JP2008207308A - Mutual invasion polymer mesh structural body, polishing pad, and manufacturing method for the mutual invasion polymer mesh structural body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a mutual invasion polymer mesh structural body having a surface for preventing a solute component and suspended matter from adhering and being deposited onto it, to provide a polishing pad achieving a high polishing rate, preventing occurrence of dishing, and extending the service life of the pad when polishing, and also to provide a manufacturing method for the same. <P>SOLUTION: This mutual invasion polymer mesh structural body contains a polymer of acrylic ester or ester methacrylate prepared from an alicyclic compound having a hydroxyl group composed of 6 carbons or more. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an interpenetrating polymer network structure, a polishing pad, and a method for producing an interpenetrating polymer network structure. In particular, the present invention relates to a polishing pad for polishing and flattening an interlayer insulating film and a metal film for forming a metal wiring formed on a semiconductor substrate such as silicon.

  A polishing pad made of a polymer polymerized from polyurethane and a vinyl compound is disclosed in Patent Document 1. Further, Patent Document 2 discloses a method for producing a polishing pad including a step of causing a polymerization reaction of a monomer after immersing a polymer molded body in a solution containing a monomer for polymerization. However, in these polishing pads, a metal thin film such as copper is polished to form fine wiring, and in the wiring-insulator flattening step, the central portion of the metal wiring is thinner than the edge, so-called “Dishing” is noticeable. The larger the dishing, the smaller the cross-sectional area of the wiring, which is not preferable because the electrical resistance of the metal wiring increases. Moreover, it is not preferable because it causes a polishing residue when an upper wiring layer is formed.

  On the other hand, Patent Document 3 discloses a polishing pad made of a thermoplastic resin having a glass transition temperature of 270K to 400K as a polishing pad that has high polishing rate stability, excellent flatness and step characteristics, and can reduce the occurrence of scratches. It is disclosed. Further, Patent Document 4 discloses a polishing pad made of a thermosetting resin containing dicyclopentadiene as a main component as a polishing pad that is less likely to be clogged and less likely to cause polishing defects such as scratches. However, these polishing pads have a relatively high glass transition temperature and heat distortion temperature, but do not have a surface on which elution components and suspended substances in the slurry are difficult to adhere and deposit, and their polishing characteristics are insufficient. Met. In particular, when polishing a metal film using a slurry having a strong chemical action, there is a problem that the polishing pad is not sufficiently rigid, so that thermal deformation is large and dishing is large.

Further, improvement of the polishing rate and extension of the pad life are strongly desired from the viewpoint of productivity improvement and cost reduction.
International Publication No. 00/122621 Pamphlet JP 2000-218551 A JP 2003-224094 A JP 2003-163190 A

  An object of the present invention is to provide an interpenetrating network structure having a surface on which solute components and suspended substances are difficult to adhere and deposit, and a method for manufacturing the same. It is another object of the present invention to provide a polishing pad having a high polishing rate, reduced dishing, and extended pad life.

In order to solve the above-mentioned problems, the present invention has the following constitutions: (1) It includes an acrylic ester or methacrylic ester polymer obtained from an alicyclic compound having 6 or more carbon atoms having a hydroxyl group. Interpenetrating polymer network structure.

  (2) The weight ratio of the polymer of acrylic acid ester or methacrylic acid ester obtained from an alicyclic compound having 6 or more carbon atoms having a hydroxyl group to other components is 5/100 to 300/100 ( The interpenetrating polymer network structure according to 1).

  (3) A polishing pad comprising the interpenetrating polymer network structure according to either (1) or (2).

  (4) The polishing pad according to (3), comprising polyurethane.

  (5) The polishing pad according to any one of (3) and (4), comprising a polishing layer having a tensile elastic modulus at 60 ° C. of 100 MPa or more.

  (6) The polishing pad according to any one of (3) to (5), which has closed cells having an average cell diameter of 10 to 200 μm.

(7) The polishing pad according to any one of (3) to (6), wherein the density of the polishing pad is 0.2 to 1.1 g / cm ³ .

  (8) The polishing pad according to any one of (3) to (7), wherein the polishing pad is used for polishing a semiconductor substrate.

