WO2013137220A1 - 研磨方法 - Google Patents
研磨方法 Download PDFInfo
- Publication number
- WO2013137220A1 WO2013137220A1 PCT/JP2013/056723 JP2013056723W WO2013137220A1 WO 2013137220 A1 WO2013137220 A1 WO 2013137220A1 JP 2013056723 W JP2013056723 W JP 2013056723W WO 2013137220 A1 WO2013137220 A1 WO 2013137220A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polishing
- insulating material
- acid
- silicon nitride
- stopper
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 103
- 238000000227 grinding Methods 0.000 title abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 180
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000000178 monomer Substances 0.000 claims abstract description 62
- 125000001424 substituent group Chemical group 0.000 claims abstract description 52
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 43
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- 239000010703 silicon Substances 0.000 claims description 17
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- LWMFAFLIWMPZSX-UHFFFAOYSA-N bis[2-(4,5-dihydro-1h-imidazol-2-yl)propan-2-yl]diazene Chemical compound N=1CCNC=1C(C)(C)N=NC(C)(C)C1=NCCN1 LWMFAFLIWMPZSX-UHFFFAOYSA-N 0.000 description 6
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F3/00—Brightening metals by chemical means
- C23F3/04—Heavy metals
- C23F3/06—Heavy metals with acidic solutions
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- 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
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30625—With simultaneous mechanical treatment, e.g. mechanico-chemical polishing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/04—Aqueous dispersions
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/06—Other polishing compositions
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1409—Abrasive particles per se
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1436—Composite particles, e.g. coated particles
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
- C09K3/1463—Aqueous liquid suspensions
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
- C09K3/1472—Non-aqueous liquid suspensions
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- 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
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/32115—Planarisation
- H01L21/3212—Planarisation by chemical mechanical polishing [CMP]
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- 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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/7684—Smoothing; Planarisation
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- 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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76898—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics formed through a semiconductor substrate
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- 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
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/31051—Planarisation of the insulating layers
- H01L21/31053—Planarisation of the insulating layers involving a dielectric removal step
Definitions
- the present invention relates to a polishing method using chemical mechanical polishing, which is used for polishing in a wiring formation process of a semiconductor device.
- CMP method chemical mechanical polishing
- the damascene method is mainly used for the formation of embedded wiring. That is, a thin film of copper or copper alloy is deposited on an insulating material (interlayer insulating material) in which concave portions (groove portions) and convex portions (protruding portions) are formed in advance, and copper or copper alloy is embedded in the concave portions, and then the convex portions are formed. In this method, a thin film (thin film other than the concave portion) deposited on the part is removed by CMP to form a buried wiring.
- the wiring metal such as copper or copper alloy
- a barrier part for preventing the diffusion of the wiring metal into the interlayer insulating material and improving adhesion for example, from a conductor such as tantalum, tantalum alloy, tantalum nitride, etc.
- the part which becomes is formed. Except for the wiring portion in which the wiring metal such as copper or copper alloy is embedded, it is necessary to remove the exposed barrier portion by CMP.
- the metal used for the barrier portion is hereinafter referred to as a barrier metal.
- polishing liquids In such a damascene method, generally, a plurality of types of CMP polishing liquids (hereinafter sometimes simply referred to as “polishing liquids”) are prepared, and only the wiring metal is removed by polishing, and then only the barrier metal or the barrier metal is removed. Polishing is performed in a plurality of steps in which the metal and interlayer insulating material are removed by polishing. This is because a polishing liquid polishes by a synergistic effect of chemical action and mechanical action, and therefore, a polishing liquid dedicated to that substance is required to remove a specific polishing target substance by polishing. It is.
- a CMP method for polishing only the wiring metal as described above is described in, for example, Patent Document 1, and a CMP method for polishing a barrier metal and an interlayer insulating material is described in, for example, Patent Document 2.
- Various additives are added to the polishing liquid for the purpose of improving the polishing rate for the object to be polished and improving the flatness of the surface after polishing.
- a polishing liquid containing a methacrylic acid-based polymer improves the polishing rate for the interlayer insulating material and suppresses erosion and seam. The technology to do is described.
- a polishing method for stopping polishing at an arbitrary thickness while removing an object to be polished at a high polishing speed is to prepare a substrate having a stopper below the object to be polished, and remove the object to be polished using a polishing liquid, Polishing must be completed when the stopper is exposed.
- a polishing method for stopping polishing using a stopper is not usually performed, and accordingly, a polishing liquid suitable for the polishing method has not been developed.
