JPWO2014051104A1 - Polishing pad - Google Patents

Abstract

Provided is a polishing pad capable of shortening a rise time during polishing and improving flatness. The polishing pad 10 includes a polyurethane sheet 2 formed by a wet film forming method. The polyurethane sheet 2 is formed without carbon black and ionic surfactant added. In the polyurethane sheet 2, the polishing surface P is constituted by the surface from which the skin layer is removed. On the polishing surface P, an opening 5 and an opening 6 are formed. In the polyurethane sheet 2, when the contact angle 0.5 seconds after dropping water droplets on the polished surface P is CA1, and the contact angle 10.5 seconds after dropping water droplets is CA2, {(CA1-CA2 ) / CA1} × 100, the contact angle change rate is adjusted to a range of 20 to 50%. Slurry supplied at the time of polishing processing easily penetrates into the polyurethane sheet 2.

Description

  The present invention relates to a polishing pad, and in particular, by a wet film formation method, carbon black for stabilizing foam formation and an ionic surfactant having a function of promoting foam formation are formed without addition, The present invention relates to a polishing pad including a soft plastic sheet in which foam is continuously formed.

  Conventionally, a polishing process using a polishing pad has been performed to flatten an object to be polished such as a semiconductor wafer, glass, or magnetic disk. Among semiconductor objects to be polished, semiconductor devices have been miniaturized, and scratches (scratches) that have not been a problem in conventional polishing processes can be fatal defects. For this reason, demands for defect-free and flattening are increasing even for polishing pads used for polishing. Among the polishing processes, even if fine scratches are allowed in the primary polishing process (rough polishing process), in the final polishing process, it is important how to flatten without generating scratches. Yes.

  Generally, a soft plastic sheet made of polyurethane resin or the like in which foam is formed by a wet film forming method is used for a polishing pad for finishing (see, for example, Japanese Patent Application Laid-Open No. 2002-059356). In the wet film forming method, carbon black is usually added to a resin solution for the purpose of stabilizing foam formation. By adding carbon black, it acts as a coagulation stabilizer (or nucleating agent) for polyurethane resin, thereby suppressing the formation of foam nonuniformly, and as a result, contributes to stabilization of foam formation. . However, since this carbon black is a hard component, when the obtained soft plastic sheet is used as a polishing pad, there is a possibility that fine scratches are generated on the object to be polished. If carbon black is not added to suppress scratching, foam formation may not be stabilized, and high-precision flattening may be difficult.

In addition, in a soft plastic sheet composed of a polyurethane resin, since the polyurethane resin is inherently hydrophobic, the familiarity of the polishing liquid (slurry) supplied during the polishing process is poor, and the slurry may be repelled. For this reason, the distribution of the slurry becomes non-uniform in the surface (polishing surface) of the polishing pad, and the flatness of the object to be polished is impaired. In order to avoid this, it takes time for the slurry to spread over the entire polishing surface, or for the polishing pad to become fully adapted to the slurry. The longer the rise time from the initial stage of the polishing process until the polishing rate is stabilized at a high level, the lower the productivity (the efficiency of the polishing process). In order to shorten the rise time, the polishing pad technology has an appropriate roughness that allows the abrasive grains in the slurry to adhere easily by setting the specific surface area of the polishing layer in the range of 0.5 to 1.0 m ² / g. Is disclosed (see Japanese Patent Application Laid-Open No. 2010-153004).

  However, in the technique of Japanese Patent Application Laid-Open No. 2010-153004, the specific surface area of the polishing layer is optimized before the polishing process, but the polishing layer wears with the polishing process, so the roughness of the polishing surface changes. Resulting in. Therefore, the surface condition of the polishing pad changes with time, and the polishing rate and the like fluctuate to reduce the polishing stability. On the other hand, from the viewpoint of improving compatibility with the slurry, a hydrophilic additive having a function of promoting foam formation can also be used. However, if a hydrophilic additive is used, the hydrophilic additive remaining in the soft plastic sheet elutes with time during the polishing process, so that the polishing rate varies and the polishing stability is affected. Therefore, if the rise time at the time of polishing can be shortened and a stable polishing rate can be obtained without causing scratches, it is effective for polishing of an object to be polished, particularly a semiconductor device.

  An object of the present invention is to provide a polishing pad capable of shortening the rise time during polishing and improving the flatness in view of the above-mentioned cases.

  In order to solve the above problems, the present invention is formed by a wet film forming method without containing carbon black for stabilizing foam formation and an ionic surfactant having a function of promoting foam formation, In a polishing pad provided with a soft plastic sheet in which foaming is continuously formed, the soft plastic sheet has an opening formed in a polishing surface for polishing an object to be polished. When the contact angle 0.5 seconds after dropping water droplets on the polished surface is CA1, and the contact angle 10.5 seconds after dropping water droplets is CA2, {(CA1-CA2) / CA1} × 100 The change rate of the contact angle represented by is in the range of 20% to 50%.

  In this case, grooving or embossing may be performed on the polishing surface side of the soft plastic sheet. At this time, a groove having at least one pattern shape selected from a radial pattern, a lattice pattern, and a spiral pattern can be formed on the polishing surface side of the soft plastic sheet. The soft plastic sheet may be made of a polyurethane resin having a resin modulus of 10 MPa or less. Moreover, the average value of the ratio of the part of the foam formed in the soft plastic sheet to the hole diameter at a depth position of at least 200 μm from the polishing surface of the hole diameter on the polishing surface is 0.65 to 0.95. Range. At this time, it is preferable that the average value of the ratio of the hole diameter of the opening on the polishing surface to the hole diameter at a depth position of at least 200 μm from the polishing surface is in the range of 0.75 to 0.95.

