WO2012077592A1 - 化学機械研磨パッドおよびそれを用いた化学機械研磨方法 - Google Patents
化学機械研磨パッドおよびそれを用いた化学機械研磨方法 Download PDFInfo
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- WO2012077592A1 WO2012077592A1 PCT/JP2011/077904 JP2011077904W WO2012077592A1 WO 2012077592 A1 WO2012077592 A1 WO 2012077592A1 JP 2011077904 W JP2011077904 W JP 2011077904W WO 2012077592 A1 WO2012077592 A1 WO 2012077592A1
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- polishing
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- chemical mechanical
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- mechanical polishing
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- 229920006122 polyamide resin Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920006146 polyetheresteramide block copolymer Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
- B24B37/11—Lapping tools
- B24B37/20—Lapping pads for working plane surfaces
- B24B37/24—Lapping pads for working plane surfaces characterised by the composition or properties of the pad materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B1/00—Processes of grinding or polishing; Use of auxiliary equipment in connection with such processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
- B24B37/11—Lapping tools
- B24B37/20—Lapping pads for working plane surfaces
- B24B37/22—Lapping pads for working plane surfaces characterised by a multi-layered structure
Definitions
- the present invention relates to a chemical mechanical polishing pad and a chemical mechanical polishing method using the chemical mechanical polishing pad.
- polishing pad for polishing glass or semiconductor elements a porous non-woven fabric or a polyurethane molded product obtained by impregnating a non-woven fabric with a polyurethane solution has been used.
- a chemical mechanical polishing pad suitable for chemical mechanical polishing hereinafter also referred to as "CMP" for planarizing the surface of a semiconductor substrate
- CMP chemical mechanical polishing pad suitable for chemical mechanical polishing
- JP-A-8-500622 discloses a polishing pad in which a filler-like component is dispersed in polyurethane
- JP-A-2000-17252 and JP 3956364 consider a polishing pad using foamed polyurethane and the like. There is.
- polishing pad When CMP is performed using such a polishing pad, frictional heat is generated when the surface to be polished such as the wafer surface rubs against the surface of the polishing pad, and the temperature of the surface of the polishing pad may locally rise. there were. Such a local temperature rise of the surface of the polishing pad changes the polishing characteristics of the polishing pad, which may cause flatness defects, polishing defects (scratches) and the like of the surface to be polished. In addition, when the frictional heat is accumulated in the polishing pad due to the long-term CMP and the temperature rise continues, the polishing characteristics of the entire polishing pad may be changed.
- foamed polyurethane which is currently widely used as a raw material for polishing pads, is a material that has a low thermal conductivity due to its foamed structure and is also used as a heat insulating material for housing.
- the polishing pad made of the foamed polyurethane having such properties the (1) frictional heat causes the local temperature rise on the surface of the polishing pad to lower the polishing characteristics, (2) the frictional heat is dissipated Since it is difficult, the temperature of the whole polishing pad rises by long-time CMP, and problems such as changing the polishing characteristics are remarkable.
- some aspects according to the present invention can achieve both the improvement of the flatness of the surface to be polished and the reduction of polishing defects (scratch) by solving the above-mentioned problems, and also for a long time.
- the present invention provides a chemical mechanical polishing pad capable of maintaining stable polishing characteristics even in continuous CMP, and a chemical mechanical polishing method using the chemical mechanical polishing pad.
- the present invention has been made to solve at least a part of the problems described above, and can be realized as the following aspects or application examples.
- One aspect of the chemical mechanical polishing pad according to the present invention is Having an abrasive layer formed from a composition containing polyurethane,
- the specific gravity of the polishing layer is 1.1 or more and 1.3 or less, and the thermal conductivity of the polishing layer is 0.2 [W / m ⁇ K] or more.
- Application Example 2 In the chemical mechanical polishing pad of Application Example 1, It has a laminate in which a support layer is formed on one side of the polishing layer, The thermal conductivity of the laminate may be 0.2 [W / m ⁇ K] or more.
- the residual strain at the time of tension of the polishing layer can be 2% or more and 10% or less.
- the volume change rate may be 0.8% or more and 5.0% or less when the polishing layer is immersed in water at 23 ° C. for 24 hours.
- the compression ratio of the support layer may be 5% or more.
- the polyurethane can be a thermoplastic polyurethane.
- composition may further comprise water soluble particles.
- Application Example 8 One aspect of the chemical mechanical polishing method according to the present invention is Chemical mechanical polishing is characterized by using the chemical mechanical polishing pad according to any one of application examples 1 to 7.
- the chemical mechanical polishing pad according to the present invention has both the improvement of the flatness of the surface to be polished and the reduction of polishing defects (scratch) by providing the polishing layer having specific gravity and thermal conductivity within a specific range. It is possible to maintain stable polishing characteristics even in CMP over a long time.
- FIG. 1 is a schematic view for explaining the concept of residual strain when the polishing layer is pulled.
- FIG. 2A is an enlarged view of region I in FIG.
- FIG. 2B is an enlarged view of region I in FIG.
- FIG. 2C is an enlarged view of region I in FIG.
- FIG. 2D is an enlarged view of region I in FIG.
- FIG. 2E is an enlarged view of region I in FIG.
- FIG. 3A is a schematic view for explaining the concept of the volume change rate in the polishing layer.
- FIG. 3B is a schematic view for explaining the concept of the volume change rate in the polishing layer.
- FIG. 4A is a schematic view for explaining the concept of Duro D hardness in the polishing layer.
- FIG. 4B is a schematic view for explaining the concept of Duro D hardness in the polishing layer.
- FIG. 5A is a schematic view for explaining the concept of surface hardness in the polishing layer.
- FIG. 5B is a schematic view for explaining the concept of surface hardness in the polishing layer.
- the “wet state” refers to a state in which the polishing layer is immersed in water at 23 ° C. for 4 hours or more.
- the term “hardness” simply refers to Duro D hardness
- the term “surface hardness” refers to universal hardness [HU: N / mm 2 ].
- the surface hardness of the polishing layer in the wet state is represented by universal hardness [HU: N / mm 2 ] when a constant pressure is applied, as also shown in the examples described later.
- the configuration of the chemical mechanical polishing pad according to the present embodiment is not particularly limited as long as at least one surface is provided with a polishing layer.
- the specific gravity of the polishing layer is 1.1 or more and 1.3 or less, and the thermal conductivity is 0.2 [W / m ⁇ K] or more.
- the chemical mechanical polishing pad according to the present embodiment will be described in detail below.
- the abrasive layer constituting the chemical mechanical polishing pad according to the present embodiment is formed of a composition containing polyurethane (hereinafter, also simply referred to as “composition”) by a manufacturing method described later.
- composition a composition containing polyurethane
- the most suitable polyurethane may be selected appropriately in consideration of the material of the object to be polished and the affinity with the slurry used at the time of polishing.
- the term "abrasive layer” refers to a single layer having a surface (hereinafter referred to as "abrasive surface") in contact with an object to be polished when chemical mechanical polishing is performed. That is, in the present invention, although another layer having no polishing surface may be included between the polishing layer and the support layer, the other layer is not a “polishing layer” because it does not have a polishing surface.
- polishing layers containing polyurethane are classified into foam type and non-foam type.
- the non-foaming type polishing layer which is widely used at present, its specific gravity and hardness are greater than that of the foam type due to its structure, and along with this, the polishing layer is used for the unevenness of the surface to be polished (surface such as wafer). Elastic deformation is reduced. As a result, the flatness of the surface to be polished tends to be good.
- the hardness of the polishing layer is larger than that of the foam type, the generation of polishing defects (scratch, etc.) tends to increase due to polishing debris and pad debris which enter between the surface to be polished and the polishing layer.
- the specific gravity and the hardness tend to be small due to the structure.
- polishing debris or pad debris that has entered between the surface to be polished (surface such as a wafer) and the polishing layer is captured by the surface of the flexible polishing layer, and the pressing force against the surface to be polished causes polishing debris or pad Since the contact of scraps can be avoided, the occurrence of polishing defects can be reduced.
- the elastic deformation of the polishing layer becomes large following the unevenness of the surface to be polished, the flatness of the surface to be polished tends to be deteriorated. From the above, it has been considered that the improvement of the flatness of the surface to be polished (the surface such as a wafer) and the reduction of the polishing defect (such as scratch) are contradictory characteristics.
- the present inventors prepared a polishing layer using a composition containing a polyurethane, and controlled the specific gravity and the thermal conductivity of the polishing layer, the surface to be polished that had been difficult in the prior art. It has been found that both the improvement of the flatness of (the surface of a wafer etc.) and the reduction of polishing defects (scratch etc.) can be achieved, and stable polishing characteristics can be obtained even in long-time CMP.
- thermoplastic polyurethane As described above, the structure and type of the polyurethane contained in the composition are not particularly limited, but when the object to be polished is a semiconductor wafer provided with a wiring, improvement in flatness of the surface to be polished and polishing defects ( It is preferable to use a thermoplastic polyurethane from the viewpoint of achieving a reduction in scratch).
- the thermoplastic polyurethane more preferably contains a repeating unit derived from at least one selected from alicyclic isocyanates and aromatic isocyanates. According to a composition containing a thermoplastic polyurethane having such a chemical structure, an abrasive layer having excellent flexibility can be produced.
- Abrasive layers containing polyurethanes in which thermally crosslinkable polyurethanes are crosslinked and molecular chains are strongly bonded are less likely to swell even in contact with water, as compared to abrasive layers prepared using thermoplastic polyurethanes. It has properties and can not reduce the surface hardness in the wet state. For this reason, when the polishing layer contains a cross-linked polyurethane, the polishing debris and the pad debris which get in between the surface to be polished and the polishing surface will be captured by the surface of the polishing layer having high surface hardness, Since they come in contact with the surface to be polished at a strong pressing pressure, the occurrence of polishing defects can not be suppressed.