- the conventional polishing liquids described in Patent Documents 1 to 3 describe the polishing rate for metals and interlayer insulating materials, respectively, but polish a substrate having a material such as other stoppers. Not touched.
- the ratio between the polishing rate of the polishing object and the polishing rate of the stopper needs to be large.
- This polishing rate ratio is also referred to as “selection ratio between polishing object and stopper”.
- a high polishing rate ratio between the polishing object and the stopper is called a high selection ratio (high selection ratio).
- a structure has become more complicated and diversified due to advances in LSI formation technology.
- a metal such as a wiring metal or a barrier metal and an insulating material such as silicon oxide are objects to be polished and silicon nitride, silicon carbide, or the like is used as a stopper.
- a metal such as a wiring metal or a barrier metal and an insulating material such as silicon oxide are used as an object to be polished and silicon nitride, silicon carbide or the like is used as a stopper
- a part of the object to be polished for example, a barrier metal and silicon oxide
- the CMP rate of the material used as a stopper is believed to be more sensitive to mechanical action than chemical action. Therefore, it is difficult to increase the selection ratio between the insulating material and the stopper while maintaining the polishing rate for the metal.
- the present invention is intended to solve these problems, and provides a polishing method having a high CMP rate with respect to a metal such as a wiring metal and a barrier metal and a high selection ratio between an insulating material and a stopper. To do. Thereby, it is possible to obtain a structure (particularly an LSI structure) that has been difficult to manufacture.
- the inventors of the present invention overcome the above-described problems by reducing the polishing rate of the stopper by forming a portion that protects the stopper and reducing the effect of abrasive grains when performing CMP using a CMP polishing liquid. I thought that I could do it, and conducted an intensive study.
- the present invention relates to a polishing method using a polishing liquid containing a wiring metal, a barrier metal, and an insulating material as an object to be polished, silicon nitride as a stopper, and a copolymer of an anionic monomer and a monomer containing a hydrophobic substituent.
- the inventors have found that the selection ratio of insulating material / stopper can be increased.
- Specific embodiments of the present invention relate to the following.
- the process to prepare A step of supplying a CMP polishing liquid between a surface to be polished of the substrate and a polishing pad to polish the wiring metal and the insulating material located on the surface to be polished side from the silicon nitride; and exposing the silicon nitride.
- the CMP polishing liquid is (A) a copolymer of (a) a monomer that is anionic and does not contain a hydrophobic substituent, and (b) a monomer that contains a hydrophobic substituent, (B) abrasive grains, (C) acid, (D) an oxidizing agent and (E) a liquid medium,
- the component (B) has a zeta potential of +10 mV or higher in the CMP polishing liquid
- the component (A) has a copolymerization ratio ((a) :( b)) of (a) and (b) in a molar ratio of 25:75 to 75:25, and pH is 5.0 or less, Polishing method.
- the CMP polishing liquid is (A) a copolymer of (a) a monomer that is anionic and does not contain a hydrophobic substituent, and (b) a monomer that contains a hydrophobic substituent, (B) abrasive grains, (C) acid, (D) an oxidizing agent and (E) a liquid medium,
- the component (B) has a zeta
- the CMP polishing liquid is (A) a copolymer of (a) a monomer that is anionic and does not contain a hydrophobic substituent, and (b) a monomer that contains a hydrophobic substituent, (B) abrasive grains, (C) acid, (D) an oxidizing agent and (E) a liquid medium,
- the component (B) has a zeta potential of +10 mV or higher in the CMP polishing liquid
- the component (A) has a copolymerization ratio ((a) :( b)) of (a) and (b) in a molar ratio of 25:75 to 75:25, and pH is 5.0 or less, Polishing method.
- a ratio of a polishing rate of the insulating material to a polishing rate of the silicon nitride is 20 or more.
- the monomer (a) that is anionic and does not contain a hydrophobic substituent is at least one selected from the group consisting of acrylic acid and maleic acid. Polishing method.
- the monomer (b) containing a hydrophobic substituent is methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylacrylic acid, 2-propylacrylic acid and 2-butyl.
- the polishing method of the present invention it is possible to realize a high selection ratio in which polishing is stopped by a stopper while removing metal and an insulating material such as an interlayer insulating material at a high polishing rate. Thereby, it is possible to shorten the process time while maintaining high processing accuracy.