  (9) A step of immersing the polymer molded article in a radical polymerizable composition containing an acrylic ester or methacrylic ester obtained from an alicyclic compound having 6 or more carbon atoms having a hydroxyl group and a radical polymerization initiator, radical polymerization A method for producing an interpenetrating polymer network structure, comprising a step of polymerizing a radically polymerizable compound in a swollen state of a polymer molded body impregnated with a functional composition.

  (10) The method for producing an interpenetrating polymer network according to (9), wherein the radical polymerizable composition contains substantially no organic solvent.

  (11) The method for producing a polishing pad according to any one of (9) and (10), wherein the polymer molded body contains polyurethane as a main component.

  An interpenetrating polymer network having a surface on which solute components and suspended matters in the slurry are difficult to adhere and deposit can be obtained. In addition, a polishing pad with a high polishing rate, less dishing, and an extended pad life can be obtained.

  In the present invention, the interpenetrating polymer network structure refers to a polymer in which independent different types of polymer networks enter each other without chemically bonding to each other in the polymer mixed system. Specifically, a structure in which a plurality of types of polymers are dispersed at several nm to several hundred nm is formed. The degree of dispersion is preferably 5 nm to 300 nm, and particularly preferably 5 nm to 100 nm. Further, a structure in which different polymers are in a continuous phase with each other may be stabilized by cross-linking point formation.

  The interpenetrating polymer network structure forms an interpenetrating polymer network structure from a manufacturing method in which a polymer molding is immersed in a radically polymerizable composition and the ethylenically unsaturated compound in the radically polymerizable composition is polymerized. can do. The polishing pad of the present invention comprises an interpenetrating polymer network structure.

  The interpenetrating polymer network structure of the present invention includes an acrylic acid ester or methacrylic acid ester polymer obtained from an alicyclic compound having a hydroxyl group and having 6 or more carbon atoms. The inventors have found that a desired effect can be obtained by using such an interpenetrating polymer network structure.

  In the present invention, an interpenetrating polymer network structure containing a polymer obtained from an acrylate ester or methacrylate ester obtained from an alicyclic compound having 6 or more carbon atoms having a hydroxyl group adheres a solute component or suspended matter. The reason why it is difficult to deposit, excellent rigidity, and difficult to thermally deform is not necessarily clear, but it is presumed that the high-order polymer structure of the interpenetrating polymer network structure suppresses the adhesion and deposition of solute components and suspended solids. Is done. As a result, the polishing pad using this interpenetrating polymer network structure prevents the solute component and suspended matter in the slurry from adhering to and accumulating on the pad surface during polishing, so that the pad surface is always stable. It seems that the surface is formed, and it is difficult for the polishing rate to decrease and the life to be shortened.

  In particular, the interpenetrating polymer network formed from a polymer of an acrylate ester or methacrylate ester obtained from an alicyclic compound having 6 or more carbon atoms having a hydroxyl group and other polymer components has an affinity for it. Submicron level compatibility can be obtained from the height and good dispersibility. Strong hydrophobicity and high glass transition temperature of acrylic acid ester or methacrylic acid ester polymer obtained from an alicyclic compound having 6 or more carbon atoms having a hydroxyl group, results in good affinity and dispersibility Reflected in the characteristics of the interpenetrating polymer network structure, it is presumed that the solute component and the suspended matter are less likely to adhere and deposit, have excellent rigidity, and are difficult to be thermally deformed.

  The interpenetrating polymer network structure of the present invention has a weight ratio of an acrylic acid ester or methacrylic acid ester polymer obtained from an alicyclic compound having 6 or more carbon atoms having a hydroxyl group to other components. It is preferable that it is 100-300 / 100. When the weight ratio is smaller than 5/100, the proportion of the polymer of acrylic ester or methacrylic ester obtained from the alicyclic compound having 6 or more carbon atoms is too small, and the alicyclic having 6 or more carbon atoms. The effect using the polymer of acrylic ester or methacrylic ester obtained from the formula compound may not be sufficiently obtained. On the other hand, when the weight ratio is larger than 300/100, the compatibility between different polymers may be lowered, which is not preferable. More preferably, the weight ratio of the polymer of acrylic acid ester or methacrylic acid ester obtained from an alicyclic compound having 6 or more carbon atoms and other components is 50/100 to 200/100.