- a polishing layer produced from a composition containing a thermoplastic polyurethane containing a repeating unit derived from at least one selected from an alicyclic isocyanate and an aromatic isocyanate facilitates control of crystallinity, It becomes easy to control the specific gravity and hardness of the polishing layer.
- alicyclic isocyanate examples include isophorone diisocyanate (IPDI), norbornene diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate (hydrogenated MDI) and the like. These alicyclic isocyanates may be used alone or in combination of two or more.
- aromatic isocyanate examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, and naphthalene.
- aromatic diisocyanates such as diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate and p-xylene diisocyanate.
- 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and 4,4'-diphenylmethane diisocyanate are preferable from the viewpoint of easy control of reaction with a hydroxyl group.
- aromatic isocyanates may be used alone or in combination of two or more.
- thermoplastic polyurethane contained in the said composition may use together alicyclic isocyanate and aromatic isocyanate, and may use other isocyanate other than these together.
- Other isocyanates include, for example, aliphatic diisocyanates such as ethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate and 1,6-hexamethylene diisocyanate.
- thermoplastic polyurethane contained in the said composition contains the repeating unit originating in alicyclic isocyanate.
- the thermoplastic polyurethane can exhibit appropriate hardness, and surface hardness in the wet state can be more appropriately controlled, and flexibility is further increased. Therefore, it is suitable for implementation of the present invention.
- thermoplastic polyurethane contained in the said composition further contains the repeating unit derived from at least 1 sort (s) selected from polyether polyol, polyester polyol, polycarbonate polyol, and polyolefin polyol.
- s the repeating unit derived from at least 1 sort (s) selected from polyether polyol, polyester polyol, polycarbonate polyol, and polyolefin polyol.
- the inclusion of the repeating units derived from the exemplified polyols tends to further improve the water resistance of the thermoplastic polyurethane.
- thermoplastic polyurethane contained in the composition may contain a repeating unit derived from a chain extender.
- chain extender include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butylene glycol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol.
- Low molecular weight dihydric alcohols such as neopentyl glycol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, diethylene glycol, triethylene glycol and 1,4-bis (2-hydroxyethoxy) benzene are mentioned Be Among these, ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butylene glycol, 1,4-butanediol, 1,5-pentanediol, from the viewpoint of easy control of reaction with an isocyanate group. 1,6-Hexanediol is preferred, and 1,4-butanediol is more preferred.
- the thermoplastic polyurethane contained in the composition contains 2 to 60% by mass of a repeating unit derived from at least one selected from alicyclic isocyanate and aromatic isocyanate, based on 100% by mass of the thermoplastic polyurethane. Preferably, the content is 3 to 55% by mass.
- a repeating unit derived from at least one selected from an alicyclic isocyanate and an aromatic isocyanate in the above range, the thermoplastic polyurethane exhibits appropriate hardness, and the surface hardness in the wet state is appropriately controlled. It is suitable for the implementation of the present invention because it can be done and its flexibility is increased.
- thermoplastic polyurethane contained in the composition is not particularly limited, and the thermoplastic polyurethane can be produced according to a general method for producing polyurethane (for example, a conventionally known batch method or prepolymer method).
- the composition may further contain a polymer compound other than the thermoplastic polyurethane.
- the other polymer compound that can be added to the composition is preferably a polymer compound having a water absorption coefficient of 3 to 3000% (hereinafter, also referred to as "water-absorbent polymer compound").
- water-absorbent polymer compound By adding the water-absorbing polymer compound, it is possible to impart appropriate water absorption to the polishing layer, and it is possible to easily control the volume change of the polishing layer which may occur due to swelling due to water absorption.
- water-absorbent polymer compounds comprising at least one bond selected from ether bonds, ester bonds and amide bonds are more preferable.
- water-absorbing polymer compound containing an ether bond examples include polyoxyethylene, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenol ether, polyether ester amide, polyether amide imide, polypropylene glycol, polyoxypropylene butyl ether, polyoxy acid Propylene glyceryl ether, polyoxypropylene sorbite, oxyethylene-epichlorohydrin copolymer, methoxypolyethylene glycol (meth) acrylate copolymer, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, poly Oxyethylene oleyl cetyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyethylene ester Oxypropylene butyl ether, polyoxyethylene polyoxypropylene hexylene glycol ether, polyoxyethylene polyoxypropylene trimethylolpropane, polyoxyethylene polyoxypropylene glyceryl ether, copolymer
- polyoxyethylene fatty acid ester for example, polyoxyethylene fatty acid ester, sucrose fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester, acrylic acid ester copolymer (acrylic rubber) Etc.
- polyoxyethylene fatty acid ester include polyethylene glycol monostearate, polyethylene glycol laurate, polyethylene glycol monooleate, polyethylene glycol distearate and the like.
- water-absorbing polymer compound containing an amide bond examples include fatty acid alkanolamides and modified polyamide resins.
- the molecular weight of the water-absorbing polymer compound is preferably 500 to 1,000,000, and more preferably 5,000 to 500,000, as the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography.
- the content thereof is preferably 1% by mass to 20% by mass, based on 100% by mass of the total amount of the thermoplastic polyurethane and the water-absorbing polymer compound. More preferably, it is 3 mass% or more and 15 mass% or less, and particularly preferably 5 mass% or more and 10 mass% or less.
- the volume change rate in the wet state can be easily adjusted to the range of 0.8% or more and 5.0% or less.
- the volume change rate of the polishing layer is in the above range, the surface of the polishing layer is appropriately softened by water absorption, so that the flatness of the surface to be polished is improved and polishing defects (scratches) can be reduced. .
- the composition may further comprise water soluble particles.
- Such water soluble particles are preferably present in the composition in a uniformly dispersed state.
- an abrasive layer in a state in which the water-soluble particles are uniformly dispersed can be obtained.
- a polishing aqueous dispersion (hereinafter also referred to as “slurry”) consisting of abrasive grains and a chemical solution, the water-soluble particles are released from the surface of the polishing layer to retain the slurry. It is used for the purpose of forming possible pores (pores). For this reason, pores are formed on the surface of the abrasive layer by using the water-soluble particles without using a polyurethane foam having a cell structure, and the retention of the slurry becomes better. In addition, since pores are formed on the surface of the polishing layer, the surface hardness in the wet state can be controlled. Furthermore, it is possible to increase the specific gravity of the polishing layer by using particles having a large specific gravity.
- the composition containing the thermoplastic polyurethane contains water-soluble particles
- the elastic deformation of the polishing layer can be reduced by the water-soluble particles acting as a reinforcing agent such as a filler, so that the surface to be polished is Flatness can be improved, (2) excellent mechanical strength due to non-foaming type polishing layer, and (3) there is no need to use a sophisticated technique to uniformly control the foam cell structure It is more preferable from the point which is excellent in productivity from this.
- the water-soluble particles are not particularly limited, and examples thereof include organic water-soluble particles and inorganic water-soluble particles. Specifically, in addition to a water-soluble polymer which is soluble in water, a water-absorbent resin which is swelled or gelled by contact with water and released from the surface of the polishing layer may be mentioned.
- Examples of the material constituting the organic water-soluble particles include saccharides (polysaccharides such as starch, dextrin and cyclodextrin, lactose, mannitol etc.), celluloses (hydroxypropyl cellulose, methyl cellulose etc.), protein, polyvinyl alcohol, Polyvinyl pyrrolidone, polyacrylic acid, polyethylene oxide, sulfonated polyisoprene, sulfonated isoprene copolymer and the like can be mentioned.
- saccharides polysaccharides such as starch, dextrin and cyclodextrin, lactose, mannitol etc.
- celluloses hydroxypropyl cellulose, methyl cellulose etc.
- protein polyvinyl alcohol
- Polyvinyl pyrrolidone polyacrylic acid
- polyethylene oxide polyethylene oxide
- sulfonated polyisoprene sulfonated isoprene copoly
- Examples of the material constituting the inorganic water-soluble particles include potassium acetate, potassium nitrate, potassium carbonate, potassium hydrogencarbonate, potassium bromide, potassium phosphate, potassium sulfate, magnesium sulfate, calcium nitrate and the like.
- the water-soluble particles materials constituting organic water-soluble particles or inorganic water-soluble particles may be used alone or in combination of two or more. From the viewpoint that the hardness and other mechanical strengths of the polishing layer can be set to an appropriate value, the water-soluble particles are preferably solid.
- the content of the water-soluble particles in the composition is preferably 3 to 150 parts by mass with respect to 100 parts by mass of the thermoplastic polyurethane.
- the content of the water-soluble particles is in the above range, it is possible to produce a polishing layer that exhibits a high polishing rate in chemical mechanical polishing, and that has appropriate hardness and other mechanical strength.
- the average particle size of the water-soluble particles is preferably 0.5 to 200 ⁇ m.
- the size of the pores formed by releasing the water-soluble particles from the surface of the polishing layer of the chemical mechanical polishing pad is preferably 0.1 to 500 ⁇ m, more preferably 0.5 to 200 ⁇ m.
- the specific gravity of the polishing layer provided in the chemical mechanical polishing pad according to the present embodiment is 1.1 or more and 1.3 or less, and preferably 1.15 or more and 1.27 or less.