- the CMP technique can be applied in addition to the wiring forming process and the metal embedding pattern forming process, and a semiconductor device with high dimensional accuracy can be designed and manufactured.
- polishing the substance A and “polishing the substance A” are defined as removing at least a part of the substance A by polishing.
- High CMP rate is defined as a high rate at which the material being polished is removed by CMP (eg, a reduction in thickness per hour).
- Selection ratio of substance A / substance B is defined as (polishing rate of substance A / polishing rate of substance B).
- (meth) acrylic acid means acrylic acid and methacrylic acid corresponding thereto.
- (Meth) acrylamide shall mean acrylamide and the corresponding methacrylamide.
- the numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
- polishing method of this invention has silicon nitride as a stopper, a wiring metal, and an insulating material, Moreover, at least one part of the said wiring metal and the above-mentioned to the to-be-polished side from the said stopper Providing a substrate having at least a portion of an insulating material; A step of supplying a CMP polishing liquid between a surface to be polished of the substrate and a polishing pad to polish the wiring metal and the insulating material located on the surface to be polished side from the silicon nitride; and exposing the silicon nitride.
- the CMP polishing liquid is (A) a copolymer of (a) a monomer that is anionic and does not contain a hydrophobic substituent, and (b) a monomer that contains a hydrophobic substituent, (B) abrasive grains, (C) acid, (D) an oxidizing agent and (E) a liquid medium,
- the component (B) has a zeta potential of +10 mV or higher in the CMP polishing liquid
- the component (A) has a copolymerization ratio ((a) :( b)) of (a) and (b) in a molar ratio of 25:75 to 75:25, and pH is 5.0 or less,
- the present invention relates to a polishing method.
- the object to be removed by polishing is a wiring metal and an insulating material located on the surface to be polished side from the stopper, and is at least a part of each of the wiring metal and the insulating material on the substrate.
- FIG. 1 shows a schematic cross-sectional view of a substrate polishing process based on the first embodiment as an example to which the polishing method of the present invention can be suitably applied.
- 1 is an interlayer insulating film formed of an insulating material
- 2 is a stopper formed of silicon nitride
- 3 is a wiring metal.
- the substrate is preferably formed by laminating an interlayer insulating film 1, a stopper 2, and an interlayer insulating film 1 in this order, and further providing a wiring metal 3.
- the wiring metal 3 may be provided so as to penetrate the laminate.
- a polishing liquid is supplied between the surface to be polished of the substrate and the polishing pad.
- the polishing liquid in the present invention will be described later.
- the interlayer insulating film 1 and the wiring metal 3 located on the surface to be polished side from the stopper 2 are removed.
- the polishing liquid used in the polishing method of the present invention has a structure as shown in FIG. 1B, since the polishing rate for silicon nitride is sufficiently low, so that the stopper 2 is completely exposed and remains without being removed. Obtainable. At this time, a part of the stopper 2 may be polished, but is not completely removed.
- a second embodiment of the polishing method of the present invention includes silicon nitride as a stopper, a wiring metal, a barrier metal, and an insulating material, and at least one of the wiring metal on the surface to be polished side from the stopper.
- the CMP polishing liquid is (A) a copolymer of (a) a monomer that is anionic and does not contain a hydrophobic substituent, and (b) a monomer that contains a hydrophobic substituent, (B) abrasive grains, (C) acid, (D) an oxidizing agent and (E) a liquid medium,
- the component (B) has a zeta potential of +10 mV or higher in the CMP polishing liquid
- the component (A) has a copolymerization ratio ((a) :( b)) of
- the prepared substrate further includes a barrier metal in the substrate prepared in the first embodiment, and the object to be polished further includes at least a part of the barrier metal. That is, the object to be removed by polishing is a barrier metal and an insulating material located on the surface to be polished side from the stopper, and is at least a part of each of the barrier metal and the insulating material in the substrate.
- the order of lamination on the surface to be polished from the stopper is preferably at least the stopper, the insulating material, and the barrier metal.
- the substrate may be provided so that the wiring metal penetrates the stack as in the first embodiment.
- the barrier metal is preferably arranged so as to cover the surface of the stack other than the wiring metal. Thereby, the barrier metal can prevent contact between the wiring metal and the insulating material.