  The acrylic acid ester or methacrylic acid ester obtained from the alicyclic compound having 6 or more carbon atoms having a hydroxyl group in the present invention is an acrylate ester or methacrylic acid ester and having 6 or more carbon atoms having a hydroxyl group. An acrylic acid ester or a methacrylic acid ester that can be synthesized by reacting a formula compound with acrylic acid or an alicyclic compound having 6 or more carbon atoms having a hydroxyl group and methacrylic acid. Specifically, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentanyl acrylate, dicyclopentanyl methacrylate, dicyclopentanyloxyethyl acrylate, dicyclopentanyloxyethyl methacrylate, Examples thereof include, but are not limited to, cyclopentenyl acrylate and dicyclopentenyl methacrylate.

  The acrylic acid ester or methacrylic acid ester polymer obtained from an alicyclic compound having 6 or more carbon atoms having a hydroxyl group in the present invention is an acrylic acid ester or acrylate compound obtained from an alicyclic compound having 6 or more carbon atoms having a hydroxyl group. Even if it consists only of methacrylic acid ester, it may be a copolymer or blend with other compounds. Acrylic ester or methacrylic acid ester obtained from an alicyclic compound having 6 or more carbon atoms having a hydroxyl group may be an acrylic ester or methacrylic acid ester obtained from a plurality of different alicyclic compounds having 6 or more carbon atoms having hydroxyl groups. An acid ester or a methacrylic acid ester may be used.

  The ethylenically unsaturated compound in the present invention refers to a compound having a radical polymerizable carbon-carbon double bond. Specifically, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate, 2-hydroxyethyl methacrylate 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, methacrylic acid, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, benzyl methacrylate, 2-phenoxyethyl methacrylate, polyethylene glycol monomethacrylate, polypropylene glycol mono Methacrylic acid ester such as tacrylate, isoamyl acrylate, lauryl acrylate, stearyl acrylate, phenoxyethyl acrylate, tetrahydrofurfuryl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, acrylic acid ester, acrylonitrile, methacrylonitrile, Monofunctional ethylenically unsaturated compounds such as styrene, α-methylstyrene, hydroxystyrene, α-methylstyrene dimer, vinylpyridine, ethyleneimine, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, neopentyl glycol diacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate 2-butyl-2-ethyl-1,3-propanediol diacrylate, 1,9-nonane diacrylate, dimethylol tricyclodecane diacrylate, trimethylol propane triacrylate, pentaerythritol tetraacrylate, etc. And polyfunctional ethylenically unsaturated compounds having two or more polymerizable unsaturated bonds.

  The radical polymerization initiator in the present invention refers to a compound that decomposes by heating, light irradiation, radiation irradiation or the like to generate radicals. Examples of such radical polymerization initiators include azo compounds and peroxides. Specifically, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 4, Azo such as 4′-azobis (4-cyanovaleric acid), 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), etc. Polymerization initiator, cumene hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, di-t-butyl peroxide, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobuty Rate, t-butyl peroxybivalate, t-butyl peroxybenzoate, t-butyl peroxyacetate, diisopropyl peroxydicarbonate , It may be mentioned di -s- butyl peroxydicarbonate, benzoyl peroxide, acetyl peroxide, lauroyl peroxide, a peroxide polymerization initiator such as. The amount of radical polymerization initiator added is preferably 0.01 to 5% by weight, more preferably 0.05 to 3% by weight, based on the ethylenically unsaturated compound.

  The organic solvent of the present invention refers to a compound that does not substantially react during the polymerization of the ethylenically unsaturated compound and is liquid at room temperature. Specific examples include hexane, dimethylformamide, dimethyl sulfoxide, ethanol and methanol. “Substantially free of organic solvent” means that the organic solvent is less than 1% by weight based on the ethylenically unsaturated compound. Carbon tetrachloride, toluene, ethylbenzene, etc. are usually known as organic solvents, but in the radical polymerization process, the growing radicals extract hydrogen and chlorine to become stable polymers, and the newly generated radicals become ethylenically unsaturated compounds. Since the effect as a chain transfer agent that the polymerization proceeds by addition to is known, these compounds do not hit an organic solvent that does not substantially react with the ethylenically unsaturated compound mentioned here.

  The radical polymerizable composition of the present invention refers to a composition comprising the ethylenically unsaturated compound, the radical polymerization initiator, and the chain transfer agent. A radical polymerization inhibitor, an antioxidant, an anti-aging agent, a filler, a colorant, an antifungal agent, an antibacterial agent, a flame retardant, and an ultraviolet absorber may be added to the radical polymerizable composition. The amount of these compounds added is preferably within a range not exceeding 3% by weight based on the ethylenically unsaturated compound.