- the specific gravity of the polishing layer is in the above range, the hardness of the polishing layer is appropriate and the flatness of the surface to be polished is good, and the elastic deformation (following) of the polishing layer to the irregularities of the surface to be polished is appropriate Therefore, polishing defects (scratch) can be reduced.
- the specific gravity of the polishing layer is less than the above range, the hardness of the polishing layer is too low, and the flatness of the surface to be polished is unfavorably deteriorated.
- the specific gravity of the polishing layer exceeds the above range, the hardness of the polishing layer becomes too high, which is not preferable because polishing defects (scratch) increase.
- the upper limit of the specific gravity of the polishing layer is 1.30 or less, in consideration of the balance between the currently known specific gravity of polyurethane and the appropriate hardness of the polishing layer.
- a material having a large specific gravity in addition to urethane in the polishing layer.
- a polishing layer having a specific gravity exceeding 1.30 can be produced by mixing a material having a large specific gravity, such as silica or alumina, with urethane as a filler.
- the hardness of the polishing layer is increased by the mixed filler, and the scratch on the surface to be polished is significantly deteriorated. Therefore, the same effects as the polishing layer of the present invention can not be exhibited.
- the specific gravity of the polishing layer can be measured by a method in accordance with “JIS Z8807”. Specifically, a sample of known mass is placed in a Le Chatelier pycnometer containing water, the volume of the sample is known from the rise of the liquid level by the sample, and the specific gravity is determined from the mass and volume of the sample.
- the polishing layer provided in the chemical mechanical polishing pad according to the present embodiment is preferably a non-foaming type from the viewpoint of making the specific gravity in the above range.
- the non-foaming type means that the polishing layer is substantially free of air bubbles.
- the specific gravity of a urethane pad having a foam-type polishing layer currently marketed, for example, a general commercial polishing pad such as “IC 1000” manufactured by ROHM & HAAS is about 0.40 to 0.90.
- the thermal conductivity of the polishing layer provided in the chemical mechanical polishing pad according to the present embodiment is 0.2 [W / m ⁇ K] or more, and is 0.3 [W / m ⁇ K] or more Is preferred. If the thermal conductivity of the polishing layer is 0.2 [W / m ⁇ K] or more, it is possible to rapidly diffuse into the polishing layer the frictional heat generated when the surface to be polished and the surface of the polishing pad rub against each other. It is possible to reduce the local temperature rise of the surface of the polishing pad. In addition, the durability of the polishing layer can be improved by reducing the accumulation of frictional heat generated by long-term CMP in the polishing layer.
- the thermal conductivity of the polishing layer is preferably 0.2 [W / m ⁇ K] or more, but a currently known general-purpose engineering plastic (general-purpose engineering plastic: polyvinyl alcohol
- general-purpose engineering plastic polyvinyl alcohol
- the upper limit of the thermal conductivity of polyvinyl chloride, epoxy resin, polyurethane, polyacrylic resin, polyester resin, etc. is naturally 0.6 [W / m ⁇ K].
- new polyurethanes with higher thermal conductivity will be developed in the future. Therefore, the technical idea of the present invention is not limited at all by the upper limit of the thermal conductivity described above.
- the polishing layer provided in the chemical mechanical polishing pad according to the present embodiment is preferably a non-foaming type from the viewpoint of the thermal conductivity in the above range. Moreover, it is preferable to contain a filler with high heat conductivity, for example, the above-mentioned water-soluble particle etc. can be contained as a filler.
- a filler with high heat conductivity for example, the above-mentioned water-soluble particle etc.
- the thermal conductivity of the polishing layer of a urethane pad having a foam-type polishing layer currently marketed for example, a general commercial polishing pad such as “IC 1000” manufactured by ROHM & HAAS, is 0.05 to 0. It is about ten.
- the chemical mechanical polishing pad according to the present embodiment has a laminate composed of a polishing layer and a support layer described later, or a laminate comprising another layer between the polishing layer and the support layer.
- the thermal conductivity of the laminate is preferably 0.2 [W / m ⁇ K] or more, and more preferably 0.3 [W / m ⁇ K] or more.
- the thermal conductivity of the laminate is 0.2 [W / m ⁇ K] or more, the frictional heat generated when the object to be polished and the polishing layer rub against each other is efficiently via the other layer or the support layer. It can be diffused to the surface plate which fixes the polishing pad.
- the thermal conductivity of the laminate can be calculated from the thickness of each layer and the thermal conductivity of each layer.
- the entire chemical mechanical polishing pad has another layer (thickness: d2, thermal conductivity ⁇ 2) between the polishing layer (thickness: d1, thermal conductivity ⁇ 1) and the support layer (thickness: d3, thermal conductivity ⁇ 3)
- the thermal conductivity can be calculated by the following equation (3).
- what is necessary is just to calculate the value of d2 and d2 / ⁇ 2 as 0 in following formula (3), when not containing the said other layer.
- Thermal conductivity [W / m ⁇ K] (d1 + d2 + d3) / ((d1 / ⁇ 1) + (d2 / ⁇ 2) + (d3 / ⁇ 3)) (3)
- thermal conductivity of a urethane pad with a foam type polishing layer currently marketed for example, a general commercial polishing pad such as "IC 1000" manufactured by ROHM & HAAS, is about 0.02 to 0.10. is there.
- the residual strain in tension of the polishing layer provided in the chemical mechanical polishing pad according to the present embodiment is preferably 2% or more and 10% or less, and more preferably 2% or more and 9% or less preferable.
- polishing debris and pad debris are gradually accumulated there, causing clogging and deteriorating the polishing characteristics. Therefore, by dressing with a diamond grindstone (hereinafter, also referred to as “diamond conditioning"), the surface of the clogged polishing layer is scraped off, and the same surface as the initial state below from the surface is exposed and used. During this diamond conditioning, fuzz and pad debris on the surface of the polishing layer are generated.
- diamond conditioning also referred to as “diamond conditioning”
- FIG. 1 is a schematic view for explaining the concept of residual strain when the polishing layer is pulled.
- FIGS. 2A to 2E are enlarged views of a region I in FIG. 1 for explaining the concept of residual strain during tension of the polishing layer.
- FIG. 1 shows that during diamond conditioning, the surface of the polishing layer 10 is scraped off by rotating the dresser 20 in the direction of the arrow in FIG.
- FIGS. 2A to 2B when the polishing layer 10 is dressed, a part of the surface of the polishing layer 10 is pulled by the dresser 20 and extended. Then, as shown in FIG. 2C, a part of the surface of the polishing layer 10 is cut to generate pad chips 10a.
- FIG. 2C shows that a part of the surface of the polishing layer 10 is cut to generate pad chips 10a.
- the unstretched portion 10b shrinks to return to the original state due to the elasticity of the polishing layer, but as shown in FIG. 2E, fuzz corresponding to the residual strain of the polishing layer Part 10b 'is generated.
- the residual strain in tension of the polishing layer is an index indicating the degree of fuzzing on the surface of the polishing layer during diamond conditioning.
- the residual strain at the time of tension of the polishing layer can be measured by a method in accordance with “JIS K6270”.
- the test apparatus includes a fixed-side clamp that holds one end of the test strip, a reciprocating clamp that holds and reciprocates the other end of the test strip, a driving device that reciprocates the clamp at a constant frequency, and a clamp It is comprised by the counter etc. which display the frequency
- a specific measurement method is to attach two dumbbell-shaped test pieces to a clamp, move the test apparatus, and stop after repeating 1 ⁇ 10 3 times. Stop at a position where stress is not applied to one test piece, and measure the distance between marks of the test piece after one minute.
- the test frequency is usually in the range of 1 to 5 Hz.
- the temperature and humidity at the time of measurement shall be in accordance with "JIS K6250" "6.1 Standard temperature of test room” and "6.2 Standard humidity of test room”. That is, the standard temperature of the test room is 23 ° C., and the tolerance is ⁇ 2 ° C. The standard humidity in the laboratory is 50% relative humidity, with a tolerance of ⁇ 10%.
- the polishing layer provided in the chemical mechanical polishing pad according to the present embodiment preferably has a volume change rate of 0.8% or more and 5% or less when the polishing layer is immersed in water at 23 ° C. for 24 hours. And 1% or more and 3% or less.
- FIGS. 3A to 3B are schematic views for explaining the concept of the volume change rate in the polishing layer.
- Chemical mechanical polishing pads are constantly exposed to the slurry during the polishing operation.
- the recess 30 of the polishing layer 10 which has been produced with a predetermined size and shape before water absorption as shown in FIG. 3A, is caused by swelling due to water absorption as shown in FIG. The degree of fuzzing may change.
- the volume change rate when immersed in water is in the above range, the surface of the polishing layer is appropriately softened by swelling due to water absorption, so that the occurrence of scratches can be reduced.
- the volume change rate is less than the above range, the swelling due to water absorption is small and the softening of the surface of the polishing layer is insufficient, so the effect of reducing the occurrence of scratches can not be sufficiently exhibited. If the volume change rate exceeds the above range, swelling due to water absorption becomes too large, and although the occurrence of scratches can be reduced, the flatness of the object to be polished is deteriorated. In particular, in the case where a recess pattern is formed on the polishing surface, if swelling due to water absorption becomes too large, the shape and dimensions of the recess pattern may change according to the polishing time, and stable polishing characteristics may not be obtained. For this reason, it is preferable to swell to soften the surface of the polishing layer, but excessive swelling is not preferable because it causes deformation of the polishing surface.
- the Duro D hardness of the polishing layer provided in the chemical mechanical polishing pad according to the present embodiment is preferably 50 D to 80 D, more preferably 55 D to 75 D, and 60 D to 70 D. Is particularly preferred.