- the substrate is polished in the same manner as in the first embodiment, the barrier metal and the insulating material on the surface to be polished are removed from the silicon nitride serving as the stopper, and the polishing is stopped with the stopper exposed. That is, the polishing liquid used in the polishing method of the present invention has a sufficiently low polishing rate for silicon nitride used as a stopper, so that the stopper is completely exposed and remains without being removed. At this time, a part of the stopper may be polished, but not completely removed. If the substrate further includes a wiring metal, the polishing is stopped with the wiring metal, barrier metal and insulating material removed and the stopper exposed.
- a through silicon via (TSV) forming step can be mentioned.
- TSV through silicon via
- VIA-LAST VIA-LAST in which a via is formed after an element is formed.
- FIG. 2 shows a substrate in an intermediate stage of TSV formation by VIA-LAST based on the second embodiment.
- the interlayer insulating material 5, the stopper 6, and the interlayer insulating material 7 are formed in this order on the silicon substrate 4.
- the interlayer insulating film 1 is preferably formed of interlayer insulating materials 5 and 7.
- a through via is formed.
- a barrier metal 8 is formed so as to cover the interlayer insulating material 5, the stopper 6, the interlayer insulating material 7, and the through via.
- the wiring metal 9 is laminated so as to fill the concave portion of the through via by a method such as sputtering or electrolytic plating to obtain a substrate having a structure shown in FIG.
- the wiring metal 9 is CMPed using a polishing liquid to expose the barrier metal 8 to obtain a substrate having a structure shown in FIG.
- the polishing liquid used in the first polishing step is not particularly limited as long as the polishing liquid has a sufficiently high polishing rate ratio of wiring metal / barrier metal.
- the substrate for polishing in this embodiment is prepared.
- the polishing step in the second embodiment is a second polishing step in which the substrate obtained in the first polishing step is subjected to CMP using the polishing liquid in the polishing method of the present invention. Since the polishing liquid can polish the wiring metal, the barrier metal and the insulating material, at least a part of the barrier metal and a part of the insulating material are removed by the polishing in the second polishing step. Specifically, the barrier metal and the insulating material are closer to the surface to be polished than the silicon nitride serving as the stopper 6.
- the polishing liquid in the polishing method of the present invention has a sufficiently low polishing rate for silicon nitride used as the stopper 6, the polishing is stopped in a state where the stopper 6 is completely exposed and remains without being removed, A substrate having the structure shown in FIG. At this time, a part of the stopper 6 may be polished, but not completely removed.
- a third embodiment of the polishing method of the present invention includes silicon nitride as a stopper, a wiring metal, a barrier metal, and an insulating material, and at least of the wiring metal closer to the surface to be polished than the stopper. Partly has at least part of the barrier metal and at least part of the insulating material, and further laminated the silicon nitride, the insulating material, the barrier metal, and the wiring metal in this order on the surface to be polished.
- Preparing a substrate having a portion Preparing a substrate having a portion; A first polishing step located on the surface to be polished side from the silicon nitride, removing at least a part of the wiring metal and exposing a part of the barrier metal; and located on the side to be polished from the silicon nitride, at least A second polishing step of removing a part of the barrier metal and a part of the insulating material by CMP to expose the silicon nitride and stopping the polishing before the silicon nitride is completely removed.
- the CMP polishing liquid is (A) a copolymer of (a) a monomer that is anionic and does not contain a hydrophobic substituent, and (b) a monomer that contains a hydrophobic substituent, (B) abrasive grains, (C) acid, (D) an oxidizing agent and (E) a liquid medium,
- the component (B) has a zeta potential of +10 mV or higher in the CMP polishing liquid
- the component (A) has a copolymerization ratio ((a) :( b)) of (a) and (b) in a molar ratio of 25:75 to 75:25, and pH is 5.0 or less,
- the present invention relates to a polishing method.
- the substrate to be prepared is a substrate including a portion in which the wiring metal is further laminated in the order of the stopper, the insulating material, and the barrier metal of the substrate prepared in the second embodiment. is there. That is, in the third embodiment, the object to be removed in the first and second polishing steps is a wiring metal, a barrier metal, and an insulating material located on the surface to be polished side from the stopper, and the wiring metal in the substrate, At least a part of each of the barrier metal and the insulating material.
- the prepared substrate has a portion in which the silicon nitride, the insulating material, the barrier metal, and the wiring metal are stacked in this order on the surface to be polished.
- a through silicon via (TSV) forming step shown in FIG. 2 can be exemplified as in the second embodiment. That is, in the third embodiment, in FIG. 2, the first polishing step from FIG. 2 (a) to FIG. 2 (b) and the second polishing step from FIG. 2 (b) to FIG. And the polishing liquid is used in at least the second polishing step.
