JP6311186B2 - Polishing pad and manufacturing method thereof - Google Patents

Description

  The present invention relates to a polishing pad [for example, a polishing pad for chemical mechanical polishing (CMP)] used for polishing processing at a low pressure [for example, 2.5 psi (17 kPa) or less] and a manufacturing method thereof.

  Since materials such as semiconductor devices (objects to be polished) are required to have surface flatness, polishing using a polishing pad is performed. As a method for planarizing the surface of a semiconductor device or the like, a chemical mechanical polishing (CMP) method is generally used. In the CMP method, a so-called free abrasive is usually used in which a slurry (polishing liquid) in which abrasive grains (polishing particles) are dispersed in an alkali solution or an acid solution is supplied between a polishing pad and an object to be polished during polishing. The grain method is adopted.

  In semiconductor devices, as the degree of integration of semiconductor circuits increases, miniaturization and multilayer wiring for the purpose of higher density have progressed, and a technique for further flattening the surface has become important. Specifically, in a semiconductor circuit, the wiring interval is about 65 nm, whereas in a so-called next-generation semiconductor device with high density and miniaturization, the wiring interval is reduced to about 45 nm. The wiring interval tends to be further narrowed in the future. Moreover, since copper wiring with low mechanical strength is used as the wiring material, it is increasingly difficult to reduce the defect occurrence rate (defect rate). In order to reduce the defect rate, polishing at a low pressure is in progress. For example, in a copper CMP process at a 90 nm node to a 65 nm node, polishing is performed with the pressure applied to the device set to 2.5 psi or less. .

  As a polishing pad for low-pressure polishing, for example, a polishing pad (Patent Document 1) having a surface centerline average roughness (Ra) of 7 to 11 μm, and all bubbles of the polishing layer having closed cells with an average cell diameter of 100 to 300 μm A polishing pad (Patent Document 2) is known in which the ratio of bubbles having a bubble diameter of 50 μm or less is 10% or less.

  However, these polishing pads cannot sufficiently reduce the occurrence of defects in the object to be polished. Reducing the defect rate is the ultimate goal of device flattening, and achieving this goal will become even more important in an era when device miniaturization is indispensable.

  In addition, since these polishing pads are used at a low pressure, the polishing rate is lower than the polishing under medium to high pressure, but when the temperature of the object to be polished gradually increases due to frictional heat during polishing, There is a tendency that the chemical action of the slurry is activated and the polishing rate is improved. However, the surface temperature of the polishing pad tends to be non-uniform in the surface, causing polishing rate irregularities in the surface of the object to be polished, resulting in a problem that flattening characteristics (dishing and erosion) are lowered, and polishing stability is still sufficient. is not.

JP 2012-238692 A Japanese Patent No. 5145683

Accordingly, a first object of the present invention is to provide a polishing pad that can significantly reduce the occurrence of defects in an object to be polished and a method for manufacturing the same.
A second object of the present invention is to provide a polishing pad excellent in polishing stability and a method for producing the same.
Furthermore, a third object of the present invention is to provide a polishing pad that can achieve both suppression of defects and polishing stability, and a method for manufacturing the same.

As a result of intensive studies to achieve the above-described problems, the present inventors have found that polishing in a low pressure [for example, 2.5 psi (17 kPa) or less]
(1) When foreign matter such as polishing agglomerates is generated, a large pressure [for example, pressure exceeding 2.5 psi (17 kPa)] is applied to the polishing pad. In order to show expansion, it is easy to cause defects by repelling foreign matter, and if a polishing pad that exhibits negative thermal expansion at the load pressure is used, it is easy to take in foreign matter to the polishing pad side by compressive deformation, and defects are generated. Friction can be significantly reduced if (2) the amount of deformation (strain constant) of the polishing pad in the polishing pressure region [eg, 1.0 psi (6.9 kPa) to 2.5 psi (17 kPa)] is adjusted to a specific range. It was found that the resistance can be kept within a desired range, the polishing rate group in the surface of the workpiece can be suppressed, high flatness can be imparted, and the polishing stability is excellent, and the present invention has been completed. It was.