  According to the present invention, since the opening is formed in the polishing surface and the contact angle change rate on the polishing surface is in the range of 20% to 50%, the polishing liquid supplied at the time of polishing processing easily penetrates and is soft plastic. Since the familiarity between the sheet and the polishing liquid is improved, the rise time during polishing can be shortened, and the soft plastic sheet does not contain carbon black, which is a hard component. It is possible to obtain an effect of reducing and improving the flatness.

It is sectional drawing which shows typically the polishing pad of embodiment to which this invention is applied. It is explanatory drawing which shows the change of the hole diameter in the foaming structure of the polishing pad of embodiment. It is a graph which shows a time-dependent change of a contact angle when a water droplet is dripped at the polishing surface of a polishing pad. It is a graph which shows the change of the polishing rate when a wafer with a TEOS film is repeatedly polished using a polishing pad. It is a graph which shows the change of a polishing rate when using a polishing pad and changing a slurry flow rate and repeatedly polishing a wafer with a TEOS film.

  Hereinafter, embodiments of a polishing pad to which the present invention is applied will be described with reference to the drawings.

(Constitution)
As shown in FIG. 1, the polishing pad 10 of this embodiment includes a polyurethane sheet 2 as a soft plastic sheet formed of a polyurethane resin by a wet film forming method. The polyurethane sheet 2 is a state in which carbon black for stabilizing foam formation and an ionic surfactant having a function of promoting foam formation are not added during wet film formation, that is, carbon black and ionic surfactant are added. It is formed without containing.

  In the polyurethane sheet 2, the skin layer formed on the surface side by the wet film forming method is removed by buffing. The surface after the buffing process constitutes a polishing surface P for polishing the object to be polished. Inside the polyurethane sheet 2, the length in the thickness direction is 70% or more of the thickness of the polyurethane sheet 2, and the long foam 3 is rounded along the thickness direction, and the length in the thickness direction is thick. It is formed so that the foam 4 of less than half the thickness is uniformly dispersed. On the polished surface P, long foam 3 and foam 4 are opened, and an opening 5 and an opening 6 are formed, respectively.

  The foam 4 is formed between the long foams 3 at a position biased toward the polishing surface P, and the length of the polyurethane sheet 2 in the thickness direction varies. For this reason, the foam 4 is formed substantially evenly between the long foams 3 formed substantially evenly. The pore diameters of the long foam 3 and foam 4 are formed such that the size on the polishing surface P side is smaller than the opposite surface side of the polishing surface P. The long foam 3 and the foam 4 are communicated in a three-dimensional mesh shape with communication holes not shown. In other words, the polyurethane sheet 2 has a continuous foam structure in which foaming is continuously formed.

  The opening 5 and the opening 6 formed in the polishing surface P have an opening diameter adjusted to a range of 40 ± 5 μm. Moreover, the aperture ratio represented by the percentage of the total area of the aperture 5 and the aperture 6 per unit area of the polished surface P is adjusted in the range of 25% to 30%. The hole diameter and the hole area ratio can be adjusted by the film forming conditions by the wet film forming method, the buffing conditions, and the like.

  As shown in FIG. 2, the opening diameter D1 of the opening 5 in the polishing surface P of the long foam 3 is such that the average value of the ratio to the hole diameter D2 at a depth position of at least 200 μm from the polishing surface P is 0.65 to 0.95. The range is adjusted. In other words, in the long foaming 3, the opening diameter of the opening 5 in the polishing surface P is larger than the opening diameter before being used for the polishing process until the thickness of at least 200 μm of the polyurethane sheet 2 is worn by the polishing process. , 1.05 to 1.54 times.

  In the polyurethane sheet 2, the rate at which the contact angle of water on the polishing surface P changes with time is adjusted to a certain range. That is, in the polyurethane sheet 2, when the contact angle 0.5 seconds after dropping water droplets on the polishing surface P is CA1, and the contact angle 10.5 seconds after dropping water droplets is CA2, {(CA1 The contact angle change rate represented by −CA2) / CA1} × 100 is adjusted to a range of 20 to 50%. The contact angle change rate can be adjusted by the degree of hydrophilicity of the polyurethane resin used for producing the polyurethane sheet 2.

  As shown in FIG. 1, the polishing pad 10 has a double-sided tape 8 for attaching the polishing pad 10 to a polishing machine on the opposite side of the polishing surface P. The double-sided tape 8 has, for example, a pressure-sensitive adhesive layer (not shown) such as an acrylic pressure-sensitive adhesive formed on both surfaces of a base material (not shown) of a flexible film such as a film made of polyethylene terephthalate (hereinafter abbreviated as PET). ing. The double-sided tape 8 is bonded to the polyurethane sheet 2 with an adhesive layer on one side of the substrate, and the adhesive layer on the other side (opposite side to the polyurethane sheet 2) is covered with a release paper (not shown). .

(Manufacturing)
In the production of the polishing pad 10, the polyurethane sheet 2 is produced by a wet film forming method, and the obtained polyurethane sheet 2 and the double-sided tape 8 are bonded together. In the wet film-forming method, a resin solution in which a polyurethane resin is dissolved in an organic solvent is continuously applied to the film-forming substrate, the resin solution is solidified in an aqueous coagulation liquid, and the polyurethane resin is regenerated into a sheet shape and washed. After drying, a belt-like (long shape) polyurethane sheet 2 is produced. Hereinafter, it demonstrates in order of a process.