- TSV through silicon via
- the polishing liquid may be used as the polishing liquid used in the first polishing step from FIG. 2 (a) to FIG. 2 (b).
- the steps from FIG. 2 (a) to FIG. 2 (c) are preferable in that they can be performed continuously without changing the composition of the polishing liquid.
- the wiring metal there is a conductive material.
- Conductive substances include copper (pure copper, copper alloy, copper oxide, copper alloy oxide, etc.), aluminum (pure aluminum, aluminum alloy, aluminum oxide, etc.), tungsten (pure tungsten, tungsten alloy, etc.) , Silver and gold.
- the wiring metal is copper (pure copper), a copper alloy, a copper oxide, or an oxide of copper in that the metal of the polishing method of the present invention can be used at a high polishing rate.
- the main component is copper, such as an oxide of a copper alloy.
- “copper is a main component” means that copper content exceeds 50 mass%.
- the conductive material can be formed by a known sputtering method, plating method or the like.
- the barrier metal is defined as a metal used for the barrier portion.
- the barrier portion is formed in order to prevent the conductive material that is the wiring metal from diffusing into the insulating material and to improve the adhesion between the insulating material and the wiring metal.
- the constituent materials of such a barrier metal include, for example, tungsten, such as tungsten, a tungsten alloy, and a tungsten compound (for example, tungsten nitride); titanium, such as titanium, a titanium alloy, and a titanium compound (for example, titanium nitride), tantalum, and a tantalum alloy.
- tantalum compounds such as tantalum compounds (for example, tantalum nitride), ruthenium compounds such as ruthenium, ruthenium alloys, and ruthenium compounds (for example, ruthenium nitride).
- tantalums and titanium are preferable, and tantalum nitride and titanium nitride are more preferable in that the metal can be removed by the polishing method of the present invention at a high polishing rate.
- the barrier metal can also be a laminated material of two or more layers.
- the barrier metal is formed by vapor deposition or CVD so as to cover at least an insulating material (and through vias if necessary).
- Examples of the substance constituting the insulating material include an insulating material and an organic insulating material.
- an insulating material is preferable, and a silicon-based insulating material (defined as an insulating material containing Si as a constituent element) is more preferable in that the characteristic that the CMP process time of the polishing method of the present invention can be shortened can be utilized.
- silicon oxides are more preferable. Examples of silicon oxides include silicon dioxide (SiO 2 ), fluorosilicate glass, tetraethyl orthosilicate, organosilicate glass (silicate glass obtained using trimethylsilane, dimethoxydimethylsilane, etc.
- the insulating material can be formed on the substrate by a CVD method, a spin coating method, a dip coating method, or a spray method.
- silicon nitride is preferable in that the high processing accuracy of the polishing method of the present invention can be utilized. Silicon nitride can also be formed on silicon oxide or the like by a CVD method or the like. In addition, silicon carbide or the like may be used in combination.
- polishing apparatus for example, when polishing with a polishing cloth, it has a holder that can hold the substrate to be polished, and a polishing surface plate that is connected to a motor or the like that can change the number of rotations and can be attached to the polishing cloth.
- a general polishing apparatus can be used. There is no restriction
- the polishing conditions are not limited, but the rotation speed of the surface plate is preferably a low rotation of 200 min ⁇ 1 or less so that the substrate does not jump out.
- the pressing pressure of the substrate having the surface to be polished against the polishing cloth is preferably 1 to 100 kPa. In order to satisfy the uniformity of the polishing rate within the surface to be polished and the flatness of the pattern on the substrate, 2 to 50 kPa. It is more preferable that During polishing, it is preferable to continuously supply the polishing liquid according to the present embodiment to the polishing cloth with a pump or the like. Although there is no restriction
- the substrate after polishing is preferably washed in running water and then dried after removing water droplets adhering to the substrate using spin drying or the like.
- polishing cloth conditioning step before polishing.
- the polishing cloth is conditioned with a conditioning liquid containing at least water. Subsequently, it is preferable to carry out the polishing method according to this embodiment and further add a substrate cleaning step.
- the polishing method of the present invention can polish the wiring metal and the barrier metal, further polish the insulating material such as silicon oxide at a good polishing rate, and the polishing rate for silicon nitride is low.
- the substrate used for polishing is not limited to the structure shown in FIGS. 1 and 2 as long as the above-described effects of the polishing method of the present invention can be used.
- the polishing liquid that can be suitably used in the embodiment of the present invention will be described.