- FIG. 4A to 4B are schematic views for explaining the concept of Duro D hardness in the polishing layer.
- the Duro D hardness is an index indicating the degree of macroscopic deflection of the polishing layer 10 when such a load is applied in the polishing process. This can be understood from the measurement method described later.
- the Duro D hardness of the polishing layer is in the above range, the Duro D hardness of the polishing layer is appropriate, so that the flatness of the surface to be polished is improved and the elastic deformation of the polishing layer to the unevenness of the surface to be polished ( Since the followability is appropriate, polishing defects (scratch) can be reduced. If the Duro D hardness of the polishing layer is less than the above range, the flatness of the surface to be polished is unfavorably deteriorated. In addition, when the Duro D hardness of the polishing layer exceeds the above range, polishing defects (scratch) increase, which is not preferable.
- the Duro D hardness of the polishing layer can be measured by a method in accordance with "JIS K6253". Specifically, place the test specimen on a flat, firm surface, keep the pressure plate of the Type D durometer parallel to the surface of the test specimen, and ensure that the push needle is perpendicular to the surface of the test specimen. Hold the Type D durometer and bring the pressure plate into contact with the test piece so as not to give an impact. The needle tip is measured at a position at least 12 mm away from the end of the test piece. A reading is taken 15 seconds after contacting the pressure plate with the test piece. The number of measurement points is measured 5 times at a position separated by 6 mm or more, and the median value is taken as Duro D hardness.
- Surface hardness in wet condition of the polishing layer comprising the chemical mechanical polishing pad according to surface hardness present embodiment in the wet state is preferably 2N / mm 2 or more 10 N / mm 2 or less, 3N / mm 2 or more 9N / more preferably mm 2 less, and particularly preferably 4N / mm 2 or more 8N / mm 2 or less.
- the surface hardness of the polishing layer in the wet state is an index indicating the surface hardness of the polishing layer in actual use of CMP.
- 5A to 5B are schematic views for explaining the concept of surface hardness in the polishing layer. As shown in FIG. 5A, a micro-sized probe 40 is pushed into the surface of the polishing layer 10.
- the polishing layer 10 immediately below the probe 40 is deformed so as to be pushed out around the probe 40.
- the surface hardness is an index that represents the degree of deformation or deflection of the electrode surface of the polishing layer. That is, while the Duro D hardness measurement, which is a hardness measurement method in millimeter units as shown in FIGS. 4A and 4B, provides data representing macro hardness of the entire polishing layer, polishing as shown in FIGS.
- the surface hardness measurement in the wet state of the layer provides data representing the microhardness of the electrode surface of the polishing layer.
- the indentation depth of the polishing layer in actual use of CMP is 5 micrometers to 50 micrometers.
- the surface hardness of the polishing layer in the wet state it is preferable to determine the surface hardness of the polishing layer in the wet state.
- the surface hardness of the polishing layer in the wet state is in the above range, the flexibility of the electrode surface of the polishing layer becomes appropriate, so that polishing defects (scratches) can be reduced.
- the surface hardness of the polishing layer in the wet state is less than the above range, the flatness of the surface to be polished may be deteriorated. If the surface hardness of the polishing layer in the wet state exceeds the above range, polishing defects (scratch) may increase, which is not preferable.
- the surface hardness of the polishing layer in the wet state is determined by using a nanoindenter (product name: HM2000) manufactured by FISCHER in a polishing layer immersed in water at 23 ° C. for 4 hours. Indicated by the universal hardness (HU) of
- the shape of the polishing layer and the recess The planar shape of the polishing layer is not particularly limited, but may be, for example, a circular shape.
- the size thereof is preferably 150 mm to 1200 mm in diameter, more preferably 500 mm to 1000 mm in diameter.
- the thickness of the polishing layer is preferably 0.5 mm to 5.0 mm, more preferably 1.0 mm to 4.0 mm, and particularly preferably 1.5 mm to 3.5 mm.
- a plurality of recesses may be formed on the polishing surface.
- the recess holds the slurry supplied during CMP and distributes it uniformly to the polishing surface, and temporarily holds waste such as polishing debris, pad debris and used slurry, to the outside. It has a function as a route for discharging.
- the depth of the recess can be preferably 0.1 mm or more, more preferably 0.1 mm to 2.5 mm, particularly preferably 0.2 mm to 2.0 mm.
- the width of the recess can be preferably 0.1 mm or more, more preferably 0.1 mm to 5.0 mm, particularly preferably 0.2 mm to 3.0 mm.
- the distance between adjacent recesses may be preferably 0.05 mm or more, more preferably 0.05 mm to 100 mm, and particularly preferably 0.1 mm to 10 mm.
- the pitch which is the sum of the width of the recess and the distance between the adjacent recesses may be preferably 0.15 mm or more, more preferably 0.15 mm to 105 mm, particularly preferably 0.6 mm to 13 mm. .
- the recess may be formed at a predetermined interval in the above range. By forming the recess having the shape in the above range, it is possible to easily manufacture a chemical mechanical polishing pad which is excellent in the scratch reduction effect of the surface to be polished and which has a long life.
- each said preferable range can be made into each combination. That is, for example, the depth is preferably 0.1 mm or more, the width is 0.1 mm or more, the interval is 0.05 mm or more, the depth is 0.1 mm to 2.5 mm, and the width is 0.1 mm to 5. 0 mm, more preferably 0.05 mm to 100 mm, particularly preferably 0.2 mm to 2.0 mm in depth, 0.2 mm to 3.0 mm in width, and 0.1 mm to 10 mm in distance .
- a multi-blade tool having a shape described in JP-A-2006-167811, JP-A-2001-18164, or JP-A-2008-183657 can be used.
- the cutting edge of the tool used is selected from diamond or at least one metal element selected from Group 4, 5 or 6 metals such as Ti, Cr, Zr, V, etc. and nitrogen, carbon and oxygen And at least one non-metallic element.
- the coating layer is not limited to the case where one layer is provided, and a plurality of layers may be provided with different materials.
- the thickness of such a coating layer is preferably 0.1 to 5 ⁇ m, and more preferably 1.5 to 4 ⁇ m.
- known techniques such as an arc ion plating apparatus can be appropriately selected and used according to the material of the tool, the coating material, and the like.
- the polishing layer used in the present embodiment can be obtained by molding the above-described composition containing polyurethane. Kneading of the composition can be performed by a known kneader or the like. As a kneader, a roll, a kneader, a Banbury mixer, an extruder (single screw, multi-screw) etc. are mentioned, for example. As a method of molding the polishing layer from the composition, the composition plasticized at 120 ° C. to 230 ° C. may be molded by a method of press molding, extrusion molding or injection molding, and plasticizing / sheeting. The specific gravity and the hardness can also be controlled by appropriately adjusting the molding conditions.
- a recess may be formed on the polished surface by cutting.
- the concave portion can be formed simultaneously with the rough shape of the polishing layer by molding the above-described composition using a mold in which a pattern to be a concave portion is formed.
- the chemical mechanical polishing pad according to the present embodiment may be composed of only the above-described polishing layer, but a support layer may be provided on the surface opposite to the polishing surface of the polishing layer.
- the support layer is used to support the polishing layer on a polishing machine platen in a chemical mechanical polishing pad.
- the support layer may be an adhesive layer or may be a cushion layer having an adhesive layer on both sides.
- the adhesive layer can be, for example, an adhesive sheet.
- the thickness of the adhesive sheet is preferably 50 ⁇ m to 250 ⁇ m. By having a thickness of 50 ⁇ m or more, the pressure from the polishing surface side of the polishing layer can be sufficiently relieved, and by having a thickness of 250 ⁇ m or less, the effect of asperities is not uniform on the polishing performance. A chemical mechanical polishing pad having a thickness as described above is obtained.
- the material of the pressure-sensitive adhesive sheet is not particularly limited as long as the polishing layer can be fixed to a platen for a polishing apparatus, but an acrylic or rubber material having a lower elastic modulus than the polishing layer is preferable.
- the adhesive strength of the pressure-sensitive adhesive sheet is not particularly limited as long as the chemical mechanical polishing pad can be fixed to the surface plate of the polishing apparatus, but when the adhesive strength of the pressure-sensitive adhesive sheet is measured in accordance with "JIS Z0237", the adhesive strength is preferable. Is 3 N / 25 mm or more, more preferably 4 N / 25 mm or more, and particularly preferably 10 N / 25 mm or more.
- the material of the cushion layer is not particularly limited as long as it is a material having a hardness lower than that of the polishing layer, and may be a porous body (foam) or a non-porous body.
- a cushion layer the layer which shape
- the thickness of the cushioning layer is preferably 0.1 mm to 5.0 mm, more preferably 0.5 mm to 2.0 mm.
- the thermal conductivity of the support layer is also preferably 0.2 [W / m ⁇ K] or more, and more preferably 0.3 [W / m ⁇ K] or more. If the thermal conductivity of the support layer is 0.2 [W / m ⁇ K] or more, the frictional heat generated when the surface to be polished and the surface of the polishing pad rub against each other is efficiently determined via the support layer. It can be diffused to the board. As a result, since the frictional heat generated in the polishing layer can be efficiently removed, the temperature rise in the polishing layer can be reduced and stable polishing characteristics can be maintained even when CMP is performed for a long time. Can.
- the thermal conductivity of the support layer can be measured by the same method as the above-described method of measuring the thermal conductivity of the polishing layer.
- the thermal conductivity of the support layer of a urethane pad having a foam type polishing layer currently marketed for example, a general commercial polishing pad such as "IC 1000" manufactured by ROHM & HAAS, is 0.01 to 0.10. It is an extent.