  In the preparation step, the polyurethane resin is dissolved by mixing a polyurethane resin and a water-miscible organic solvent capable of dissolving the polyurethane resin. As the organic solvent, N, N-dimethylformamide (hereinafter abbreviated as DMF), N, N-dimethylacetamide, or the like can be used. In this example, DMF is used. The polyurethane resin is dissolved so that the concentration is 20 to 50%. If the concentration of the polyurethane resin is less than 20%, the bulk density of the resulting polyurethane sheet is low. On the other hand, if it exceeds 50%, the density becomes too high and the desired foam cannot be formed. Further, the resin solution is not added with an additive such as a pigment such as carbon black for stabilizing foam formation and an ionic surfactant having a function of promoting foam formation. Commonly used ionic surfactants are soluble in an organic solvent used to dissolve the polyurethane resin, and examples thereof include anionic surfactants, cationic surfactants and amphoteric surfactants having ionic properties. Specific examples of the anionic surfactant include carboxylate, sulfonate, sulfate ester salt, phosphate ester salt and the like. Specific examples of the cationic surfactant include amine salt and quaternary ammonium salt. And the like. The amphoteric surfactant includes both characteristics. When dissolved in water, the surfactant exhibits the properties of an anionic surfactant in the alkaline region and the properties of the cationic surfactant in the acidic region. It is. In this example, none of these ionic surfactants are added. The obtained solution is degassed under reduced pressure to obtain a resin solution.

  As the polyurethane resin, a soft resin having a resin modulus of 10 MPa or less is used among resins such as polyester, polyether, and polycarbonate. The polyurethane resin is obtained by reacting a polyvalent isocyanate component having two or more isocyanate groups in the molecule with a polyhydric alcohol component having two or more hydroxyl groups in the molecule. The resin modulus is an index representing the hardness of the resin, and is a value obtained by dividing the load applied when the non-foamed resin sheet is stretched 100% (up to twice the original length) by the unit area ( Hereinafter, it may be referred to as 100% modulus). It means that it is a hard resin, so that this value becomes large.

  As the polyvalent isocyanate component, a diisocyanate compound, a triisocyanate compound, or the like can be used, and two or more of a diisocyanate compound and a triisocyanate compound may be used in combination. On the other hand, a diol compound, a triol compound, or the like can be used as the polyhydric alcohol component. For example, polyether polyol compounds such as polyethylene glycol (PEG) and polytetramethylene glycol (PTMG), and polyester polyol compounds such as a reaction product of ethylene glycol and adipic acid, which are conventionally used in general wet film formation methods Polycarbonate polyol compounds and the like can be used. In this example, since the carbon black and the ionic surfactant are not added, it is preferable to use a hydrophilic diol compound in order to stabilize foam formation. The “hydrophilic diol compound” used in this example is not in a specific range as a measure of hydrophilicity or the like, but has improved hydrophilicity over a conventionally used diol compound. For example, a hydrophilic diol compound can be obtained by increasing the ratio of oxygen atoms to methylene groups in the diol compound, introducing a hydrophilic functional group, or the like. Specifically, for example, adipic acid is replaced with succinic acid for a compound obtained by reaction of adipic acid, which is a conventionally used polyester diol compound, with a polyol containing 1,4-butanediol or ethylene glycol. The hydrophilicity can be improved by using a compound in which the molar ratio of ethylene glycol in the polyol is increased. That is, the number of methylene groups is 4 for adipic acid, but 2 for succinic acid, and the number of methylene groups per repeating unit of the polymer is 4 for 1,4-butanediol. In contrast, ethylene glycol has two. For this reason, in any case, the ratio of oxygen atoms to methylene groups is increased, and hydrophilicity is improved.

  By reacting the hydrophilic diol compound with the polyvalent isocyanate compound, the resulting polyurethane resin has improved hydrophilicity. That is, the higher the degree of hydrophilicity of the diol compound, the higher the hydrophilicity of the polyurethane resin. For this reason, in the obtained polyurethane sheet 2, the affinity with respect to water increases, and the contact angle of water decreases in a short time. In other words, the contact angle change rate of the polyurethane sheet 2 can be increased by increasing the hydrophilicity of the diol compound.

  In the application step, the resin solution prepared in the preparation step is applied to the belt-shaped film forming substrate at a normal temperature by an application device such as a knife coater. At this time, the application thickness (application amount) of the resin solution is adjusted by adjusting the gap (clearance) of the application device. In this example, in order to form the above-described foamed structure, it is preferable to adjust the coating thickness as appropriate in the range of 1.0 to 3.0 mm. If the coating thickness is less than 1.0 mm, the hole diameter at a depth of at least 200 μm from the surface tends to be larger than the hole diameter in the vicinity of the surface, and the polyurethane sheet 2 described above cannot be obtained. On the other hand, when the coating thickness exceeds 3.0 mm, dripping and coating spots are likely to occur before the resin solution is immersed in the aqueous coagulation liquid, and the above-described foamed structure is difficult to be formed. Moreover, although a flexible film, a nonwoven fabric, a woven fabric, etc. can be used for the film-forming base material, in this example, the film-forming base material is described below as a PET film.