  The radically polymerizable composition is preferably a composition that does not substantially contain an organic solvent from the viewpoint of economy that an organic solvent removing step is not required.

  Examples of the radical polymerization inhibitor that can be added to the radical polymerizable composition and are solid at room temperature include hydroquinone, hydroquinone monomethyl ether, topanol A, catechol, t-butylcatechol, 2,6-di-t-butyl-4-methylphenol. Phenothiazine, diphenylamine, N, N′-diphenyl-p-phenylenediamine, p-phenylenediamine, and the like. One or two or more compounds selected from these compounds can be used. The radical polymerization inhibitor may be used by being added to the radical polymerizable composition. Moreover, you may add beforehand at the time of polymer molded object manufacture. Furthermore, you may make it contain in both a radically polymerizable composition and a polymer molded object. When a radical polymerization inhibitor is used for both the radical polymerizable composition and the polymer molded article, the type of radical polymerization inhibitor may be the same compound or different. In addition, for the purpose of enhancing the polymerization inhibition effect, it is preferable to perform impregnation and / or polymerization in the presence of oxygen gas or oxygen-containing gas.

  As radical polymerization inhibitors that are preferably impregnated and / or polymerized in the presence of oxygen gas or oxygen-containing gas, phenothiazine, hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, phenyl-β-naphthylamine, p-phenylenediamine, topanol A etc. can be mentioned. As the oxygen-containing gas, air, oxygen, or a gas obtained by diluting oxygen with an inert gas is used. Examples of the inert gas include nitrogen, helium, and argon. The oxygen concentration when diluted is not particularly limited, but is preferably 1% by volume or more. As the oxygen-containing gas to be used, dry air and gas obtained by diluting dry air with nitrogen are preferable because they are inexpensive.

  The chain transfer agent that can be added to the radically polymerizable composition refers to a compound that reacts with a growing radical to stop an increase in the polymer chain length and generate a low-molecular radical capable of reinitiating.

  The chain transfer agent is a first alkyl group or substituted alkyl group such as n-butyl mercaptan, isobutyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, sec-butyl mercaptan, sec-dodecyl mercaptan, t-butyl mercaptan. Aromatic mercaptans such as secondary, tertiary or tertiary mercaptan, phenyl mercaptan, thiocresol, 4-t-butyl-o-thiocresol, thioglycolic acid esters such as 2-ethylhexyl thioglycolate and ethyl thioglycolate And C3-C18 mercaptan such as ethylenethioglycol, α-methylstyrene dimer, carbon tetrachloride, toluene, ethylbenzene, triethylamine, and the like. These may be used alone or in combination of two or more. Of these, alkyl mercaptans such as t-butyl mercaptan, n-butyl mercaptan, n-octyl mercaptan, and n-dodecyl mercaptan, and α-methylstyrene dimer are preferably used.

  The amount of chain transfer agent used is preferably 0.01 to 5% by weight, more preferably 0.05 to 3% by weight, based on the ethylenically unsaturated compound. When the amount used is less than 0.01% by weight, the effect of the chain transfer agent is not exhibited. On the other hand, when the content is more than 5% by weight, mechanical properties such as strength and elastic modulus are deteriorated.

  The polymer molded body of the present invention refers to a polymer substance that is solid at room temperature. The molded body may be solid, hollow or foamed. The characteristics are not particularly limited, but it is necessary that the composition can be taken into the molded body and impregnated by being immersed in the radical polymerizable composition. Therefore, it is necessary to be made of a material having an affinity for the radical polymerizable composition, and to be flexible enough to take in the radical polymerizable composition and swell the polymer molded body itself.

  The polymer molded body has a high chemical structure that includes a polyethylene glycol chain, a polypropylene glycol chain, a polytetramethylene glycol chain, a poly (oxyethylene / oxypropylene) chain, etc. as a chemical structure that is flexible and can be swollen by a radically polymerizable composition. Molecular shaped bodies are preferred. Specific examples include polyester and polyurethane. Although depending on the density and the amount of impregnation of the radical polymerizable composition, the volume of the polymer molded body after impregnation swells to about 1.03 to 5 times the original volume, and most of the volume is about 1.03 to 3 Swells about twice.