- the compressibility of the support layer is preferably 5% or more, more preferably 6% or more.
- the pressing pressure per unit area differs between the central portion and the end portion, and the pressing pressure at the end portion tends to be larger. Then, the difference between the polishing rate at the central portion of the object to be polished and the polishing rate at the end increases, making it difficult to polish the surface to be polished at a uniform polishing rate.
- the compression ratio of the support layer is in the above range, the increase in the pressing pressure at the end can be reduced by effectively deforming the support layer, so that the entire surface to be polished is polished at a uniform polishing rate.
- the compression ratio of the polishing layer is in the above range, the pressing pressure exerted on the object to be polished is too low, the polishing rate may be significantly reduced, and the flatness of the surface to be polished may be impaired. Therefore, in order to achieve the object of the present invention, it is desirable that the compression ratio of the support layer be in the above range.
- the chemical mechanical polishing method according to the present embodiment is characterized by chemical mechanical polishing using the above-mentioned chemical mechanical polishing pad.
- the aforementioned chemical mechanical polishing pad is formed of a composition containing polyurethane and has a polishing layer having a specific range of specific gravity and thermal conductivity. Therefore, according to the chemical mechanical polishing method according to the present embodiment, it is possible to simultaneously improve the flatness of the surface to be polished in the CMP step and reduce the polishing defect (scratch), and in the CMP for a long time. Also, stable polishing characteristics can be maintained.
- a commercially available chemical mechanical polishing apparatus can be used.
- a commercially available chemical mechanical polishing apparatus for example, model “EPO-112”, model “EPO-222” (above, manufactured by Ebara Corp.); model “LGP-510”, model “LGP-552” (above, Lapmaster SFT Corporation); model “Mirra”, model “Reflexion LK” (above, manufactured by Applied Materials, Inc.) and the like.
- an optimum slurry can be selected appropriately according to the object to be polished (copper film, insulating film, low dielectric constant insulating film, etc.).
- Example 1 100 parts by mass of non-alicyclic thermoplastic polyurethane (manufactured by BASF, trade name "Elastol 1174D, hardness 70D), ⁇ -cyclodextrin (made by salt water port semi-sugar Co., Ltd., trade name” Dexipearl ⁇ - "as water-soluble particles
- a thermoplastic polyurethane composition was prepared by kneading 29 parts by mass of 100 ", average particle diameter 20 ⁇ m) with a router adjusted to a temperature of 200 ° C. The produced thermoplastic polyurethane composition was compression molded at 180 ° C.
- Example 2 First, in the same manner as in Example 1, a polishing layer was obtained. A sheet-like urethane (product name: Nippa Rey EXY) to be a support layer on the tape surface by laminating a double-sided tape # 550PS5 (manufactured by Sekisui Chemical Co., Ltd.) on the surface of the polishing layer produced in this manner and having no recess formed. "Nippon Kasho Co., Ltd.” was laminated, and a double-sided tape # 442JA (manufactured by 3M) was laminated to prepare a chemical mechanical polishing pad.
- a sheet-like urethane product name: Nippa Rey EXY
- Examples 3 and 4 Chemical mechanical polishing pads of Examples 3 and 4 were produced in the same manner as Example 1 except that the types and contents of the respective components of the composition were changed to those described in Table 1.
- Example 5 First, in the same manner as in Example 1, a polishing layer was obtained. A double-sided tape # 550PS5 (manufactured by Sekisui Chemical Co., Ltd.) is laminated on the surface of the polishing layer thus produced in which no recess is formed, and a support layer having a compression ratio and a thermal conductivity described in Table 1 is obtained. It stuck, it laminated on double-sided tape # 442JA (made by 3M company), and produced the chemical mechanical polishing pad.
- a double-sided tape # 550PS5 manufactured by Sekisui Chemical Co., Ltd.
- a support layer having a compression ratio and a thermal conductivity described in Table 1 is obtained. It stuck, it laminated on double-sided tape # 442JA (made by 3M company), and produced the chemical mechanical polishing pad.
- the support layer which is the compression ratio and thermal conductivity described in Table 1 is spherical ethylene oxide (trade name "WF-15C") to hydrogenated ethylene-butylene block copolymer (trade name "DYNARON", manufactured by JSR Corporation).
- WF-15C spherical ethylene oxide
- DYNARON hydrogenated ethylene-butylene block copolymer
- Example 6 In the same manner as in Example 5, a chemical mechanical polishing pad was produced.
- the support layer which is the compression ratio and thermal conductivity described in Table 1 is spherical alumina (trade name "DAM-70") to hydrogenated ethylene-butylene block copolymer (trade name "DYNARON", manufactured by JSR Corporation). What was added by an appropriate amount so as to obtain the compression ratio and thermal conductivity described in Table 1 was manufactured by kneading with a kneader and forming into a sheet.
- DAM-70 spherical alumina
- DYNARON hydrogenated ethylene-butylene block copolymer
- Example 7 A chemical mechanical polishing pad was produced in the same manner as in Example 2 except that Sanmorph (manufactured by Sun Delta Co., Ltd.) was used as a support layer.
- Comparative Example 1 A commercially available chemical mechanical polishing pad (manufactured by ROHM & HAAS, trade name "IC 1000", the polishing layer is made of a thermally crosslinked polyurethane resin) was used. When the physical property of the polishing layer was measured by the method mentioned later, it was specific gravity 0.81 and thermal conductivity 0.05 W / m * K.
- Comparative example 2 100 parts by mass of 1,2-polybutadiene (manufactured by JSR Corporation, trade name “RB 830", hardness 47 D), ⁇ -cyclodextrin (trade name "Dixipearl ⁇ -100", manufactured by Salt Water Port Segarase Co., Ltd., as water-soluble particles A composition was obtained in which 38 parts by mass of average particle diameter 20 ⁇ m were mixed.
- Example 1 100 parts by mass of the composition obtained was further mixed with 1 part by mass of an organic peroxide (manufactured by NOF Corporation, trade name "PARK MIL D-40") to obtain a composition, followed by Example 1
- a polishing layer comprising a water-soluble particle-containing thermally crosslinked polybutadiene resin was obtained.
- a double-sided tape # 550PS5 (manufactured by Sekisui Chemical Co., Ltd.) is laminated on the surface of the polishing layer produced in this manner on which the concave portion is not formed, and a high density thin sheet-like hydrogenated ethylene to be a support layer is formed on the tape surface.
- a butylene block copolymer (trade name "DAYNARON", manufactured by JSR Corporation) was attached, and a double-sided tape # 442JA (manufactured by 3M Corporation) was laminated to prepare a chemical mechanical polishing pad.
- volume change rate was measured for the polishing layer and the polishing layer of IC 1000 produced in the above-mentioned “3.1. Production of chemical mechanical polishing pad”.
- the surface hardness in the wet state of the polishing layer was measured for the polishing layer prepared in “3.1. Production of chemical mechanical polishing pad” and the polishing layer of IC 1000.
- the surface hardness of the polishing layer in the wet state is as follows: Using a nano indenter (manufactured by FISCHER, model “HM 2000”) for the polishing layer immersed in water at 23 ° C. for 4 hours ) was measured as surface hardness. The results are shown in Table 1 together.
- Support layer thickness at 600 gf (10 gf support layer Support layer thickness at a thickness of -600 gf) Support layer thickness at a 100 gf ⁇ 100 compression ratio (%) (6)
- the object to be polished is subjected to chemical mechanical polishing treatment for 1 minute under the conditions described in “3.4. Evaluation of chemical mechanical polishing”, and the film thickness before and after the treatment is measured by an electroconductive film thickness meter (manufactured by KLA Tencor Corporation) The polishing rate was calculated from the film thickness before and after the treatment and the polishing treatment time, using the type “Omni map RS 75”).
- the end point time to clear Cu is calculated by the time from the start of polishing to the end point detected by the change of the table torque current, and the time 1.2 times the end point detection time for the patterned wafer
- a pattern where a copper wiring portion with a width of 100 ⁇ m and an insulating portion with a width of 100 ⁇ m are alternately continuous is 3.0 mm in the vertical direction with respect to the length direction.
- the dishing was evaluated by measuring the amount of depression (hereinafter, also referred to as “the amount of dishing”) of copper wiring in a portion with a width of 100 ⁇ m using the type “HRP-240”), and was used as an index of flatness. The results are shown in Table 1 together.
- the amount of dishing is preferably less than 400 ⁇ , more preferably less than 300 ⁇ , and particularly preferably less than 200 ⁇ .
- the number of scratches on the entire surface of the wafer was measured using a wafer defect inspection device (model "KLA 2351" manufactured by KLA-Tencor Co., Ltd.) on the surface to be polished of the patterned wafer after polishing processing. The results are shown in Table 1 together.
- the number of scratches is preferably less than 50, more preferably less than 30, and particularly preferably less than 20.
- the PETEOS film is a silicon oxide film formed by a chemical vapor deposition method using tetraethyl silicate (TEOS) as a raw material and plasma as acceleration conditions.
- TEOS tetraethyl silicate
- an optical interference type film thickness measuring device (Nanometrics Japan Co., Ltd., type “about 33 points uniformly taken except the range of 5 mm from both ends respectively in the diameter direction
- the thickness of the PETEOS film before and after chemical mechanical polishing was measured using Nano Spec 6100 ′ ′). From this measurement result, the polishing rate was calculated by the following formulas (7) and (8).