  In the coagulation regeneration process, the resin solution applied to the film forming substrate in the application process is immersed in a coagulation liquid (water-based coagulation liquid) whose main component is water that is a poor solvent for the polyurethane resin. In the coagulation liquid, first, a skin layer having a thickness of about several μm is formed on the surface side of the resin solution. As the substitution of DMF and coagulating liquid proceeds, the resin solution coagulates and the polyurethane resin is regenerated into a sheet on the film-forming substrate. That is, when DMF is removed from the resin solution and DMF and the coagulating liquid are replaced, long foam 3 and foam 4 are formed inside the skin layer (in the polyurethane resin). A communication hole (not shown) that communicates in a mesh shape is formed. Since the PET film of the film-forming substrate does not allow water to permeate, desolvation occurs on the skin layer side, and a long foam 3 having a larger film-forming substrate side than the skin layer side is formed. By increasing the hydrophilicity of the polyurethane resin and increasing the coating thickness of the resin solution, the progress of substitution between the DMF and the coagulation liquid in the resin solution is delayed. Further, when the temperature of the coagulating liquid is increased, the formation of the skin layer is accelerated, and the progress of substitution between the DMF in the resin solution and the coagulating liquid is further delayed. In this example, in order to form the above-described foamed structure, the coagulating liquid temperature is appropriately adjusted in the range of 20 to 50 ° C. If the coagulating liquid temperature is less than 20 ° C., the bulk density is low, the number of foaming in the vicinity of the surface is increased, and the pore diameter is decreased, which is not preferable. In particular, when the coating thickness is 1.0 mm or more, if the coagulation liquid temperature is too low, it is not preferable because the coagulation liquid cannot be completely solidified and brought into the drying process. On the other hand, if it is too high, the formation of the skin layer becomes too early, the progress of the substitution of the DMF and the coagulating liquid in the resin solution becomes extremely slow, the above-mentioned foam structure is difficult to form, and the working environment is deteriorated. This is not preferable.

  Here, formation of the long foam 3 and the foam 4 will be described. In this example, a polyurethane resin having a hydrophilicity enhanced by a diol compound that has been made hydrophilic without adding carbon black and an ionic surfactant to the resin solution and using a hydrophilic diol compound is used. For this reason, since the replacement speed of DMF and the coagulating liquid becomes slow, the long foams 3 are formed in an almost uniformly dispersed manner inside the polyurethane resin inside the skin layer. Further, since the solvent removal occurs through the skin layer, the foam 4 is elongated between the long foams 3 at a position biased toward the skin layer.

  In the cleaning / drying process, the polyurethane resin coagulated and regenerated in the coagulation regeneration process (hereinafter referred to as film forming resin) is peeled off from the film forming substrate and remains in the film forming resin by washing in a cleaning solution such as water. Remove DMF. After cleaning, the film forming resin is dried with a cylinder dryer. The cylinder dryer includes a cylinder having a heat source therein. The film-forming resin is dried by passing along the peripheral surface of the cylinder. The film-forming resin after drying is wound up in a roll shape.

  In the buffing process, buffing is performed on the skin layer side of the film-forming resin after drying. That is, the surface of the pressure welding jig having a substantially flat surface is pressed against the surface opposite to the skin layer, and the skin layer side is buffed. In this example, since the continuously formed film-forming resin is strip-shaped, the skin layer side is continuously buffed while pressing the pressing roller against the surface opposite to the skin layer. Thereby, as shown in FIG. 1, the skin layer is removed, and openings 5 and 6 are formed in the polishing surface P of the polyurethane sheet 2. Moreover, the thickness of the polyurethane sheet 2 becomes substantially uniform by performing this buffing process. In the obtained polyurethane sheet 2, the contact angle change rate on the polished surface P is in the range of 30 to 50% because the hydrophilicity of the used polyurethane resin is enhanced. Further, since the resin modulus of the polyurethane resin is 10 MPa or less, the hardness is Shore A type in the range of 11 to 16 degrees, the compression rate is in the range of 32 to 42%, and the compression modulus is in the range of 95 to 100%. Hardness, compression rate, and compression modulus are not particularly limited, but if it is too soft, it becomes difficult to stably polish the object to be polished. On the other hand, if it is too hard, scratches are likely to occur on the object to be polished. It is preferable that These numerical values can be adjusted by the type and concentration of the polyurethane resin used.

  In the laminating process, the surface opposite to the polishing surface P of the buffed polyurethane sheet 2 is bonded to the double-sided tape 8. Then, it is cut into a desired shape such as a circle, and inspections such as confirming that there is no adhesion of dirt, foreign matter, etc. are performed to complete the polishing pad 10.

  When polishing the object to be polished with the obtained polishing pad 10, for example, a single-side polishing machine is used. In a single-side polishing machine, a polishing pad 10 is mounted on a polishing surface plate. When the polishing pad 10 is mounted, the release paper of the double-sided tape 8 is peeled off and attached with the exposed adhesive layer. At the time of polishing, the object to be polished is held on a holding surface plate arranged opposite to the polishing surface plate, and a polishing liquid (slurry) containing abrasive particles is supplied between the processed surface of the object to be polished and the polishing surface P of the polishing pad 10. However, the processing surface of the object to be polished is polished by rotating the polishing surface plate or holding surface plate while applying pressure between the object to be polished and the polishing pad 10.

(Function)
Next, the operation and the like of the polishing pad 10 of this embodiment will be described.

  In the polishing pad 10 of the present embodiment, the contact angle change rate when water droplets are dropped on the polishing surface P is adjusted to a range of 20 to 50%. For this reason, the slurry supplied at the time of a grinding | polishing process becomes easy to osmose | permeate the polyurethane sheet 2, and familiarity with the polyurethane sheet 2 and slurry improves. As a result, at the initial stage of polishing, the slurry reaches the entire polishing surface P, or the slurry is easily adapted to the polishing surface P, so that the rise time can be shortened and productivity can be improved.

  Further, in the polishing pad 10 of the present embodiment, the polyurethane sheet 2 contains carbon black for stabilizing foam formation in the resin solution during wet film formation, and an ionic surfactant having a function of promoting foam formation. It is formed in an additive-free state. Since carbon black is a hard component, if it is contained in a polyurethane sheet, it may be exposed on the polishing surface during polishing, and may cause scratches on the object to be polished. In addition, if an ionic surfactant is blended during wet film formation, the ionic surfactant remaining in the polyurethane sheet may elute over time during polishing, resulting in fluctuations in the polishing rate. May impair the stability. In the polishing pad 10, since carbon black, which is a hard component, is not added, scratches on the object to be polished can be reduced and flatness can be improved. In addition, since no ionic surfactant is added, the ionic surfactant is not eluted during polishing, and fluctuations in the polishing rate are suppressed, so that stable polishing can be performed.