  The polymer molded body is preferably a foam containing closed cells having an average cell diameter of 10 to 200 μm, more preferably a foam containing closed cells of 20 to 150 μm, and 30 to 120 μm. Particularly preferred is a foam containing the closed cells. The average bubble diameter can be obtained by forming the surface or sliced surface of the polishing pad into a scanning electron microscope (SEM) image at a magnification of 200 times and subjecting the average bubble diameter to image processing.

Moreover, as an apparent density of a polymer molded object, 0.1-1.2 g / cm < ³ > is preferable and 0.5-1.0 g / cm < ³ > is more preferable. The apparent density can be measured by the method described in Japanese Industrial Standard JIS K 7112. Furthermore, the radically polymerizable composition taken into the polymer molded body does not enter into the bubbles in the polymer molded body, and the polymer is polymerized after the ethylenically unsaturated compound is polymerized under the swelling state of the polymer molded body. It is preferable that the air bubbles in the molded body remain as air bubbles. The density of the obtained polishing pad as a result of which, preferably 0.2~1.1g / cm ^3, more preferably 0.6~1.1g / cm ^3.

  The polymer molded body of the present invention is preferably a polyurethane molded body obtained from a polyol and a polyisocyanate, and particularly preferably a polyurethane molded body obtained by mixing two liquids of a polyol and a polyisocyanate. Here, the polyol refers to a compound having two or more hydroxyl groups. Examples thereof include one or a mixture of two or more selected from polyether polyol, polyester polyol, polycarbonate polyol, polycaprolactone polyol, ethylene glycol, propylene glycol, glycerin and the like.

  Polyisocyanates include aromatic isocyanates such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymeric MDI, and naphthalene diisocyanate, aliphatic diisocyanates such as tetramethylene diisocyanate and hexamethylene diisocyanate, isophorone diisocyanate, hydrogen Examples thereof include alicyclic diisocyanates such as added TDI and hydrogenated MDI. It can be used as a mixture of one or more selected from these isocyanates.

  In preparation of the polymer molded body, in addition to polyol and polyisocyanate, crosslinking agent, chain extender, foam stabilizer, foaming agent, resination catalyst, foaming catalyst, antioxidant, anti-aging agent, filler, It may contain a plasticizer, a colorant, an antifungal agent, an antibacterial agent, a flame retardant, and an ultraviolet absorber, and may be molded. Although the preparation method of a polymer molded object is not specifically limited, It can prepare by methods, such as injection molding and reaction molding. In particular, in the preparation of a polyurethane molded body, a high-pressure injection machine that instantaneously mixes raw materials by colliding each other in the mixing head, and a so-called low-pressure injection machine that mechanically mixes each raw material supplied to the mixing head with a stirring blade or the like. It is preferable to use it and apply it to molding or slab molding.

  The weight ratio between the polymer molded body and the polymer polymerized from the impregnated ethylenically unsaturated compound is preferably 100/5 to 100/300, more preferably 100/50 to 100/200. When the content weight ratio of the polymer polymerized from the polymerized polymer impregnated with the polymer molded product is smaller than 100/5, the characteristics are not so different from those of the polymer molded product alone, and the polymer is impregnated and polymerized. The benefits may be small. On the other hand, when the weight ratio of the polymer polymerized from the polymer molded body and the polymer polymerized from the impregnated ethylenically unsaturated compound is larger than 100/300, it may not be preferable because the time required for impregnation becomes too long. The step of immersing the polymer molded article in the radical polymerizable composition is preferably 3 hours to 20 days at a temperature of 15 to 60 ° C., more preferably 3 hours to 10 days.

  The polishing pad of the present invention preferably has a tensile elastic modulus at 60 ° C. of 70 MPa or more, and more preferably 100 MPa or more. More preferably, it is 120 MPa or more. It is usually difficult for the tensile modulus at 60 ° C. to exceed 1000 MPa, and scratches may increase when it exceeds 500 MPa.