Specifically, the present invention includes the following aspects.
[1] A polishing pad provided with a urethane foam sheet on the surface, and when the urethane foam sheet is subjected to a pressure exceeding 2.5 psi (17 kPa) at a temperature of 40 to 50 ° C., negative thermal expansion (positive The polishing pad exhibiting thermal shrinkage).
[2] The polishing pad according to [1], wherein the urethane foam sheet exhibits positive thermal expansion when a pressure of less than 1.0 psi (6.9 kPa) is applied at a temperature of 40 to 50 ° C.
[3] A polishing pad provided with a foamed urethane sheet on the surface, wherein the foamed urethane sheet has a strain constant of 45 to 150 μm / psi when a pressure of 1.0 to 2.5 psi is applied. pad.
[4] A method for producing a polishing pad provided with a foamed urethane sheet on the surface, the step (a) of preparing a urethane resin-containing solution by dissolving the urethane resin in a soluble organic solvent, and the urethane resin-containing solution A step (b) of coating a base material, a step (c) of immersing the base material coated with the urethane resin-containing solution in a coagulation liquid, and a foamed urethane sheet obtained by coagulation on the base material. A polishing pad comprising a step (e) of embossing, wherein the modulus of the urethane resin is 5 MPa or less in the step (a), and the coagulation liquid temperature is less than 35 ° C. in the step (c). Manufacturing method.

  Since the polishing pad of the present invention exhibits negative thermal expansion when a pressure exceeding 2.5 psi is applied, the occurrence of defects in the object to be polished can be significantly reduced. Therefore, various problems [for example, an increase in resistance due to scratches on the wiring, disconnection, damage to an interlayer insulating film such as a low-k film (low dielectric constant film)] that hinders a smooth manufacturing process can be solved. . Moreover, since the polishing pad of the present invention has a predetermined strain constant when a pressure of 1.0 to 2.5 psi is applied, it can suppress variations in the polishing rate and can impart high flatness to improve polishing stability. can do.

FIG. 1 is a cross-sectional view of a polishing pad A produced in the example. FIG. 2 is a cross-sectional view of the polishing pad B produced in the example. FIG. 3 is a graph showing the relationship between temperature and elongation when a pressure of 0.8 psi (5.5 kPa) is applied to the polishing pads A to D produced in the example. FIG. 4 is a graph showing the relationship between temperature and elongation when a pressure of 2.6 psi (18 kPa) is applied to the polishing pads A to D produced in the example.

<Polishing pad>
(1) Features of the first aspect The first aspect of the polishing pad of the present invention comprises a foamed urethane sheet (polishing layer) on the surface, and the foamed urethane sheet is 2.5 psi at a temperature of 40 to 50 ° C. When a pressure exceeding (17 kPa) is applied, negative thermal expansion is exhibited.

  The above temperature range means the polishing temperature. Since the polishing rate decreases at a low pressure, the polishing temperature is increased to increase the polishing rate. The present invention is characterized by exhibiting a desired thermal expansion at such a relatively high polishing temperature. Moreover, said pressure range means the pressure loaded locally on a foaming urethane sheet, when foreign materials, such as a polishing aggregate, generate | occur | produce. The pressure range is not particularly limited as long as it is in a range exceeding 2.5 psi, but may be, for example, more than 2.5 psi and 4 psi or less, and more than 2.5 psi and 3.5 psi or less (for example, 2 psi). .6-3 psi).

  “Thermal expansion” is a phenomenon in which the foamed urethane sheet expands due to heat, and whether the thickness of the foamed urethane sheet extends when the temperature is changed while applying a load is determined as an index. More specifically, whether the thermal expansion is positive or negative is determined by measuring the elongation at each temperature when a predetermined load is applied using a conventional measuring device such as a thermomechanical analyzer. And it can confirm with the temperature-elongation change curve created from this measurement result.

  In the present invention, the foamed urethane sheet exhibits negative thermal expansion and suppresses thermal expansion when a high pressure (pressure exceeding 2.5 psi) is applied due to the occurrence of foreign matters such as polishing aggregates at the polishing temperature. Since foreign matter can be taken into the urethane foam sheet side instead of the object to be polished, the occurrence of defects in the object to be polished can be remarkably suppressed.

  The foamed urethane sheet has a pressure of extremely low pressure [for example, less than 1.0 psi (6.9 kPa), preferably 0.1 to 0.9 psi] at a temperature of 40 to 50 ° C. in order to suppress a decrease in polishing rate. It preferably exhibits positive thermal expansion when loaded.

  The thermal expansion of the foamed urethane sheet at a temperature of 40 to 50 ° C. is a practical polishing pressure region (for example, 1.. 0 to 2.5 psi) preferably exhibits a behavior in which positive and negative are reversed. Specifically, it is preferable that positive thermal expansion is exhibited at less than 1.0 psi, positive or negative thermal expansion is exhibited at 1.0 to 2.5 psi, and negative thermal expansion is exhibited above 2.5 psi.