- Polishing amount (nm) film thickness before polishing (nm)-film thickness after polishing (nm) (7)
- Polishing rate (nm / min) average value of polishing amount at 33 points (nm) / polishing time (minutes) (8)
- Table 1 also shows the evaluation results of the polishing rate. In addition, when the polishing rate was 200 nm / min or more, it was judged that the polishing characteristics were good, and when the polishing rate was less than 200 nm / min, it was determined that the polishing characteristics were poor.
- polishing rate change rate (%) (((polishing rate after dressing for 10 hours ⁇ initial polishing rate) / initial polishing rate) ⁇ 100 (9)
- the rate of change of the polishing rate at the edge portion is preferably as small as possible, but if it is 30 or less, it can be judged that the performance can be put to practical use.
- the evaluation results of the rate of change of the polishing rate at the edge portion are also shown in Table 1.
- the polishing layer has a low thermal conductivity of 0.10 [W / m ⁇ K], so polishing is performed. There is a tendency for frictional heat to be accumulated in the layer. Therefore, it is considered that the durability of the polishing layer of the chemical mechanical polishing pad according to Comparative Example 1 is poor.
- the chemical mechanical polishing pad according to Comparative Example 1 has a laminate of the polishing layer and the support layer, the thermal conductivity of the laminate is also as low as 0.05 [W / m ⁇ K]. It is thought that it makes the diffusion of frictional heat difficult.
- the thermal conductivity is sufficiently high at 0.24 [W / m ⁇ K] but the hydrophilicity of the surface is poor, and polishing is Since the heat transfer to the slurry on the surface of the layer becomes insufficient, the durability of the polishing layer becomes poor. In addition, the polishing characteristics of the scratch were inferior.
- the chemical mechanical polishing pad according to the present invention has a flatness and a balance by defining the balance between the specific gravity and the thermal conductivity of the polishing layer containing polyurethane. It was possible to manufacture a chemical mechanical polishing pad excellent in polishing characteristics such as scratch performance and durability.
- the present invention is not limited to the embodiments described above, and various modifications are possible.
- the invention includes configurations substantially the same as the configurations described in the embodiments (for example, configurations having the same function, method and result, or configurations having the same purpose and effect).
- the present invention also includes configurations in which nonessential parts of the configurations described in the embodiments are replaced.
- the present invention also includes configurations that can achieve the same effects as the configurations described in the embodiments, or configurations that can achieve the same purpose.
- the present invention includes a configuration in which a known technique is added to the configuration described in the embodiment.
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Abstract
Description
本発明に係る化学機械研磨パッドの一態様は、
ポリウレタンを含有する組成物から形成された研磨層を有し、
前記研磨層の比重が1.1以上1.3以下であり、且つ、前記研磨層の熱伝導率が0.2[W/m・K]以上であることを特徴とする。
適用例1の化学機械研磨パッドにおいて、
前記研磨層の一方の面側に支持層が形成された積層体を有し、
前記積層体の熱伝導率が0.2[W/m・K]以上であることができる。
適用例1または適用例2の化学機械研磨パッドにおいて、
前記研磨層の引張時における残留歪が2%以上10%以下であることができる。
適用例1ないし適用例3のいずれか一例の化学機械研磨パッドにおいて、
前記研磨層を23℃の水に24時間浸漬したときの体積変化率が0.8%以上5.0%以下であることができる。
適用例2の化学機械研磨パッドにおいて、
前記支持層の圧縮率が5%以上であることができる。
適用例1ないし適用例5のいずれか一例の化学機械研磨パッドにおいて、
前記ポリウレタンが熱可塑性ポリウレタンであることができる。
適用例1ないし適用例6のいずれか一例の化学機械研磨パッドにおいて、
前記組成物は、水溶性粒子をさらに含むことができる。
本発明に係る化学機械研磨方法の一態様は、
適用例1ないし適用例7のいずれか一例の化学機械研磨パッドを用いて化学機械研磨することを特徴とする。
本実施の形態に係る化学機械研磨パッドの構成としては、少なくとも一方の面に研磨層を備えていれば特に限定されない。前記研磨層の比重は1.1以上1.3以下であり、且つ、熱伝導率は0.2[W/m・K]以上である。以下、本実施の形態に係る化学機械研磨パッドについて、詳細に説明する。
本実施の形態に係る化学機械研磨パッドを構成する研磨層は、ポリウレタンを含有する組成物(以下、単に「組成物」ともいう)から後述する製造方法により形成される。研磨層が前記範囲の比重および熱伝導率を有すれば、組成物中に含まれるポリウレタンの構造や種類については特に制限されない。したがって、被研磨物の材質や研磨時に使用するスラリーとの親和性等も考慮しながら、適宜最適なポリウレタンを選定すればよい。なお、本発明において、「研磨層」とは、化学機械研磨を行う際に被研磨物と接触する面(以下、「研磨面」という)を有する単層のことをいう。すなわち、本発明では、研磨層と支持層との間に研磨面を有しない他の層を含んでいてもよいが、該他の層は研磨面を有しないので「研磨層」ではない。
1.1.1.1.ポリウレタン
前述したように、組成物中に含まれるポリウレタンの構造や種類については特に制限されないが、被研磨物が配線を備えた半導体ウエハである場合、被研磨面の平坦性の向上と研磨欠陥(スクラッチ)の低減とを両立させる観点から、熱可塑性ポリウレタンを使用することが好ましい。熱可塑性ポリウレタンとしては、脂環式イソシアネートおよび芳香族イソシアネートから選択される少なくとも1種に由来する繰り返し単位を含むことがより好ましい。かかる化学構造を有する熱可塑性ポリウレタンを含有する組成物によれば、柔軟性に優れた研磨層を作製することができる。柔軟な研磨層の表面で被研磨面と研磨面との間に入り込んだ研磨屑やパッド屑を捕捉することにより、それらが強い押し付け圧で被研磨面に接触することを回避させることができるので、研磨欠陥の発生を低減できると考えられる。これに対して、熱架橋性ポリウレタン(熱硬化性ポリウレタン)を用いて架橋されたポリウレタンを含有する研磨層を作製した場合、研磨層に充分な柔軟性を付与することは困難であり、研磨欠陥の発生を抑制することは困難である。
前記組成物は、熱可塑性ポリウレタン以外の高分子化合物をさらに含んでもよい。前記組成物中に添加し得る他の高分子化合物としては、吸水率が3~3000%となる高分子化合物(以下、「吸水性高分子化合物」ともいう)であることが好ましい。吸水性高分子化合物を添加することにより、研磨層に適度な吸水性を付与することができ、吸水による膨潤によって生じ得る研磨層の体積変化をコントロールしやすくすることができる。