- the wiring metal and the barrier metal are also collectively referred to as “metal”.
- the polishing liquid in the present invention comprises (A) a copolymer of (a) an anionic monomer that does not contain a hydrophobic substituent and (b) a monomer that contains a hydrophobic substituent, (B) abrasive grains,
- the present invention relates to a polishing liquid containing an acid (D) oxidizing agent and (E) a liquid medium, and having a pH of 5.0 or less.
- the insulating material / stopper selection ratio can be increased (for example, 20 or more) while removing the metal and the insulating material at a high polishing rate.
- the monomer (a) which is anionic and does not contain a hydrophobic substituent is also referred to as (a) an anionic monomer.
- the present inventors presume the mechanism that increases the insulating material / stopper selection ratio when the polishing liquid of the present invention is used as follows.
- the (A) copolymer contained in the polishing liquid in the present invention is negatively charged due to the dissociation of the substituent (a) derived from the anionic monomer. This presumes that the copolymer is electrostatically attracted to the positively charged stopper and forms a protective part on the stopper surface. Further, since the copolymer contains a hydrophobic group derived from the monomer containing (b) a hydrophobic substituent, it is presumed that hydrophilic abrasive grains are inhibited from approaching the stopper. These synergistic effects are thought to reduce the polishing rate for the stopper.
- the copolymer since the copolymer does not adsorb to the negatively charged insulating material, it is considered that the polishing rate of the insulating material is not slowed down. As a result, the selection ratio between the insulating material and the stopper is estimated to increase.
- polishing rate for metal is not only mechanically affected but also chemically affected, a good polishing rate can be obtained by using the composition of the polishing liquid.
- the polishing liquid according to the present invention adjusts the mechanical action and the chemical action on the respective substances of the object to be polished and the stopper, and removes the metal and the insulating material at a high polishing rate, while insulating material / stopper. It is considered that the selection ratio can be increased.
- the insulating material / stopper selection ratio is preferably 20 or more, more preferably 25 or more, and still more preferably 30 or more.
- the polishing liquid in the present invention contains a copolymer of (A) (a) an anionic monomer and (b) a monomer containing a hydrophobic substituent.
- a copolymer of (A) (a) an anionic monomer and (b) a monomer containing a hydrophobic substituent.
- copolymer examples include random copolymerization, alternating copolymerization, block copolymerization, and graft copolymerization of (a) an anionic monomer and (b) a monomer containing a hydrophobic substituent.
- the (a) anionic monomer is preferably a monomer having an anionic substituent, and the monomer is not particularly limited as long as it has an anionic substituent and does not contain a hydrophobic substituent.
- the anionic substituent include a hydroxy group, an aldehyde group, a carbonyl group, a carboxy group, a nitro group, a sulfone group, and a phosphone group. Among them, a carboxy group is preferable. Among these, a monomer that dissociates in the polishing liquid and has a negative charge is preferable.
- Specific examples of (a) anionic monomers include acrylic acid and maleic acid.
- the anionic monomer is more preferably at least one selected from the group consisting of acrylic acid and maleic acid.
- the monomer containing a hydrophobic substituent is not particularly limited as long as it contains a hydrophobic substituent, and may further contain a hydrophilic substituent, and the substituent is anionic. Also good.
- examples of the hydrophobic substituent include an alkyl group and a phenyl group.
- Specific examples of the monomer (b) containing a hydrophobic substituent include methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethyl acrylic acid, 2-propyl acrylic acid, 2- Examples include butyl acrylic acid.
- the monomer containing a hydrophobic substituent is composed of methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylacrylic acid, 2-propylacrylic acid and 2-butylacrylic acid. More preferably, it is at least one selected from the group.
- acrylic and methacrylic acid are effective in that the effect of increasing the insulating material / stopper selection ratio while removing the metal and the insulating material at a high polishing rate can be obtained more efficiently.
- the copolymer of is more preferable.
- the (A) (a) anionic monomer and (b) the hydrophobic substituent are included in that the enlarging of the abrasive grains can be sufficiently suppressed and sedimentation of the abrasive grains can be prevented.
- (b) a monomer containing a hydrophobic substituent is preferably present in a certain ratio.
- the copolymerization ratio expressed as ((a) anionic monomer: (b) monomer containing a hydrophobic substituent) is preferably 25:75 to 75:25 in terms of molar ratio, and 35:65 ⁇ 65: 35 is more preferable, and 45:55 to 55:45 is still more preferable.