(2) Features of the second aspect The second aspect of the polishing pad of the present invention comprises a foamed urethane sheet (polishing layer) on the surface, and the foamed urethane sheet has a pressure of 1.0 to 2.5 psi. Has a strain constant of 45 to 150 μm / psi. The strain constant is measured at room temperature (for example, temperature 20 ° C.).

  The “strain constant” is an index of how much the thickness of the urethane foam sheet changes when a predetermined load is applied. The strain constant is the reciprocal of the slope of the tangent line based on the stress-strain curve created from the measurement result by measuring the compression amount (strain) and the compression load using a conventional measuring device, for example, a micro autograph. Can be calculated by calculating.

  The strain constant of the foamed urethane sheet is preferably 48 to 140 μm / psi, more preferably 50 to 130 μm / psi when a pressure of 1.0 to 2.5 psi is applied. When the strain constant of the foamed urethane sheet is within the above range, the frictional resistance can be within a desired range, and the polishing stability is excellent. If the strain constant is too small, polishing rate spots tend to be large in the surface of the object to be polished, and the polishing stability tends to decrease. If the strain constant is too large, the amount of deformation of the polishing pad tends to be large, the flatness of the object to be polished is deteriorated, and the polishing stability tends to decrease.

(3) Feature of the third aspect The third aspect of the polishing pad of the present invention combines the feature of the first aspect and the feature of the second aspect. More specifically, the third aspect includes a foamed urethane sheet (abrasive layer) on the surface, and the foamed urethane sheet is negative when a pressure exceeding 2.5 psi is applied at a temperature of 40 to 50 ° C. And a strain constant of 45 to 150 μm / psi when a pressure of 1.0 to 2.5 psi is applied. According to the above aspect, it is possible to achieve both suppression of defects and polishing stability. Furthermore, in the above aspect, the urethane foam sheet preferably exhibits positive thermal expansion when a pressure of less than 1.0 psi is applied at a temperature of 40 to 50 ° C.

(4) Structure common to the first to third aspects The foamed urethane sheet is not particularly limited as long as it has the above thermal expansion and / or the above strain constant, and the urethane resin constituting the foamed urethane sheet Various types can be used. Hereinafter, the polymerization component of the urethane resin, that is, the polyisocyanate compound and the polyol compound will be described.

  The polyisocyanate compound is not particularly limited as long as it has two or more isocyanate groups in the molecule. Examples of the polyisocyanate compound include aliphatic polyisocyanates [for example, tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, hexamethylene triisocyanate, undecane triisocyanate], alicyclic polyisocyanates [for example, cyclohexane diisocyanate, Isophorone diisocyanate, methylene bis (cyclohexyl isocyanate), hydrogenated xylylene diisocyanate, hydrogenated bis (isocyanatophenyl) methane, norbornane diisocyanate, trimethylisocyanatocyclohexane], aromatic polyisocyanates [eg phenylene diisocyanate, naphthylene diisocyanate, xylylene diisocyanate Isocyanate, te Lamethylxylylene diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, toluidine diisocyanate, diphenyl ether diisocyanate, bis (isocyanatophenyl) propane, triisocyanatomethylbenzene, triphenylmethane triisocyanate], derivatives thereof (eg, dimers, trimers, Biuret and allophanate) can be exemplified. These polyisocyanate compounds can be used alone or in combination of two or more. Of these polyisocyanate compounds, diisocyanate compounds are preferable, and aromatic diisocyanates such as diphenylmethane diisocyanate are particularly preferable.

  The polyol compound is not particularly limited as long as it has two or more hydroxyl groups in the molecule. Examples of the polyol compound include aliphatic polyols [for example, alkane diols such as ethylene glycol, propylene glycol, butylene glycol; alkane polyols such as glycerin, trimethylolpropane, and pentaerythritol], alicyclic polyols [for example, cyclohexane such as cyclohexanediol Alkanediols; hydrogenated bisphenols such as hydrogenated bisphenol A], aromatic polyols [eg, bisphenols such as bisphenol A; xylylene glycol], polyether polyols [eg, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc. Polyalkylene glycol], polyester polyol [for example, reaction product of ethylene glycol and adipic acid, butylene Reaction products of glycols and adipic acid, polycarbonate polyols, and polyacrylic polyol can be exemplified. These polyols can be used alone or in combination of two or more. Of these polyols, polyether polyols and polyester polyols are preferred.

  Urethane resins containing these polyisocyanate compounds and polyol compounds as polymerization components can be used alone or in combination of two or more. Of these urethane resins, polyether-based urethane resins (those using polyether polyols as polyol compounds) and polyester-based urethane resins (those using polyester polyols as polyol compounds) are preferred. Among them, polyester-based urethane resins are preferred. preferable.