  Furthermore, in the polishing pad 10 of the present embodiment, a polyurethane resin having a resin modulus of 10 MPa or less is used for producing the polyurethane sheet 2. For this reason, since the obtained polyurethane sheet 2 becomes soft and can come into soft contact with the object to be polished during polishing, scratches can be reduced.

  Furthermore, the conventional polyurethane film formed by the wet film forming method is made of a polyurethane resin using a polyether polyol compound, a polyester polyol compound, a polycarbonate polyol compound or the like as a polyhydric alcohol component, and carbon black or ion is added to the resin solution. It is common to add a surfactant. On the other hand, in the polishing pad 10 of this embodiment, the polyurethane resin formed by reaction with the polyvalent isocyanate component and the polyhydric alcohol component is used for the production of the polyurethane sheet 2, and the polyhydric alcohol component is used as the polyhydric alcohol component. Hydrophilic diol compounds are used. For this reason, as described above, foam formation can be stabilized even when carbon black or an ionic surfactant is not added. As a result, the polyurethane sheet 2 having a continuous foamed structure with a pore diameter of 40 ± 5 μm and a porosity of 25% to 30% in the polished surface P can be produced.

  About the range of an aperture diameter, it is desirable to adjust to the range of an aperture diameter of 35-45 micrometers by grinding the surface of a polyurethane sheet. When the number of small-diameter holes having an opening diameter of less than 35 μm is increased, clogging due to slurry or polishing debris is likely to occur. On the other hand, when the number of large-diameter holes having an opening diameter of more than 45 μm is increased, polishing scraps and the like are likely to be accumulated on the bottom side of the long foam 3 and foam 4, and the polyurethane sheet 2 is caused by wear accompanying the progress of the polishing process. When the thickness is reduced, the accumulated polishing waste and the like are released, and the possibility of causing scratches on the object to be polished increases. Moreover, about the range of an aperture ratio, it is desirable for an aperture ratio to be the range of 25-30%. When the open area ratio is within this range, 75 to 70% is secured as a region that can be a contact point of slurry (especially, abrasive particles contained in the slurry) with the object to be polished, so that the polishing rate can be improved. it can. If the open area ratio is less than 25%, the slurry circulation retention is insufficient and the rising of the polishing process is worsened. On the other hand, when the hole area ratio exceeds 30%, the area that can be a contact point of the slurry is reduced, which leads to a decrease in the polishing rate.

  Furthermore, in the polishing pad 10 of the present embodiment, the foamed foam 3 having a length of 70% or more of the length in the thickness direction is formed on the polyurethane sheet 2, and the long foamed foam 3 is opened on the polishing surface P. The average value of the ratio of the hole diameter D1 to the hole diameter D2 at a depth position of at least 200 μm from the polishing surface P is adjusted to a range of 0.65 to 0.95 (see also FIG. 2). For this reason, even if the polyurethane sheet 2 is worn during the polishing process, the expansion of the hole diameter is suppressed, so that the ratio of the holes occupying the polishing surface P, that is, the hole area ratio is hardly changed. Further, in the thickness range of at least 200 μm from the polishing surface P, a capillary phenomenon occurs due to the elongated foam shape, so that the water absorption of the slurry can be increased. Accordingly, since the storage and supply of the slurry during the polishing process is stabilized, the object to be polished can be polished flatly for a long time, and the life of the polishing pad 10 can be improved. In consideration of improving the storage and supply stability of the slurry, it is preferable to adjust the average value of the ratio of the opening diameter D1 to the hole diameter D2 in the range of 0.75 to 0.95. This can be realized, for example, by film forming conditions in a wet film forming method.

  Further, in the polishing pad 10 of the present embodiment, since the long foam 3 and the foam 4 communicate with each other through the communication holes, the slurry moves between the long foam 3 and the foam 4 through the communication holes. Slurry can be supplied approximately evenly between the pads 10. As a result, the object to be polished is polished substantially evenly, so that the processed surface can be uniformly polished and the flatness can be improved. Moreover, in the polishing pad 10 of this embodiment, the double-sided tape 8 which has the base material of the film made from PET on the opposite side to the grinding | polishing surface P of the polyurethane sheet 2 is bonded together. For this reason, since the flexible polyurethane sheet 2 is supported by the base material of the double-sided tape 8, the handling at the time of conveyance of the polishing pad 10 or attachment to a polishing machine can be facilitated.

  Although not particularly mentioned in the present embodiment, grooving or embossing may be performed on the polishing surface P side of the polishing pad 10 in consideration of supply of slurry and discharge of polishing debris. The pattern shape of the groove to be formed may be any of a radial shape, a lattice shape, a spiral shape, and the like, or a combination thereof. Further, the cross-sectional shape of the groove is not particularly limited, and may be any shape such as a rectangular shape, a U shape, a V shape, and a semicircular shape. Furthermore, the pitch, width, and depth of the grooves are not particularly limited as long as the polishing waste can be discharged and the slurry can be moved. The method for forming the groove is not particularly limited as long as it is a method capable of forming a desired groove. Considering that the polyurethane sheet 2 is soft, embossing with heating and pressing can be performed.

  In the present embodiment, an example is shown in which the skin layer is removed to form the opening by buffing the film-forming resin after the wet film formation, but the present invention is not limited to this. As a method of forming the opening in the polished surface P, any method that can remove the skin layer may be used. For example, a slicing process may be performed. When the slicing process is performed, considering that the film-forming resin is flexible and elastic, for example, a substantially flat polyurethane sheet 2 from which the skin layer has been removed can be obtained by performing the slicing process while applying tension. .