The polishing pad of the present invention preferably has 10 to 200 μm closed cells, more preferably a foam containing 20 to 150 μm closed cells, and a foam containing 30 to 120 μm closed cells. It is particularly preferred. The average bubble diameter is obtained by imaging the surface of the polishing pad or the sliced surface with an image of a scanning electron microscope (SEM) at a magnification of 200 and processing the average bubble diameter. It is preferable that the surface of the polishing pad has a flat surface and openings derived from bubbles at an appropriate ratio. Cell count at any slice plane is preferably 20 to 1000 pieces / mm ^2, and more preferably 200 to 600 pieces / mm ^2. The density of the polishing pad is preferably 0.2 to 1.1 g / cm ³ . The density can be measured by the method described in Japanese Industrial Standard JIS K7112.

  The polishing pad of the present invention can be used for polishing semiconductor substrates such as silicon wafers, optical members such as lenses, electronic materials such as magnetic heads and hard disks. In particular, it can be used as a polishing pad for polishing a semiconductor wafer, which is an object to be polished, for the purpose of planarizing the semiconductor wafer by a chemical mechanical polishing (CMP) technique. In the CMP process, a polishing pad made up of a polishing agent and a chemical solution is used to polish the semiconductor wafer surface by moving the semiconductor wafer and the polishing pad relative to each other, thereby making the semiconductor wafer surface flat and smooth. Is used.

  The polishing pad of the present invention can be used for polishing optical members such as optical lenses, optical prisms, optical filters, and optical waveguides. Examples of the material of the optical member to be polished include glass, quartz, crystal, sapphire, transparent resin, lithium tantalate, and lithium niobate.

  In other applications, it can be used for polishing gallium arsenide, gallium phosphide, indium phosphide, ferrite, alumina, silicon carbide, silicon nitride, ceramics, alloys, resins, and the like.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, these do not limit this invention. The evaluation method was performed as follows.
[Slurry immersion evaluation] A prepared slurry was prepared by adding and mixing 3 mL of 30 wt% hydrogen peroxide water to 1000 mL of polishing slurry for copper (iCue5003 manufactured by Cabot Corporation). In this prepared slurry, a polyurethane molded body-impregnated cured product sheet of 30 mm × 30 mm × about 1.5 mm thickness was immersed and allowed to stand at 25 ° C. for 4 weeks. On the way, the immersion liquid was replaced with a prepared slurry that was newly prepared every week. After 4 weeks, the sheet was taken out, rinsed with pure water, further ultrasonically cleaned in pure water for 5 minutes, vacuum dried, and then observed for adhesion and deposit on the sheet surface with a scanning electron microscope (SEM). .
[Average bubble diameter] The surface or sliced surface of the polishing pad was observed at a magnification of 200 times with a scanning electron microscope “SEM2400” (Hitachi), and the image was analyzed with an image processing apparatus. The bubble diameter was measured, and the average value was taken as the average bubble diameter.
[Density] Measured using a pycnometer (Harvard type) according to the method described in JIS K7112.
[Tensile Test] Using a tensile tester RTM-100 (manufactured by Orientec Co., Ltd.), the breaking strength, breaking elongation, and tensile modulus were measured under the following measurement conditions. The average value of the five test pieces was taken as the measured value.
Test temperature: 60 ° C
Test piece shape: No. 1 type small test piece Test piece thickness: 1-2 mm
Distance between chucks: 58mm
Test speed: 50 mm / min [polishing evaluation]
A double-sided adhesive tape was bonded to the polishing layer sheet to produce a single-layer polishing pad. A single layer polishing pad was affixed on the surface plate of the polishing apparatus, and the diamond conditioner was pressed against the polishing surface plate at a pressure of 0.8 psi, a polishing surface plate rotation speed of 30 rpm, and a conditioner rotation speed of 28 rpm. The polishing pad was conditioned for 30 minutes while supplying purified water onto the polishing pad at a rate of 100 mL / min.