- the reason why the settling of the abrasive grains can be suppressed by controlling the copolymerization ratio is considered as follows. That is, when the abrasive grains are positively charged, for example, in the homopolymer of (a) anionic monomer, the portion where the anionic group is dissociated and becomes negatively charged is electrostatically combined with a stopper such as silicon nitride. Not only attracts but also electrostatically attracts abrasive grains. This adsorption occurs one after another, and the abrasive grains become enormous and settle.
- the copolymer (A) is more preferably a copolymer of acrylic acid and methacrylic acid in that such an effect can be obtained more efficiently.
- the weight average molecular weight (Mw) of the component (A) is preferably 500 or more, more preferably 1,500 or more, in that it tends to adsorb uniformly on the stopper surface and effectively suppress the stopper polishing rate. Is more preferable.
- the upper limit of the weight average molecular weight of the component (A) is not particularly limited, but is preferably 5 million or less in order to have sufficient water solubility from the viewpoint of solubility.
- the weight average molecular weight of the component (A) can be measured using a standard polystyrene calibration curve by gel permeation chromatography under the following conditions.
- the content of the component (A) is preferably 0.001 part by mass or more with respect to 100 parts by mass of the polishing liquid in that the selection ratio between the insulating material and the stopper can be effectively increased.
- the above is more preferable, and 0.005 parts by mass or more is still more preferable.
- the content of the component (A) is preferably 5 parts by mass or less, more preferably 2 parts by mass or less, and 1 part by mass or less in that the stability of the abrasive grains contained in the polishing liquid tends to be improved. Further preferred.
- the polishing liquid in the present invention contains abrasive grains.
- the abrasive grains are not particularly limited, but are preferably at least one selected from the group consisting of silica, alumina, zirconia, ceria, titania, germania, and modified products thereof.
- Examples of the modified product include those obtained by modifying the surface of abrasive grains with an alkyl group.
- silica is preferable from the viewpoint of availability, and colloidal silica is more preferable from the viewpoint of suppressing generation of polishing scratches.
- the primary diameter of the particles constituting the abrasive grains is preferably 10 nm or more, and more preferably 25 nm or more in terms of obtaining a good polishing rate for the insulating material.
- the primary particle diameter is preferably 60 nm or less, and more preferably 50 nm or less, from the viewpoint of excellent dispersion stability in the polishing liquid.
- the primary particle diameter is calculated as follows from the result of observing 20 arbitrary particles with a scanning electron microscope (SEM). That is, taking an example of abrasive grains having a solid content concentration of 5 to 40 wt%, which is usually dispersed in water, an appropriate amount of abrasive dispersion is taken, and a wafer with a copper film is cut into 2 cm squares in a container containing the liquid. After soaking the chip for about 30 seconds, it is transferred to a container containing pure water and rinsed for about 30 seconds, and the chip is blown dry with nitrogen.
- SEM scanning electron microscope
- the sample is placed on a sample stage for SEM observation, an acceleration voltage of 10 kV is applied, the abrasive grains are observed at a magnification of 100,000, and an image is taken. Any 20 images are selected from the obtained images.
- a circumscribed rectangle that circumscribes the abrasive grains and has the longest diameter is guided.
- the major axis of the circumscribed rectangle is X
- the minor axis is Y
- the biaxial average primary particle diameter is calculated as (X + Y) / 2. This operation is carried out for 20 arbitrary abrasive grains, and the average value of the obtained values is defined as the biaxial average primary particle diameter, which is referred to as the primary particle diameter.
- the surface potential of the particles constituting the abrasive grains in the polishing liquid is preferably +10 mV or more, more preferably +15 mV or more in that a good polishing rate for the insulating material can be obtained.
- the surface potential of the abrasive grains is preferably less than +35 mV, and more preferably less than +30 mV, from the viewpoint of excellent dispersion stability in the polishing liquid.
- the positively charged stopper repels electrostatically, and the abrasive grains cannot approach the stopper, so that the polishing effect of the abrasive grains is reduced to an appropriate level. Can do. From the viewpoint of suppressing the polishing rate of a stopper such as silicon nitride, better results can be obtained when the surface potential of the abrasive grains is positive.
- the surface potential is a zeta potential that can be converted from the electrophoretic mobility of particles using the Henry formula. More specifically, the zeta potential obtained by laser Doppler detection electrophoresis can be used as the surface potential by using a zeta potential measuring device (trade name: Delsa Nano C, manufactured by Beckman Coulter, Inc.) for the polishing liquid. it can.