  The modulus of the urethane resin constituting the foamed urethane sheet is not particularly limited, but is, for example, 5 MPa or less, preferably 1 to 4 MPa (for example, 1.5 to 3.5 MPa) from the viewpoint of reducing the defect rate. More preferably, it is 1.8 to 3.3 MPa (for example, 2 to 3 MPa). The 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% (when stretched twice the original length) by the unit area. . The modulus can be appropriately adjusted depending on the type and ratio of the polymerization component of the urethane resin. However, when the modulus is reduced, it is easy to form a foamed urethane sheet exhibiting the above thermal expansion.

  The softening temperature at which the thickness is reduced at the time of load obtained by thermomechanical analysis of the urethane resin constituting the foamed urethane sheet is not particularly limited, but is in a range exceeding 50 ° C. under a pressure of less than 1 psi (for example, 80 to 160 ° C., preferably 100 to 150 ° C., and preferably under 50 ° C. (for example, 20 to 45 ° C., preferably 25 to 40 ° C.) under a pressure exceeding 2.5 psi. If a foamed urethane sheet is used, where the softening temperature starts to compress to a low temperature under such a large load region, foreign matter such as abrasive debris is generated and soft deformation occurs when high pressure is applied. The occurrence of object defects can be reduced.

  The shape of the bubbles contained in the urethane foam sheet is not particularly limited, and may be, for example, a tear shape (for example, a shape in which the diameter gradually narrows or expands in the thickness direction). It is preferable that the shape has a shape (also referred to as a bent portion or the like) (for example, a shape in which the diameter suddenly narrows or expands at a predetermined position in the thickness direction). The neck portion may be formed at any position of the bubble, but is preferably formed near the bottom of the bubble. If the foamed urethane sheet contains bubbles with a neck part, the bubbles and the resin wall near the neck part are positively and stably deformed as if they were creased, and the cushioning against polishing load is increased. Thus, the polishing pad is easily deformed during polishing, the frictional resistance during polishing can be lowered, and the polishing stability can be improved. That is, when the bubble which has a neck part is contained, it will be easy to form the foaming urethane sheet which has said distortion constant.

  FIG. 1 is a cross-sectional view showing an example of the polishing pad of the present invention. The bubble shown to a of FIG. 1 is a bubble which has a neck part. Thus, the bubble shape is a bubble that extends (or hangs down) from the front surface (polishing surface) to the back surface (surface on the surface plate attachment side), and the side wall of the bubble is pushed into the inside of the bubble. It may be a bubble having a different shape. If it has such a shape, when the pressure (polishing pressure) is applied to the polishing pad from the polishing surface side, the bubbles may be easily crushed, or the elasticity of the polishing pad can be improved.

  An embossed recess may be formed on the surface of the urethane foam sheet. The embossed concave portions may be formed randomly, but may be formed regularly (for example, in a lattice shape, a concentric circle shape, a radial shape, or a honeycomb shape). The width of the embossed recess is, for example, 0.5 to 1.5 mm, preferably 0.8 to 1.2 mm. The average center-to-center distance between adjacent embossed recesses is, for example, 1 to 5 mm, preferably 2 to 4 mm.

The density of the urethane foam sheet [when the embossed recess is formed on the surface of the urethane foam sheet, the density of the foamed urethane sheet before the embossed recess is formed (or the portion where the embossed recess is not formed)] is usually urethane. Lower than the true density of, for example, 1.0 g / cm ³ or less (for example, 0.5 g / cm ³ or less), preferably 0.4 g / cm ³ or less (for example, 0.3 g / cm ³ or less), More preferably, it is 0.25 g / cm ³ or less (for example, 0.1 to 0.2 g / cm ³ ).

  The foamed urethane sheet is preferably soft, and the Shore A hardness of the foamed urethane sheet [when the embossed recess is formed on the surface of the foamed urethane sheet, before the embossed recess is formed (or the portion where the embossed recess is not formed). The Shore A hardness of the foamed urethane sheet) is, for example, 5 or less, preferably 4 or less, more preferably 3 or less, when measured according to JIS K7311.

  The thickness of the foamed urethane sheet (when embossed recesses are formed on the surface of the foamed urethane sheet, the thickness of the portion where the embossed recesses are not formed) is not particularly limited. However, from the viewpoint of strength and life, for example, 0.5 ~ 2mm.