吸水率(%)=((M3-M1)/M1)×100 …(1)
前記組成物は、水溶性粒子をさらに含んでもよい。かかる水溶性粒子は、組成物中に均一に分散された状態で存在していることが好ましい。このような組成物を用いることで、水溶性粒子が均一に分散された状態の研磨層が得られる。
本実施の形態に係る化学機械研磨パッドが備える研磨層の比重は、1.1以上1.3以下であり、1.15以上1.27以下であることが好ましい。研磨層の比重が前記範囲にあると、研磨層の硬度が適度となるため被研磨面の平坦性が良好になると共に、被研磨面の凹凸に対する研磨層の弾性変形(追随性)が適度となるため研磨欠陥(スクラッチ)を低減させることができる。研磨層の比重が前記範囲未満である場合、研磨層の硬度が低くなりすぎて、被研磨面の平坦性が悪化するため好ましくない。また、研磨層の比重が前記範囲を超える場合、研磨層の硬度が高くなりすぎて、研磨欠陥(スクラッチ)が増大するため好ましくない。
本実施の形態に係る化学機械研磨パッドが備える研磨層の熱伝導率は、0.2[W/m・K]以上であり、0.3[W/m・K]以上であることが好ましい。研磨層の熱伝導率が0.2[W/m・K]以上であれば、被研磨面と研磨パッドの表面とが擦れ合うことにより発生する摩擦熱を研磨層中に迅速に拡散させることができ、研磨パッドの表面の局部的な温度上昇を低減させることができる。また、長時間のCMPにより発生する摩擦熱を研磨層中に蓄積することを低減させることで、研磨層の耐久性を向上できる。
熱伝導率(W/m・K)=D/(ρ×Cp) …(2)
熱伝導率[W/m・K]=(d1+d2+d3)/((d1/Λ1)+(d2/Λ2)+(d3/Λ3)) …(3)
参考までに、現在市販されている発泡タイプの研磨層を備えるウレタンパッド、例えばROHM&HAAS社製の「IC1000」等の一般的な市販研磨パッドの熱伝導率は、0.02~0.10程度である。
本実施の形態に係る化学機械研磨パッドが備える研磨層の引張時における残留歪は、2%以上10%以下であることが好ましく、2%以上9%以下であることがより好ましい。
引張時における残留歪(%)=((In-I0)/I0)×100 …(4)
本実施の形態に係る化学機械研磨パッドが備える研磨層は、研磨層を23℃の水に24時間浸漬したときの体積変化率が0.8%以上5%以下であることが好ましく、1%以上3%以下であることがより好ましい。
体積変化率(%)=(((M3-M4)-(M1-M2))/(M1-M2))×100 …(5)
本実施の形態に係る化学機械研磨パッドが備える研磨層のデュロD硬度は、50D以上80D以下であることが好ましく、55D以上75D以下であることがより好ましく、60D以上70D以下であることが特に好ましい。
本実施の形態に係る化学機械研磨パッドが備える研磨層のウエット状態における表面硬度は、2N/mm2以上10N/mm2以下であることが好ましく、3N/mm2以上9N/mm2以下であることがより好ましく、4N/mm2以上8N/mm2以下であることが特に好ましい。研磨層のウエット状態における表面硬度は、CMP実使用時における研磨層の表面硬度を表す指標となる。図5A~Bは、研磨層における表面硬度の概念を説明するための模式図である。図5Aに示すように、微小なサイズの探針40を研磨層10の表面へ押し込む。そうすると、図5Bに示すように、探針40直下の研磨層10は、探針40の周囲へ押し出されるように変形する。このように、表面硬度とは、研磨層の極表面の変形や撓みの程度を表す指標となる。すなわち、図4A~Bに示すようなミリメートル単位の硬度測定法である前記デュロD硬度測定では研磨層全体のマクロな硬度を表すデータが得られるのに対し、図5A~Bに示すような研磨層のウエット状態における表面硬度測定では研磨層の極表面のミクロな硬度を表すデータが得られる。CMP実使用時における研磨層の押し込み深さは、5マイクロメートルから50マイクロメートルである。したがって、このような研磨層の極表面の柔軟性を判断するためには、研磨層のウエット状態における表面硬度により判断することが好ましい。研磨層のウエット状態における表面硬度が前記範囲にあると、研磨層の極表面の柔軟性が適度となるため研磨欠陥(スクラッチ)を低減させることができる。研磨層のウエット状態における表面硬度が前記範囲未満であると、被研磨面の平坦性が悪化することがあるため好ましくない。また、研磨層のウエット状態における表面硬度が前記範囲を超えると、研磨欠陥(スクラッチ)が増大することがあるため好ましくない。なお、本発明において、研磨層のウエット状態における表面硬度は、23℃の水に4時間浸漬させた研磨層において、FISCHER社製のナノインデンター(製品名:HM2000)を使用し、300mN押し込み時のユニバーサル硬さ(HU)で示される。
研磨層の平面形状は、特に限定されないが、例えば円形状であることができる。研磨層の平面形状が円形状である場合、その大きさは、好ましくは直径150mm~1200mm、より好ましくは直径500mm~1000mmである。研磨層の厚さは、好ましくは0.5mm~5.0mm、より好ましくは1.0mm~4.0mm、特に好ましくは1.5mm~3.5mmである。
本実施の形態で用いられる研磨層は、前述したポリウレタンを含有する組成物を成型することにより得られる。組成物の混練は、公知の混練機等により行うことができる。混練機としては、例えば、ロール、ニーダー、バンバリーミキサー、押出機(単軸、多軸)等が挙げられる。組成物から研磨層を成型する方法としては、120℃~230℃で可塑化した前記組成物をプレス成形、押出成形または射出成形し、可塑化・シート化する方法により成型すればよい。かかる成型条件を適宜調整することで比重や硬度をコントロールすることもできる。
本実施の形態に係る化学機械研磨パッドは、前述した研磨層のみで構成される場合もあるが、前記研磨層の研磨面とは反対側の面に支持層を設けてもよい。
本実施の形態に係る化学機械研磨方法は、前述の化学機械研磨パッドを用いて化学機械研磨することを特徴とする。前述の化学機械研磨パッドは、ポリウレタンを含有する組成物から形成され、特定の範囲の比重および熱伝導率を兼ね備えた研磨層を有している。そのため、本実施の形態に係る化学機械研磨方法によれば、CMP工程における被研磨面の平坦性の向上と研磨欠陥(スクラッチ)の低減とを両立させることができると共に、長時間に亘るCMPにおいても安定した研磨特性を維持することができる。
以下、本発明を実施例により詳細に説明するが、本発明はこれらの実施例により何ら限定されるものではない。
3.1.1.実施例1
非脂環式熱可塑性ポリウレタン(BASF社製、商品名「エラストラン1174D」、硬度70D)を100質量部、水溶性粒子としてβ-サイクロデキストリン(塩水港精糖株式会社製、商品名「デキシパールβ-100」、平均粒径20μm)29質量部を、200℃に調温されたルーダーにより混練して熱可塑性ポリウレタン組成物を作製した。作製した熱可塑性ポリウレタン組成物を、プレス金型内にて180℃で圧縮成型し、直径845mm、厚さ3.2mmの円柱状の成型体を作製した。次に、作製した成型体の表面をサンドペーパーで研磨し、厚みを調整し、さらに切削加工機(加藤機械株式会社製)により幅0.5mm、深さ1.0mm、ピッチ1.5mmの同心円状の凹部を形成し外周部を切り離すことで、直径600mm、厚さ2.5mmの研磨層を得た。このようにして作製した研磨層のうち凹部を形成していない面へ両面テープ#422JA(3M社製)をラミネートし、化学機械研磨パッドを作製した。
まず、実施例1と同様にして研磨層を得た。このようにして作製した研磨層のうち凹部を形成していない面へ両面テープ#550PS5(積水化学工業株式会社製)をラミネートし、テープ面に支持層となるシート状ウレタン(商品名「ニッパレイEXY」、日本発条株式会社製)を貼り付け、両面テープ#442JA(3M社製)をラミネートして化学機械研磨パッドを作製した。
組成物の各成分の種類および含有量を表1に記載のものに変更したこと以外は、実施例1と同様にして実施例3、4の化学機械研磨パッドを作製した。
まず、実施例1と同様にして研磨層を得た。このようにして作製した研磨層のうち凹部を形成していない面へ両面テープ#550PS5(積水化学工業株式会社製)をラミネートし、表1に記載の圧縮率と熱伝導率である支持層を貼り付け、両面テープ#442JA(3M社製)をラミネートして化学機械研磨パッドを作製した。なお、表1に記載の圧縮率と熱伝導率である支持層は、水添エチレン-ブチレンブロックコポリマー(商品名「DYNARON」、JSR株式会社製)へ、球状黒鉛(商品名「WF-15C」、株式会社中越黒鉛工業所製)を、表1に記載の圧縮率と熱伝導率になるように適量添加したものをニーダーにて混練し、シート化することにより作製した。
実施例5と同様にして化学機械研磨パッドを作製した。なお、表1に記載の圧縮率と熱伝導率である支持層は、水添エチレン-ブチレンブロックコポリマー(商品名「DYNARON」、JSR株式会社製)へ、球状アルミナ(商品名「DAM―70」電気化学工業株式会社製)を、表1に記載の圧縮率と熱伝導率になるように適量添加したものをニーダーにて混練し、シート化することにより作製した。
支持層としてサンモルフィ(サンデルタ株式会社製)を使用した以外は、実施例2と同様にして化学機械研磨パッドを作製した。
市販の化学機械研磨パッド(ROHM&HAAS社製、商品名「IC1000」、熱架橋ポリウレタン樹脂により研磨層が作製されている)を使用した。後述する方法により研磨層の物性を測定したところ、比重0.81、熱伝導率0.05W/m・Kであった。
1,2-ポリブタジエン(JSR株式会社製、商品名「RB830」、硬度47D)100質量部に、水溶性粒子としてβ-サイクロデキストリン(塩水港精糖株式会社製、商品名「デキシパールβ-100」、平均粒径20μm)38質量部を混合した組成物を得た。得られた組成物100質量部に対して、さらに有機過酸化物(日油株式会社製、商品名「パークミルD-40」)を1質量部加え混練した組成物を得た後、実施例1と同様にして、水溶性粒子含有熱架橋ポリブタジエン樹脂からなる研磨層を得た。このようにして作製した研磨層のうち凹部を形成していない面へ両面テープ#550PS5(積水化学工業株式会社製)をラミネートし、テープ面に支持層となる高密度薄物シート状水添エチレン-ブチレンブロックコポリマー(商品名「DAYNARON」、JSR株式会社製)を貼り付け、両面テープ#442JA(3M社製)をラミネートして化学機械研磨パッドを作製した。
・「PU1-1」:非脂環式熱可塑性ポリウレタン(BASF社製、商品名「エラストラン1174D」、硬度70D)
・「PU2-1」:脂環式熱可塑性ポリウレタン(BASF社製、商品名「エラストランNY1197A」、硬度61D)
・「β-CD」:β-サイクロデキストリン(平均粒径20μm、塩水港精糖株式会社製、商品名「デキシパールβ-100」)
・「熱架橋ポリブタジエン樹脂」:1,2-ポリブタジエン(硬度47D、JSR株式会社製、商品名「RB830」)
・「有機過酸化物」:ジクミルパーオキサイド(日油株式会社製、商品名「パークミルD-40」、架橋剤)
3.2.1.比重