An 8-inch wafer for evaluation is mounted on a polishing head of a polishing apparatus, rotated at 33 rpm, a single-layer polishing pad is fixed to a platen of a polishing machine, and rotated at 30 rpm in the same direction as the polishing head. A polishing slurry for copper (iCue 5003 manufactured by Cabot Corporation) was supplied at 220 mL / min, and polishing was performed at a polishing pressure of 4 psi for 1 minute to measure the polishing rate of the copper film. The polishing rates of the 50th and 400th copper films were measured. After measuring the polishing rate of the 50th wafer, the wafer with a pattern for dishing evaluation was polished, and the dishing amount was measured. The polishing was completed by detecting an optical end point signal. Subsequently, the copper solid film was polished, and the number of particles was measured.
[Polishing Rate] The amount of polishing (polishing rate) per unit time was calculated by measuring the wafers before and after polishing with a resistivity meter VR-120S (manufactured by Kokusai Denki Alpha Co., Ltd.). A copper film having a thickness of 10,000 angstroms formed on an 8-inch silicon wafer was used.
[Number of Particles] The number of particles on the wafer without pattern was evaluated using a defect / foreign particle inspection apparatus (SP-1 manufactured by KLA-Tencor Corporation). The total number of particles of 0.2 μm or more was measured.
[Dishing Amount] Polishing was performed using a patterned wafer having copper wiring (wiring width 10 μm) isolated in the oxide film, and evaluation was performed using a surface measurement profiler (P-15 manufactured by KLA Tencor).

(Comparative Example 1)
The raw material composition is charged into the first raw material tank and the second raw material tank of the RIM molding machine as shown below, and after loading nitrogen gas into the first raw material tank, the raw material composition is injected from both tanks into a mold and cured. Thus, a polyurethane molded body having a size of 600 mm × 600 mm and a thickness of 20 mm was obtained. The apparent density of the polyurethane was 0.82 g / cm ³ , and closed cells having an average cell diameter of 35 μm were formed.
<First raw material tank>
Polypropylene glycol 83 parts by weight 1,4-butanediol 17 parts by weight Tin octylate 0.5 parts by weight Silicone foam stabilizer 3 parts by weight Purified water 0.3 parts by weight <Second raw material tank>
120 parts by weight of diphenylmethane diisocyanate Next, the following radical polymerizable composition was prepared at a weight ratio of the polyurethane molded product to the radical polymerization composition of 100/120, and the polyurethane molded product was immersed at 20 ° C. for 7 days. However, the entire amount of the radical polymerizable composition was impregnated in the polyurethane molded product.
Methyl methacrylate 300 parts by weight Azobisisobutyronitrile 0.9 part by weight The polyurethane molded body swollen by impregnation was sandwiched between two glass plates via a vinyl chloride gasket, and the periphery was fixed and sealed. Curing was carried out by heating at 0 ° C. for 5 hours followed by heating in a 100 ° C. oven for 3 hours. After the impregnated cured product of the polyurethane molded product was released from the glass plate, the weight was measured. Drying was carried out at 50 ° C. for 12 hours and subsequently at 100 ° C. for 12 hours. Furthermore, when it dried at normal temperature for 12 hours and measured the weight immediately, there was no weight reduction before and after normal temperature drying.

A central portion in the thickness direction of the impregnated cured product of the polyurethane molded body was sliced and subjected to surface grinding to obtain a sheet having a thickness of 2 mm. The apparent density of the radically polymerizable composition-impregnated cured product of the polyurethane molded product was 0.80 g / cm ³ , and the average cell diameter of closed cells was 43 μm. Openings derived from 360 bubbles / mm ² bubbles were observed on the surface. The tensile elastic modulus was 56 MPa.

  When the sheet piece was immersed in the slurry, an adhering deposit was formed so as to cover the surface.

  Next, after bonding a double-sided adhesive tape, it was punched into a circle having a diameter of 600 mm, and a grid-like groove having a width of 1.5 mm, a depth of 0.5 mm, and a pitch of 25 mm was formed on one side.

  When the polishing evaluation was performed, the polishing rates were 290 nm / min and 240 nm / min, respectively. The dishing amount was 52 nm. The number of particles was as large as 63.

(Example 1)
A polishing pad was produced in exactly the same manner as in Comparative Example 1 except that the following composition was used as the radical polymerizable composition.
Isobornyl methacrylate 300 parts by weight Azobisisobutyronitrile 0.8 part by weight n-octyl mercaptan 0.5 part by weight The apparent density of the radically polymerizable composition-impregnated cured product of the polyurethane molded product is 0.80 g / cm ³ , The average cell diameter of the closed cells was 46 μm. Openings derived from 350 bubbles / mm ² bubbles were observed on the surface. The tensile elastic modulus was 110 MPa.

  When the sheet piece was immersed in the slurry, almost no deposit was observed on the surface.

  When the polishing evaluation was performed, the polishing rates were 405 nm / min and 410 nm / min, respectively. The dishing amount was 27 nm. The number of particles was 11.