  The polishing pad is not particularly limited as long as it has the above urethane foam sheet on its surface, and may contain a layer other than the urethane foam sheet. For example, the polishing pad may be a laminate in which a base material layer and a foamed urethane sheet are laminated. Examples of the base material layer include plastic films (for example, thermoplastic resin films such as acrylic resins, vinyl resins, olefin resins, styrene resins, polyester resins, polycarbonate resins, and polyamide resins), nonwoven fabrics, and the like. . The thickness of the base material layer is not particularly limited, but can be selected from a range of 0.1 to 2 mm.

<Polishing pad manufacturing method>
The polishing pad of the present invention is a wet film-forming method, for example, a step (a) of preparing a urethane resin-containing solution by dissolving a urethane resin in an organic solvent, and a step of applying the urethane resin-containing solution to a substrate (b And a step (c) of immersing the substrate coated with the urethane resin-containing solution in a coagulation liquid.

  The modulus of the urethane resin used in the step (a) is, for example, 5 MPa or less, preferably 1 to 4 MPa (for example, 1.5 to 3.5 MPa), more preferably 1.8 to 3.3 MPa (for example, 2 to 3 MPa). ). When the modulus is in the above range, it is easy to form a urethane foam sheet having a desired thermal expansion and foam structure.

  The organic solvent used in the step (a) is not particularly limited as long as it can dissolve the urethane resin and is miscible with water. Examples of the organic solvent include N, N-dimethylformamide (DMF), methyl ethyl ketone, N, N-dimethylacetamide (DMAc), tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), acetone and the like. Is mentioned. These organic solvents can be used alone or as a mixed solvent. Of these organic solvents, DMF and DMAc are preferred.

  The density | concentration of the urethane resin in a urethane resin containing solution is 10-50 mass%, for example, Preferably it is 20-40 mass%. If it is said density | concentration range, a sheet density will be adjusted to an appropriate range and a desired foam structure can be formed.

  The urethane resin-containing solution may further contain an organic solvent for viscosity adjustment, if necessary. The organic solvent for adjusting viscosity is not particularly limited as long as it can be mixed or dispersed substantially uniformly without solidifying the urethane resin in the urethane resin-containing solution. Examples of the organic solvent for adjusting viscosity include ethyl acetate and isopropyl alcohol in addition to DMF. These organic solvents can be used alone or in combination of two or more. The compounding quantity of the organic solvent for viscosity adjustment is 10-100 mass parts with respect to 100 mass parts of urethane resin containing solutions, Preferably it is 20-60 mass parts.

  The urethane resin-containing solution may further contain an additive as necessary. Although it does not restrict | limit especially as an additive, From the point which adjusts a coagulation | solidification speed | rate and forms desired foaming shape, film-forming stabilizers, such as pigments, such as carbon black, a hydrophobic active agent, and foaming, such as a hydrophilic active agent A modifier is preferred. These additives can be used alone or in combination of two or more. The compounding quantity of an additive is not restrict | limited in particular, For example, it is 30 mass parts or less with respect to 100 mass parts of urethane resin containing solutions, Preferably it is 20 mass parts or less (for example, 1-15 mass parts).

  The base material used in the step (b) may be any material having flexibility, and examples thereof include a plastic film (for example, a polyester film and a polyolefin film) and a nonwoven fabric.

  In the step (b), the method of applying the urethane resin-containing solution is not particularly limited, and examples thereof include a method of applying using a conventional coater (knife coater, reverse coater, roll coater, etc.). The coating thickness is, for example, 0.5 to 2.5 mm, preferably 1.0 to 2.0 mm, and more preferably 1.2 to 1.8 mm from the viewpoint of forming a predetermined foam structure.

  The coagulation liquid used in the step (c) contains a poor solvent (such as water) for the urethane resin as a main component. Examples of the coagulation liquid include water, a mixed solution of water and a polar solvent (for example, DMF, DMAc, THF, DMSO, NMP, acetone, and the like). In addition, the concentration of the polar solvent in the mixed solution is preferably 0.5 to 30% by mass. When a substrate coated with a urethane resin-containing solution is immersed in such a coagulating liquid, a skin layer is formed on the surface of the coating layer, and the organic solvent (and the organic solvent for adjustment) is replaced with the coagulating liquid. Bubbles are generated inside the skin layer (in the urethane resin).

  The temperature of the coagulation liquid is, for example, less than 35 ° C. (for example, 33 ° C. or less), preferably 10 to 30 ° C., more preferably 15 to 25 ° C. When a low modulus resin having a modulus of less than 10 Mpa is used and the temperature of the coagulation liquid is in the above range, a vertically long foam is easily formed. By embossing a urethane sheet containing the foam, bubbles having a neck portion are formed. Is easily formed. The time for immersing in the coagulation liquid is not particularly limited, and is, for example, 10 to 120 minutes, preferably 20 to 60 minutes.