  Furthermore, in the present embodiment, an example in which a PET film is used as a film formation substrate at the time of wet film formation is shown, but the present invention is not limited to this, and for example, a nonwoven fabric or a woven fabric is used. It may be. In this case, since it is difficult to peel off the solidified and regenerated polyurethane resin from the film forming substrate, the double-sided tape 8 may be bonded to the surface opposite to the polyurethane resin after washing and drying without peeling. Moreover, although the example which affixes the double-sided tape 8 on the surface on the opposite side to the grinding | polishing surface P of the polyurethane sheet 2 was shown, the support material which supports the polyurethane sheet 2 between the polyurethane sheet 2 and the double-sided tape 8 is shown, for example. You may make it stick together. In this way, the polishing pad 10 can be more easily transported and handled.

  Furthermore, in the present embodiment, the polyurethane sheet 2 is exemplified by a polyurethane resin such as a polyester-based, polyether-based, or polycarbonate-based material. However, the present invention is not limited to this, for example, a polyester resin or the like. It may be used. If a polyurethane resin is used, a sheet having a foam structure in which long foam 3 and foam 4 are formed by a wet film forming method can be easily formed.

  Hereinafter, examples of the polishing pad 10 manufactured according to the present embodiment will be described. A comparative polishing pad manufactured for comparison is also shown.

Example 1
In Example 1, as a polyurethane resin, a polyol having succinic acid and ethylene glycol and 1,4-butanediol as structural units (the structural unit ratio of ethylene glycol and 1,4-butanediol is an equivalent ratio of 5: 5). ) And 30 parts of a 30% polyester MDI (diphenylmethane diisocyanate) polyurethane resin solution containing a polyester diol obtained by reaction with 36 parts of DMF for viscosity adjustment was mixed to prepare a resin solution. The resin modulus of the polyurethane resin used is 6 MPa. Using the obtained resin solution, a polyurethane sheet 2 was produced by a wet film-forming method with a coating thickness of 1.30 mm when the resin solution was applied to the film-forming substrate. The polyurethane layer 2 was buffed on the skin layer side with a buff treatment amount of 0.14 mm using a sandpaper of buff count # 180, and a double-sided tape 8 was bonded to produce a polishing pad 10.

(Example 2)
In Example 2, as a polyurethane resin, a polyol having succinic acid and ethylene glycol and 1,4-butanediol as structural units (the structural unit ratio of ethylene glycol and 1,4-butanediol is an equivalent ratio of 4: 6). A resin solution was prepared in the same manner as in Example 1 except that a polyester MDI polyurethane resin containing a polyester diol obtained by reacting was prepared, and a polishing pad 10 was produced. The resin modulus of the polyurethane resin used is 6 MPa.

(Example 3)
Example 3 is the same as Example 1 except that a polyester MDI polyurethane resin containing a polyester diol obtained by reacting malonic acid with a polyol having 1,4-butanediol as a structural unit was used as the polyurethane resin. Thus, a resin solution was prepared and a polishing pad 10 was manufactured. The resin modulus of the polyurethane resin used is 6 MPa.

Example 4
A polishing pad 10 was produced in the same manner as in Example 1 except that a groove was formed on the polishing surface P side of the polyurethane sheet 2 produced in Example 1. In the formation of the grooves, grooves of a lattice pattern having a rectangular cross section with a groove width of 1 mm and a groove interval of 3 mm were formed by embossing.

(Comparative Example 1)
In Comparative Example 1, a polyester MDI polyurethane resin containing a polyester diol obtained by reacting adipic acid and a polyol having 1,4-butanediol as a structural unit was used as the polyurethane resin. The resin modulus of the polyurethane resin used is 6 MPa. To 100 parts of this 30% polyurethane resin solution, 5 parts of hydrophilic additive sodium lauryl sulfate (SLS) was added, and 36 parts of DMF for viscosity adjustment were mixed to prepare a resin solution. Using the obtained resin solution, a polyurethane sheet was produced by a wet film forming method to produce a polishing pad.

(Comparative Example 2)
In Comparative Example 2, a polishing pad was produced in the same manner as in Example 1 except that carbon black was added to the resin solution at a ratio of 5.0% by mass of the total solid content and mixed.

(Comparative Example 3)
In Comparative Example 3, a polishing pad was produced in the same manner as in Example 1 except that a polyurethane resin having a resin modulus of 15 MPa was used.

(Comparative Example 4)
In Comparative Example 4, a polyester MDI polyurethane resin containing a polyester diol obtained by reacting adipic acid and a polyol having 1,4-butanediol as a structural unit is used as the polyurethane resin, and no hydrophilic additive is added. A resin solution was prepared. The resin modulus of the polyurethane resin used is 6 MPa. When a polyurethane sheet was produced by a wet film formation method using the obtained resin solution, it could not be produced as a polishing pad due to film formation failure.

(Contact angle evaluation)
The contact angle change rate of water was calculated for each polishing pad of the example and the comparative example. The contact angle was measured using a solid-liquid interface analyzer (DropMaster 500: manufactured by Kyowa Interface Science Co., Ltd.) as a contact angle meter. In the measurement of the contact angle, one drop of water was dropped on the surface of the polishing pad from the injection needle under the conditions of a temperature of 20 ° C. and a humidity of 60%, and after 0.5 seconds to 10.5 seconds after dropping. The time-dependent change of the dynamic contact angle for 10 seconds was measured. That is, from the contact angle CA1 measured 0.5 seconds after dropping a water drop and the contact angle CA2 measured 10.5 seconds after dropping the water drop, the contact angle is {(CA1-CA2) / CA1} × 100. The rate of change was calculated. The results of the contact angles CA1, CA2 and the contact angle change rate are shown in Table 1 below. In addition, the measurement was performed 4 times and the average value was shown.

