad comprising a polishing layer comprising a polyurethane resin foam having closed cells,
A process of preparing a foaming reaction liquid by adding water and a curing agent to a foam dispersion in which a non-reactive gas is dispersed as fine bubbles in a polyurethane resin raw material composition by a mechanical stirring method, and a foaming reaction liquid in a mold After casting 50 volume% or more, a casting process in which an upper lid having a vent hole is installed on the upper surface of the mold and clamping is performed, and the foaming reaction liquid is heated and reaction-cured, and the carbon dioxide generated by the reaction is used to generate the gold. by increasing the pressure in the mold seen including a step of preparing a polishing layer by slicing curing step to discharge excess foaming reaction mixture from the vent hole, and a polyurethane foam block obtained in the curing step,
The closed cells contain 50% or more of elliptical bubbles, the polishing layer has elliptical bubbles in the entire thickness direction, and the ratio of the average major axis L to the average minor axis S of the elliptical bubbles on the cut surface of the polishing layer ( L / S) is 1.5-3, The manufacturing method of the polishing pad characterized by the above-mentioned . Method for producing a polishing pad according to any one the ellipse bubbles major axis of claims 1-4 you slicing a polyurethane foam block so as to be parallel to the thickness direction of the polishing layer.

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