  The form of bubbles in the foamed urethane sheet obtained by solidification on the substrate is not particularly limited, but is preferably vertically long. The length of the bubbles is, for example, 70 or more, preferably 80 or more, more preferably 85 or more (for example, 90 to 99) when the thickness of the sheet is 100. By embossing a sheet containing such vertically elongated bubbles, it is easy to form bubbles having a neck portion.

  The manufacturing method of the polishing pad of the present invention may further include a step (d) of cleaning and drying the urethane foam sheet obtained by coagulation on the substrate, if necessary, after peeling from the substrate. . By washing, the organic solvent remaining in the urethane resin is removed. Water is usually used as the cleaning liquid used for cleaning. Drying is usually performed at 80 to 150 ° C. for about 5 to 60 minutes.

  The method for producing a polishing pad of the present invention may further include a step (e) of subjecting the foamed urethane sheet obtained by coagulation on the substrate to a surface treatment after peeling from the substrate, if necessary. Examples of the surface treatment include grinding and embossing.

  The method for grinding (buffing) is not particularly limited, and examples thereof include a sandpaper method. The surface to be ground (buffed) may be either a polished surface (surface on the skin layer side) or a non-polished surface (surface on the surface plate attaching side). The grinding amount (buffing amount) is, for example, 0.05 to 0.3 mm, preferably 0.1 to 0.2 mm, depending on the desired surface shape.

  In embossing, the processing temperature and the processing pressure are not particularly limited, but the processing temperature is, for example, 100 to 200 ° C., preferably 120 to 180 ° C., and the processing pressure is, for example, 3 to 6 MPa, preferably Is 4-5 MPa. The processing time is not particularly limited, but is, for example, 30 to 300 seconds, preferably 60 to 180 seconds.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these Examples.

In the following description, “part” means “part by mass” unless otherwise specified. Each abbreviation is used in a conventional meaning. Typical abbreviations and their meanings are as follows.
MDI: Diphenylmethane diisocyanate DMF: N, N-dimethylformamide

[Preparation of polishing pad]
(Polishing pad A)
A resin solution was prepared by mixing 70 parts of DMF for viscosity adjustment with 100 parts by mass of a DMF solution of 30% by mass of a polyester MDI (diphenylmethane diisocyanate) polyurethane resin (100% modulus: 3 MPa). Using the obtained resin solution, immersing a film-forming substrate formed with a coating thickness of 1.60 mm when applying the resin solution on the substrate in a coagulating liquid (water) at a temperature of 20 ° C. for 30 minutes. Thus, a foamed urethane sheet was produced on the film forming substrate. The surface of the foamed urethane sheet obtained by peeling off the film-forming substrate was buffed on the skin layer side with a buffing amount of 0.15 mm using a sandpaper of buff count # 180, and then the thickness of the supporting substrate was 188 μm. The substrate made of polyethylene terephthalate was affixed, and the groove of the lattice pattern with a rectangular cross section with a groove width of 1 mm and a groove interval of 3 mm was embossed (processing pressure 4.5 MPa, processing (mold) temperature 145 ° C., The processing time was 120 seconds). A polishing pad A was manufactured by bonding a double-sided tape for fixing to a polishing surface plate to a surface not embossed.

(Polishing pad B)
A resin solution was prepared by mixing 43 parts of DMF for viscosity adjustment with 100 parts by mass of a DMF solution of 30% by mass of polyester MDI (diphenylmethane diisocyanate) polyurethane resin (100% modulus: 3.5 MPa). Using the obtained resin solution, immersing a film-forming substrate formed with a coating thickness of 1.30 mm when applying the resin solution on the substrate in a coagulating liquid (water) at a temperature of 35 ° C. for 30 minutes. Thus, a foamed urethane sheet was produced on the film forming substrate. The skin layer side of the foamed urethane sheet obtained by peeling the film-forming substrate was buffed with a buffing amount of 0.12 mm and buffing using a sandpaper with a buff count of # 180, and then a thickness of 188 μm as a supporting substrate. The substrate made of polyethylene terephthalate was affixed, and the groove of the lattice pattern with a rectangular cross section with a groove width of 1 mm and a groove interval of 3 mm was embossed (processing pressure 4.5 MPa, processing (mold) temperature 145 ° C., The processing time was 120 seconds). A polishing pad B was manufactured by attaching a double-sided tape for fixing to a polishing surface plate to a surface not embossed.