  As shown in Table 1, in the polishing pad of Comparative Example 1, the contact angle change rate was 15%. On the other hand, in the polishing pad 10 of Examples 1 to 4, the contact angle change rates were 47%, 39%, 28%, and 22%, respectively. In addition, as shown in FIG. 3, in Comparative Example 1, although the hydrophilic additive sodium lauryl sulfate was added to the resin solution, the contact angle gradually decreased with time and showed about 50 degrees even after 100 seconds. It was. On the other hand, in Examples 1 to 3, the contact angle rapidly decreased, and decreased to about 10 degrees after 20 to 30 seconds. In Example 1 to Example 3, compared with Comparative Example 1, the polyurethane sheet 2 was made of a polyurethane resin whose hydrophilicity was increased by a diol compound hydrophilized, so that water penetrated the polyurethane sheet 2. This is considered to be because the contact angle became small in a short time. It has been confirmed that Example 4 has the same result. On the other hand, it can be considered that the contact angle change rate in Example 4 was decreased because the measured value of the contact angle CA1 was increased. The cause of this is not clear, but since embossing was used when forming the groove on the polishing surface P side, it was expected that the degree of hydrophilicity of the resin on the surface was affected. Further, in Comparative Example 2 in which carbon black was added to the resin solution and Comparative Example 3 in which the resin modulus was 15 MPa exceeding 10 MPa, the degree of hydrophilicity of the polyurethane resin itself was equivalent to that in Example 1, and thus Comparative Example As a result, the contact angle change rate increased as compared with the case of 1.

(Water absorption speed evaluation)
The water absorption speed was calculated using the solid-liquid interface analyzer used in the contact angle evaluation. In the measurement, under the conditions of a temperature of 20 ° C. and a humidity of 60%, one drop of water was dropped from the injection needle onto the surface of the polishing pad, and the speed until the contact angle decreased 10 degrees from the contact angle immediately after dropping (degree / Sec) was measured. That is, the water absorption speed was calculated by 10 / t, where time t (seconds) required to decrease by 10 degrees from the contact angle immediately after dropping the water droplet was used. The results of water absorption speed are shown in Table 1. In addition, the measurement was performed 4 times and the average value was shown.

  As shown in Table 1, the water absorption speed of the polishing pad of Comparative Example 1 was 0.6. On the other hand, in the polishing pad 10 of Examples 1 to 4, the water absorption speeds were 4.3, 5.0, 3.3, and 2.5, respectively. Similar to the results of the contact angle change rate, the results of the water absorption speed revealed that Examples 1 to 4 were easier to adjust to water than Comparative Example 1. Therefore, in the polishing pad 10 of the first to fourth embodiments, the familiarity of the slurry supplied during the polishing process is improved, and the rise time can be expected to be shortened. On the other hand, about the water absorption speed of the comparative example 2 and the comparative example 3, it became a result larger than the thing of the comparative example 1 similarly to the result of a contact angle change rate.

(Evaluation of hole diameter)
About each polishing pad of an Example and a comparative example, the average hole diameter, the hole area ratio, and the hole diameter ratio were measured. In the measurement of the average hole diameter (μm) and the hole area ratio (%), the range of about 5 mm square was enlarged 50 times with a scanning electron microscope (manufactured by JEOL Ltd., JSM-5000LV), and 9 spots were observed. . This image was binarized by image processing software (Image Analyzer V20LAB Ver. 1.3, manufactured by Nikon) to check the number of holes, and the equivalent circle diameter and the average value were calculated from the respective opening areas as the average hole diameter. Calculated as In the measurement of the hole area ratio, the cut-off value (lower limit) of the hole diameter was 11 μm, and noise components were excluded. For the polishing pad 10 of Example 4 in which the groove was formed on the polishing surface P side, the area of 2 mm square of the land surface that directly contributes to the polishing process was observed, and the minimum portion surrounded by the lattice-like grooves One land surface (corresponding to a polished surface) was measured at one place, a total of nine places. On the other hand, in the measurement of the aperture diameter ratio, for the aperture diameter of the long foam 3, from the cross-sectional photograph (scanning electron microscope) of the polyurethane sheet 2, the aperture diameter D1 on the polishing surface P and the thickness of the polyurethane sheet 2 from the polishing surface P. The hole diameter D2 at a position of 200 μm in the vertical direction was measured, and the average value of the ratio of the opening diameter D1 to the hole diameter D2 (opening diameter ratio = D1 / D2) was calculated. Table 1 also shows the measurement results of the average hole diameter, the hole area ratio, and the hole diameter ratio.

  As shown in Table 1, in each of the polishing pads 10 of Examples 1 to 4, the average hole diameter was in the range of 35 to 45 μm, and the coating thickness on the film forming substrate was 1.30 mm. The hole diameter ratio was in the range of 0.65 to 0.95.