前記「3.1.化学機械研磨パッドの製造」で作製した研磨層およびIC1000の研磨層について、比重を測定した。研磨層の比重は、「JIS Z8807」に準拠して測定した。その結果を表1に併せて示す。
前記「3.1.化学機械研磨パッドの製造」で作製した研磨層およびIC1000の研磨層について、熱伝導率を測定した。熱伝導率は、以下のようにして測定した。センサー上に試験片を置き、マイクロヒーターを備えた固定治具を上から被せて50gの錘を載せた。マイクロヒーターの表面から発生させた温度波が厚さ方向へ拡散して裏面に達した時に生じる振幅の減衰と位相の遅れから熱拡散係数Dを測定した。得られた熱拡散係数Dと試験片の比熱ρおよび比重Cpより、下記式(2)により熱伝導率(W/m・K)を算出した。その結果を表1に併せて示す。
熱伝導率(W/m・K)=D/(ρ×Cp) …(2)
前記「3.1.化学機械研磨パッドの製造」で作製した研磨層およびIC1000の各研磨層の凹部が形成されていない部分から試験片を作製し、引張時における残留歪を測定した。引張時における残留歪は、「JIS K6270」に準拠して測定した。なお、測定時の温度は23℃であり、湿度は相対湿度で50%であった。その結果を表1に併せて示す。
前記「3.1.化学機械研磨パッドの製造」で作製した研磨層およびIC1000の研磨層について、体積変化率を測定した。研磨層の体積変化率は、「JIS K6258」に準拠した以下の方法により測定した。まず、厚さ2.8mmに成形した研磨層を2cm×2cmの角形に切り出して、これを測定用試料とした。この測定用試料を23℃の水に24時間浸漬させた。浸漬前の空気中の質量(M1)と浸漬前の水中の質量(M2)、浸漬後の空気中の質量(M3)と浸漬後の水中の質量(M4)を電子天秤(チョウバランス株式会社製、型式「JP-300」)を用いて測定し、下記式(5)により、体積変化率を算出した。その結果を表1に併せて示す。
体積変化率(%)=(((M3-M4)-(M1-M2))/(M1-M2))×100 …(5)
前記「3.1.化学機械研磨パッドの製造」で作製した研磨層およびIC1000の研磨層について、デュロD硬度を測定した。研磨層のデュロD硬度は、「JIS K6253」に準拠して測定した。その結果を表1に併せて示す。
前記「3.1.化学機械研磨パッドの製造」で作製した研磨層およびIC1000の研磨層について、研磨層のウエット状態の表面硬度を測定した。研磨層のウエット状態における表面硬度は、23℃の水に4時間浸漬させた研磨層について、ナノインデンター(FISCHER社製、型式「HM2000」)を使用し、300mN押し込み時のユニバーサル硬さ(HU)を表面硬度として測定した。その結果を表1に併せて示す。
3.3.1.圧縮率
前記「3.1.化学機械研磨パッドの製造」で使用した支持層およびIC1000より剥離した支持層について、一辺が2cm四方の正方形に切り出した小片を作製した。COMPRESSIVE ELASTICITY TESTER Model.SE-15(インテック株式会社製)を使用し、該小片を該測定装置のプローブに載せ、10gf、600gfの荷重をかけ、荷重一定のまま1分間放置した後の厚みを測定し、仮の小片厚みとした。また、小片を載せずブランクの状態でも同様に測定し、ブランクの状態での厚みを測定した。その測定結果から下記式(6)により圧縮率を算出した。
|10gfでの仮の小片厚み―10gfでのブランク厚み|=10gfでの支持層厚み
|600gfでの仮の小片厚み―600gfでのブランク厚み|=600gfでの支持層厚み
(10gfでの支持層厚み―600gfでの支持層厚み)/10gfでの支持層厚み×100=圧縮率(%) …(6)
前記「3.1.化学機械研磨用パッドの製造」で製造した化学機械研磨パッドを化学機械研磨装置(株式会社荏原製作所製、形式「EPO-112」)に装着し、ドレッサー(アライド社製、商品名「#325-63R」)を用いてテーブル回転数20rpm、ドレッシング回転数19rpm、ドレッシング荷重5.1kgfの条件でドレッシングを30分行った。その後、ドレッシングした化学機械研磨パッドを用いて以下の条件にて化学機械研磨を行い、研磨特性を評価した。
・ヘッド回転数:60rpm
・ヘッド荷重:3psi(20.6kPa)
・テーブル回転数:61rpm
・スラリー供給速度:300cm3/分
・スラリー:CMS8401/CMS8452(JSR株式会社製)
被研磨物として、シリコン基板上にPETEOS膜を5,000Å順次積層させた後、「SEMATECH 854」マスクパターン加工し、その上に250Åのタンタルナイトライド膜、1,000Åの銅シード膜および10,000Åの銅膜を順次積層させたテスト用の基板を用いた。
研磨処理後の前記パターン付きウエハの被研磨面において、ウエハ欠陥検査装置(ケーエルエー・テンコール社製、型式「KLA2351」)を使用して、ウエハ全面におけるスクラッチの個数を測定した。その結果を表1に併せて示す。なお、スクラッチは、好ましくは50個未満、より好ましくは30個未満、特に好ましくは20個未満である。
膜厚1000nmのPETEOS膜付き8インチウエハを被研磨体として前記「3.3.化学機械研磨の評価」と同じ条件にて化学機械研磨を行った。なお、PETEOS膜とは、テトラエチルシリケート(TEOS)を原料とし、促進条件としてプラズマを利用した化学気相成長法で成膜した酸化ケイ素膜である。
研磨量(nm)=研磨前の膜厚(nm)-研磨後の膜厚(nm) …(7)
研磨速度(nm/分)=33点の研磨量の平均値(nm)/研磨時間(分) …(8)
研磨速度の評価結果を表1に併せて示す。なお、研磨速度が200nm/分以上である場合には研磨特性が良好であると判断し、研磨速度が200nm/分未満である場合には研磨特性が不良であると判断した。
前記「3.4.3.研磨速度の評価」の方法に基づき、ウエハを連続的に研磨した時の研磨速度の変化率を下記式(9)により算出して研磨層の耐久性を評価した。具体的には、ウエハを連続的に研磨する状態を擬似的に再現するために、ドレッシングによるドレッサーとパッドの摩擦状態を10時間継続させ、その前後における研磨速度から下記式(9)により変化率を算出した。研磨速度の変化率が5%未満である場合には耐久性が良好(表1では「○」)であると判断し、5%以上10%未満である場合には耐久性が可(表1では「△」)であると判断し、10%以上である場合には耐久性が不良(表1では「×」)であると判断した。
研磨速度変化率(%)=((10時間ドレッシング後の研磨速度-初期研磨速度)/初期研磨速度)×100 …(9)
膜厚1000nmのTEOS膜付き8インチウエハを被研磨体として前記「3.4.化学機械研磨の評価」と同じ条件にて化学機械研磨を行った。前記被研磨体である8インチPETEOS膜付きウエハにつき、ウエハ中心から直径方向に0mm、4mm、8mm、98mmについて光干渉式膜厚測定器(ナノメトリクス・ジャパン社製、型式「Nano Spec 6100」)を用いて化学機械研磨前後のPETEOS膜の厚さを測定した。この測定結果から、下記式によりエッジ部RRの変化率を算出した。
研磨量(nm)=研磨前の膜厚(nm)-研磨後の膜厚(nm)
中心部の研磨量(nm)=0mm、4mm、8mmの研磨量の平均値
中心部の研磨速度(nm/分)=中心部の研磨量(nm)/研磨時間(分)
エッジ部の研磨量(nm)=98mmの研磨量の平均値
エッジ部の研磨速度(nm/分)=エッジ部の研磨量(nm)/研磨時間(分)
エッジ部研磨速度の変化率=|(エッジ部の研磨速度―中心部の研磨速度)/中心部の研磨速度|
なお、エッジ部研磨速度の変化率は、小さいほど好ましいが、30以下であれば実用できる性能と判断できる。エッジ部研磨速度の変化率の評価結果を表1に併せて示す。
表1によれば、実施例1~7に係る化学機械研磨パッドの研磨層が0.20[W/m・K]以上の熱伝導率を有しているため、被研磨面と研磨層とが擦れ合うことにより発生する摩擦熱の蓄積を低減させることができる。この作用により、実施例1~7に係る化学機械研磨パッドの研磨層の耐久性が良好であったと考えられる。また、平坦性、スクラッチの2項目の研磨特性においていずれも好ましい結果が得られた。
Claims (8)
- ポリウレタンを含有する組成物から形成された研磨層を有し、
前記研磨層の比重が1.1以上1.3以下であり、且つ、前記研磨層の熱伝導率が0.2[W/m・K]以上であることを特徴とする、化学機械研磨パッド。 - 前記研磨層の一方の面側に支持層が形成された積層体を有し、
前記積層体の熱伝導率が0.2[W/m・K]以上である、請求項1に記載の化学機械研磨パッド。 - 前記研磨層の引張時における残留歪が2%以上10%以下である、請求項1または請求項2に記載の化学機械研磨パッド。
- 前記研磨層を23℃の水に24時間浸漬したときの体積変化率が0.8%以上5.0%以下である、請求項1ないし請求項3のいずれか一項に記載の化学機械研磨パッド。
- 前記支持層の圧縮率が5%以上である、請求項2に記載の化学機械研磨パッド。
- 前記ポリウレタンが熱可塑性ポリウレタンである、請求項1ないし請求項5のいずれか一項に記載の化学機械研磨パッド。
- 前記組成物は、水溶性粒子をさらに含む、請求項1ないし請求項6のいずれか一項に記載の化学機械研磨パッド。
- 請求項1ないし請求項7のいずれか一項に記載の化学機械研磨パッドを用いて化学機械研磨する、化学機械研磨方法。
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WO2023048265A1 (ja) * | 2021-09-27 | 2023-03-30 | 株式会社クラレ | 研磨パッド |
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US20150056895A1 (en) * | 2013-08-22 | 2015-02-26 | Cabot Microelectronics Corporation | Ultra high void volume polishing pad with closed pore structure |
US9649741B2 (en) * | 2014-07-07 | 2017-05-16 | Jh Rhodes Company, Inc. | Polishing material for polishing hard surfaces, media including the material, and methods of forming and using same |
JP6248857B2 (ja) * | 2014-08-05 | 2017-12-20 | 信越半導体株式会社 | 研磨布の評価方法 |
JP2016087770A (ja) | 2014-11-11 | 2016-05-23 | 株式会社東芝 | 研磨布および研磨方法 |
JP7105334B2 (ja) * | 2020-03-17 | 2022-07-22 | エスケーシー ソルミックス カンパニー,リミテッド | 研磨パッドおよびこれを用いた半導体素子の製造方法 |
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