(Polishing pad C)
30 parts by mass of polyester MDI (diphenylmethane diisocyanate) polyurethane resin (100% modulus: 6.0 MPa) in 100 parts by mass of DMF solution, 4.6 parts of hydrophilic additive, 2 parts of hydrophobic active agent, carbon A resin solution was prepared by mixing 47 parts of DMF for viscosity adjustment containing 7.5% by mass of black. Using the obtained resin solution, immersing a film-forming substrate formed with a coating thickness of 1.60 mm when applying the resin solution on the substrate in a coagulating liquid (water) at a temperature of 20 ° C. for 75 minutes. Thus, a foamed urethane sheet was produced on the film forming substrate. The surface of the foamed urethane sheet obtained by peeling the film-forming substrate was buffed using a sandpaper of buff count # 180 with a buff treatment amount of 0.10 mm, and then a thickness of 188 μm as a support substrate. The substrate made of polyethylene terephthalate was affixed, and the groove of the lattice pattern with a rectangular cross section with a groove width of 1 mm and a groove interval of 3 mm was embossed (processing pressure 4.5 MPa, processing (mold) temperature 145 ° C., The processing time was 120 seconds). A polishing pad C was manufactured by bonding a double-sided tape for fixing to a polishing surface plate to a surface not embossed.

(Polishing pad D)
A resin solution was prepared by mixing 55 parts of DMF for viscosity adjustment with 100 parts by mass of DMF solution of 30% by mass of polyester MDI (diphenylmethane diisocyanate) polyurethane resin (100% modulus: 5.4 MPa). Using the obtained resin solution, immersing a film-forming substrate formed with a coating thickness of 1.50 mm when applying the resin solution to the substrate in a coagulating liquid (water) at a temperature of 35 ° C. for 30 minutes. Thus, a foamed urethane sheet was produced on the film forming substrate. The skin layer side of the foamed urethane sheet obtained by peeling the film-forming substrate was buffed with a buffing amount of 0.12 mm and buffing using a sandpaper with a buff count of # 180, and then a thickness of 188 μm as a supporting substrate. The substrate made of polyethylene terephthalate was affixed, and the groove of the lattice pattern with a rectangular cross section with a groove width of 1 mm and a groove interval of 3 mm was embossed (processing pressure 4.5 MPa, processing (mold) temperature 145 ° C., The processing time was 120 seconds). A polishing pad D was manufactured by attaching a double-sided tape for fixing to a polishing surface plate to a surface not embossed.

[Section observation]
When the cross sections of the polishing pads A to D were observed using a microscope, bubbles having a neck portion (bubbles as shown in FIG. 1a) were observed in the polishing pads A and C. However, the polishing pads B and D No bubble having a neck portion was observed.

[Measurement of density and Shore A hardness]
The density and Shore A hardness of the urethane foam sheet cut out from the polishing pads A to D before embossing were measured by the following methods.
(density)
For the density, a foamed urethane sheet sample piece (10 cm × 10 cm) was cut out from the polishing pad, and the mass of the sample piece was measured with an automatic balance.
Density (g / cm ³ ) = mass (g) / (10 (cm) × 10 (cm) × sample piece thickness (cm))
It calculated and calculated | required by.
(Shore A hardness)
The Shore A hardness was obtained by cutting out a foamed urethane sheet sample piece (10 cm × 10 cm) from a polishing pad and stacking a plurality of the sample pieces to a thickness of 4.5 mm or more. Measured according to JIS K7311).
The measurement results of the density and Shore A hardness of the urethane foam sheet cut out from the polishing pads A to D before embossing are shown in Table 1 below.

[Measurement of thermal expansion and defect properties]
The thermal expansion and defect properties of the polishing pads A to D were measured by the following method.
(Thermal expansion)
Polishing pads A to D were measured using a thermomechanical analyzer “RSAIII” manufactured by T.A. Instrument Japan, 8 mm wide × 12 mm long (the polishing pads A to D have embossing, (Corresponding to the size of 6 convex portions), and a 30 g (0.8 psi pressure) compression load is applied to the embossed surface, and the temperature rise rate is 5 ° C./min. The temperature-elongation change curve is drawn, and in this curve, the thermal expansion in the temperature region corresponding to the polishing temperature in the range of 40 to 50 ° C. is measured, and either negative (shrinkage) or positive (expansion) I checked if there was. The same measurement was performed using a newly cut sample piece with the load changed to 100 g (2.6 psi as the pressure). Note that the number of the convex portions and the area of the sample piece may be adjusted according to the emboss size and shape, and in this measurement, the convex portion is completely included, not the sample piece partially including the convex portion. Sample pieces were used.
(Defect)
Defects were evaluated using polishing pads A to D. In the defect evaluation, 25 silicon wafers with TEOS were polished (the same processing conditions as the polishing stability), and the unpatterned wafer surface inspection device (KLA Tencor) was applied to the 25th silicon wafer after polishing. Defects were measured in a high-sensitivity measurement mode (Surfscan SP1DLS, manufactured by the company), and defects on the substrate surface were evaluated. At the time of measurement, measurement was performed under two conditions: Wide, which is a mode capable of detecting defects of 0.16 μm or more, and Narrow, 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.
The evaluation results of the thermal expansion and defect property of the polishing pads A to D are shown in Table 2 below.