(Polishing evaluation)
Using the polishing pads of the examples and comparative examples, 100 wafers of TEOS (Tetro Ethyl Silicon Silicate) -coated silicon wafers were repeatedly subjected to polishing processing under the following conditions to determine the polishing rate, the rising situation, and the polishing rate. Stability was evaluated. The polishing rate is expressed by dividing the polishing amount, which is the difference in film thickness before and after polishing, by the polishing time, and was obtained from the average value of the thickness measurement results at 121 locations for each of the silicon wafers before and after polishing. . For the thickness measurement, an optical film thickness measuring device (manufactured by KLA Tencor, trade name “ASET-F5x”, measurement: DBS mode) was used. The measurement results of the polishing rate after polishing 25 silicon wafers are shown in Table 2 below.
<Polishing conditions>
Polishing machine used: Product name “F-REX300” manufactured by Ebara Corporation
Polishing speed (rotation speed of surface plate): 70 rpm
Processing pressure: 176 g / cm ²
Slurry: Colloidal silica slurry (pH: 11.5)
Slurry flow rate: 200mL / min
Polishing time: 60 seconds Object to be polished: Silicon wafer with TEOS

  As shown in Table 2, in Comparative Example 1, the polishing rate was 542 mm. On the other hand, in Examples 1 to 4, the polishing rates were 643 mm, 622 mm, 617 mm, and 594 mm, respectively, which were higher than those in Comparative Example 1 and the polishing process was started up well. This is probably because the polyurethane sheet 2 is made of a polyurethane resin having improved hydrophilicity, so that the familiarity of the slurry is improved and the circulation retention of the slurry is improved. On the other hand, in Comparative Example 2, since carbon black was added to the resin solution, it was considered that the carbon black was exposed to the polished surface due to abrasion of the polyurethane sheet accompanying the polishing process, and the polishing rate was increased. In Comparative Example 3, it is considered that the polyurethane sheet was hardened and the polishing rate was increased because a polyurethane resin having a resin modulus of 15 MPa was used.

  FIG. 4 shows changes in the polishing rate of Example 1 and Comparative Example 1. With the polishing pad of Comparative Example 1, the polishing rate gradually increased even when polishing was performed up to 100 sheets, and fluctuations in the polishing rate were also observed. In contrast, with the polishing pad 10 of Example 1, it was found that the polishing rate rapidly increased up to about 20 sheets, and thereafter the polishing rate was stabilized. It has been confirmed that the results of the polishing pad 10 of Examples 2 to 4 and the polishing pads of Comparative Examples 2 to 3 are the same as those of Example 1. Therefore, in the polishing pad 10 of each example whose contact angle change rate is in the range of 20 to 50%, it becomes clear that the time until the polishing rate is stabilized is shortened and the stable polishing rate can be maintained for a long time. It was.

(Defect evaluation)
Defects were evaluated using the polishing pads of Examples and Comparative Examples. In the defect evaluation, 25 silicon wafers with TEOS were repeatedly polished three times in succession (for a total of 75 wafers), and the unpatterned wafer surface inspection was performed on the 71st to 75th silicon wafers after polishing. Defects were measured in a high-sensitivity measurement mode of the apparatus (Surfscan SP1DLS, manufactured by KLA Tencor), and defects on the substrate surface were evaluated. At the time of measurement, the measurement was performed twice under two conditions of Wide (wide), which is a mode capable of detecting defects of 0.16 μm or more, and Narrow (mode), which is a mode capable of detecting defects of 0.20 μm or more. Defect evaluation results are also shown in Table 2. In the defect column in Table 2, Wide is a result of measurement for a defect having a size of 0.16 μm or more, and Narrow is a measurement of 0.20 μm or more.

  As shown in Table 2, the polishing pad 10 of Examples 1 to 4 showed 58 to 74 defects in Wide mode and 26 to 39 defects in Narrow mode. Also in Comparative Example 1, there were 75 in the Wide mode and 35 in the Narrow mode. This is considered to be because in Examples 1 to 4 and Comparative Example 1, carbon black was not added to the resin solution, so that defects on the object to be polished could be suppressed. On the other hand, in Comparative Example 2 in which carbon black was added, the defects increased remarkably in both the Wide mode and the Narrow mode. Further, in Comparative Example 3 using a polyurethane resin having a resin modulus of 15 MPa, the defect increased in both the Wide mode and the Narrow mode due to the hardened polyurethane sheet.

(Slurry retention evaluation)
In the evaluation of slurry retention, changes in the polishing rate when the slurry flow rate of 200 mL / min described above was changed to 300 mL / min and 100 mL / min for the polishing pads of Example 1 and Comparative Example 1 were compared. As shown in FIG. 5, the polishing pad of Comparative Example 1 was inferior in slurry retention, so that the polishing rate was reduced with a decrease in the slurry flow rate. On the other hand, in Example 1, it was found that there was little drop in the polishing rate even when the slurry flow rate was changed. This is presumably because the slurry retention was increased by setting the rate of change in the contact angle of water on the polished surface P within the above-described range.

  Since the present invention provides a polishing pad that can shorten the rise time during polishing and improve the flatness, it contributes to the manufacture and sale of the polishing pad, and thus has industrial applicability.

Claims (5)

  A soft plastic sheet formed without a carbon black for stabilizing foam formation and an ionic surfactant having a function of promoting foam formation by a wet film-forming method, in which foam is continuously formed. In the polishing pad provided, the soft plastic sheet has an opening formed in a polishing surface for polishing an object to be polished, and the polishing surface drops water droplets on the polishing surface for 0.5 seconds. The contact angle change rate represented by {(CA1−CA2) / CA1} × 100 is 20% when the subsequent contact angle is CA1 and the contact angle after 10.5 seconds from the dropping of the water droplet is CA2. A polishing pad characterized by being in the range of 50%.   The polishing pad according to claim 1, wherein the soft plastic sheet is grooved or embossed on the polishing surface side.   3. The polishing pad according to claim 2, wherein the soft plastic sheet has grooves of at least one pattern shape selected from a radial pattern, a lattice pattern, and a spiral pattern on the polishing surface side. .   The polishing pad according to claim 1, wherein the soft plastic sheet is made of a polyurethane resin having a resin modulus of 10 MPa or less.   Among the foams formed on the soft plastic sheet, some of the foams have an average value of the ratio of the hole diameter of the opening in the polishing surface to the hole diameter at a depth position of at least 200 μm from the polishing surface is 0.65 to 0 The polishing pad according to claim 1, which is in a range of .95.

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