(Example 2)
A polishing pad was produced in exactly the same manner as in Comparative Example 1 except that the following composition was used as the radical polymerizable composition.
Dicyclopentanyl methacrylate 300 parts by weight Azobisisobutyronitrile 0.9 part by weight The apparent density of the radically polymerizable composition-impregnated cured product of the polyurethane molded product is 0.79 g / cm ³ , and the average cell diameter of closed cells is 45 μm. Met. On the surface, openings derived from 348 bubbles / mm ² were observed. The tensile modulus was 118 MPa.

  When the sheet piece was immersed in the slurry, almost no deposit was observed on the surface.

  When the polishing evaluation was performed, the polishing rates were 440 nm / min and 444 nm / min, respectively. The dishing amount was 23 nm. The number of particles was nine.

(Example 3)
A polishing pad was produced in exactly the same manner as in Comparative Example 1 except that the following composition was used as the radical polymerizable composition.
180 parts by weight of dicyclopentanyl methacrylate 120 parts by weight of methyl methacrylate
Azobisisobutyronitrile 0.7 parts by weight n-octyl mercaptan 0.5 parts by weight
The apparent density of the radically polymerizable composition-impregnated cured product of the polyurethane molded product was 0.81 g / cm ³ , and the average cell diameter of closed cells was 41 μm. On the surface, openings derived from 365 bubbles / mm ² bubbles were observed. The tensile elastic modulus was 102 MPa.

  When the sheet piece was immersed in the slurry, almost no deposit was observed on the surface.

  When the polishing evaluation was performed, the polishing rates were 422 nm / min and 421 nm / min, respectively. The dishing amount was 26 nm. The number of particles was 12.

  From the above, prepared from an interpenetrating polymer network containing a polymer of acrylic acid ester or methacrylic acid ester obtained from an alicyclic compound having 6 or more carbon atoms having a hydroxyl group in a polymer molded body such as polyurethane. Since the polished pad has a surface on which suspended substances such as solute components and abrasive grains in the slurry are difficult to adhere and deposit, the polishing rate is high and the life is long. Moreover, it turns out that there are few particles and dishing is reduced.

  The interpenetrating polymer network structure of the present invention has a surface on which inorganic and organic substances are difficult to adhere and deposit, and can be used not only in the field of electronic materials but also in the field of medical materials, for example.

    The polishing pad of the present invention can be used for polishing semiconductor substrates such as silicon wafers, optical members such as lenses, electronic materials such as magnetic heads and hard disks. In particular, it can be used as a polishing pad for polishing a semiconductor wafer as an object to be polished for the purpose of planarizing the semiconductor wafer by chemical mechanical polishing (CMP) technology.

Claims (11)

An interpenetrating polymer network structure comprising an acrylic ester or methacrylic ester polymer obtained from an alicyclic compound having 6 or more carbon atoms having a hydroxyl group. The weight ratio of the polymer of acrylic acid ester or methacrylic acid ester obtained from an alicyclic compound having 6 or more carbon atoms having a hydroxyl group to other components is 5/100 to 300/100. The interpenetrating polymer network structure described. A polishing pad comprising the interpenetrating polymer network structure according to claim 1. The polishing pad according to claim 3, comprising polyurethane. The polishing pad according to claim 3, comprising a polishing layer having a tensile elastic modulus at 60 ° C. of 100 MPa or more.   The polishing pad according to claim 3, which has closed cells having an average cell diameter of 10 to 200 μm. The polishing pad according to any one of claims 3 to 6, wherein the density of the polishing pad is 0.2 to 1.1 g / cm ³ .   The polishing pad according to claim 3, wherein the polishing pad is used for polishing a semiconductor substrate. A step of immersing the polymer molded article in a radical polymerizable composition containing an acrylic ester or methacrylic ester obtained from an alicyclic compound having 6 or more carbon atoms having a hydroxyl group and a radical polymerization initiator, a radical polymerizable composition A method for producing an interpenetrating polymer network structure comprising polymerizing a radically polymerizable compound in a swollen state of a polymer molded body impregnated with a polymer. The method for producing an interpenetrating polymer network according to claim 9, wherein the radically polymerizable composition does not substantially contain an organic solvent. The manufacturing method of the polishing pad in any one of Claim 9 or 10 in which a polymer molded object has a polyurethane as a main component.