  As is apparent from the results in Table 2, the polishing pad A had the least number of defects because it exhibited negative thermal expansion when a pressure of 2.6 psi was applied. On the other hand, since the polishing pads B to D exhibited positive thermal expansion when a pressure of 2.6 psi was applied, many defects occurred.

[Measurement of strain constant and polishing stability]
The strain constants and polishing stability of the polishing pads A to D were measured by the following methods.
(Strain constant)
A polishing pad piece was cut into 8 mm × 12 mm (corresponding to the size of the polishing pads A to D having embossed and 6 convex portions after embossing), and used as a strain constant measurement sample. Microautograph (Shimadzu Corporation) The amount of compression and the load were measured using a circular pressure plate (indenter) having a temperature of 20 ° C., a compression speed of 0.1 mm / min, and a diameter of 20 mm, using MST-1). Specifically, a stress-strain curve (polynomial approximation curve) with a compression load on the Y axis and a stroke length on the X axis is created, and tangent lines are drawn at 1.0, 1.5, 2.0, and 2.5 psi, The strain constant was determined from the reciprocal of the slope.
(Polishing stability)
Polishing pads A to D were attached to a surface plate of a polishing machine (“F-REX300” manufactured by Ebara Corporation). As a low-k material, a wafer on which a SiOC layer having a thickness of 800 nm was formed by CVD was used, and the processing pressure was 2.5 psi, the platen rotation speed / polishing head rotation speed was 70/71 rpm, slurry [Cabot Corporation, SS- 25 (KOH, pH 11, Silica 12.5 wt%)] was diluted 1: 2 with pure water, flowed at a flow rate of 200 mL / min, and polished with a 3M dresser for 60 seconds under the conditions of the polishing time. Polishing 25 silicon wafers with TEOS according to the thickness measurement result before and after the polishing process on the insulating film of the substrate before and after the polishing process, the polishing stability (the standard deviation ÷ the average) Value) (%) was calculated, and the case where the polishing stability was within 10% was evaluated as ◯, and the case where the polishing stability exceeded 10% was evaluated as x.
Table 3 below shows the evaluation results of the strain constants and polishing stability of the polishing pads A to D.

  As is apparent from the results in Table 3, the polishing pads A and C have a high polishing stability because they have a large strain constant when a pressure of 1.0 to 2.5 psi is applied. On the other hand, since the polishing pads B and D have a small strain constant when the same pressure is applied, the polishing stability is low.

  The polishing pad of the present invention can remarkably reduce the occurrence of defects of an object to be polished and / or improve the polishing stability in polishing at a low pressure. Therefore, the polishing pad of the present invention polishes various objects to be polished such as a wiring layer (such as a wiring layer wired at a wiring interval of 45 nm or less), an interlayer insulating film (such as a low-k film), etc. It can be suitably used for finishing polishing.

Claims (3)

A polishing pad provided with a foamed urethane sheet on the surface , formed by a wet film formation method ,
The urethane foam sheet, when the temperature was raised at 5 ° C. / minute heating rate in a state loaded with a pressure of 2.6 psi (18 kPa), a negative thermal expansion at a temperature 40 to 50 ° C., the polishing pad. Urethane foam sheet, when the temperature was raised at 5 ° C. / minute heating rate in a state loaded with a pressure of 0.8 psi (5.5 kPa), a positive thermal expansion at a temperature 40 to 50 ° C., wherein Item 10. A polishing pad according to Item 1. A method for producing a polishing pad according to claim 1 or 2 ,
The step (a) of preparing a urethane resin-containing solution by dissolving the urethane resin in a soluble organic solvent, the step (b) of applying the urethane resin-containing solution to a substrate, and the urethane resin-containing solution are applied. A step (c) of immersing the prepared substrate in a coagulation liquid, and a step (e) of embossing a foamed urethane sheet obtained by coagulation on the substrate,
In the step (a), the modulus of the urethane resin is 5 MPa or less,
The manufacturing method of the said polishing pad whose coagulating liquid temperature is less than 35 degreeC in the said process (c).