- a zeta potential measuring device trade name: Delsa Nano C, manufactured by Beckman Coulter, Inc.
- abrasive grains can be used alone or in combination of two or more.
- the content of the abrasive grains is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, with respect to 100 parts by mass of the polishing liquid, in that a good polishing rate for a polishing object can be obtained.
- 0.1 parts by mass or more is more preferable, 1.0 part by mass or more is particularly preferable, and 3.0 parts by mass or more is extremely preferable.
- the content of the abrasive grains is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, and more preferably 10 parts by mass or less in that the generation of polishing scratches tends to be suppressed. Is particularly preferred.
- the polishing liquid in the present invention contains an acid.
- the object to be polished contains a metal other than the insulating material and the stopper, the metal can be removed at a good polishing rate by containing an acid.
- Examples of the acid include organic acids such as organic acids, esters of organic acids, and salts of organic acids; inorganic acids such as inorganic acids and salts of inorganic acids, and the like.
- Examples of the salt include ammonium salts, alkali metal (sodium, potassium, etc.) salts, alkaline earth metal (magnesium, calcium) salts, and the like. These acids can be used alone or in combination of two or more.
- organic acids in the organic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, 2-methylbutyric acid, n-hexanoic acid, 3,3-dimethylbutyric acid, 2-ethylbutyric acid, 4-ethyl Methylpentanoic acid, n-heptanoic acid, 2-methylhexanoic acid, n-octanoic acid, 2-ethylhexanoic acid, benzoic acid, glycolic acid, salicylic acid, glyceric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipine Examples thereof include acid, pimelic acid, maleic acid, phthalic acid, malic acid, tartaric acid, citric acid, and p-toluenesulfonic acid.
- inorganic acids in the inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, chromic acid, and the like.
- inorganic acid salts in the inorganic acids include ammonium persulfate, ammonium nitrate, ammonium chloride, ammonium dichromate, and ammonium dichromate.
- Organic acids are preferable from the viewpoint of metal etching characteristics.
- Organic acids include lactic acid, oxalic acid, succinic acid, adipic acid, glutaric acid, malic acid, malonic acid, maleic acid, tartaric acid, benzoic acid, salicylic acid, quinaldic acid, butyric acid, valeric acid, glycolic acid, glutaric acid Is preferred.
- the content of the acid is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, with respect to 100 parts by mass of the polishing liquid, in that the metal polishing rate tends to be obtained practically sufficiently.
- 0.05 mass part or more is still more preferable, and 0.1 mass part or more is especially preferable.
- the acid content is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and more preferably 5 parts by mass in that the suppression of etching becomes easy and the occurrence of roughness of the surface to be polished tends to be suppressed.
- the following is more preferable, 3 parts by mass or less is particularly preferable, and 1 part by mass or less is extremely preferable.
- the polishing liquid in the present invention further contains an oxidizing agent.
- an oxidizing agent is not particularly limited, but examples include periodate such as hydrogen peroxide and potassium periodate, persulfate (peroxosulfate), hypochlorite, ozone water, and the like. Of these, hydrogen peroxide is preferred.
- These oxidizing agents can be used alone or in combination of two or more. In the case where the substrate to be applied is a silicon substrate including an integrated circuit element, contamination with an alkali metal, an alkaline earth metal, a halide, or the like is not preferable.
- an oxidizing agent that does not include a nonvolatile component is preferable.
- the substrate to be applied is a glass substrate or the like that does not include a semiconductor element
- an oxidizing agent including a nonvolatile component may be used.
- the content of the oxidizing agent is preferably 0.01 parts by mass or more, and 0.02 parts by mass or more with respect to 100 parts by mass of the polishing liquid in that metal oxidation is sufficient and the polishing rate tends to be improved. More preferably, it is 0.05 parts by mass or more. In addition, 50 parts by mass or less is preferable with respect to 100 parts by mass of the polishing liquid, 30 parts by mass or less is more preferable, and 20 parts by mass or less in that the surface to be polished tends to be suppressed. Is more preferable.
- the barrier in order to obtain a high polishing rate for the barrier, it is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, further preferably 3 parts by mass or less, and 1.5 parts by mass or less with respect to 100 parts by mass of the polishing liquid. Is particularly preferred.
- the polishing liquid in the present invention is a liquid (a liquid in which solid abrasive grains are dispersed) by containing a liquid medium.
- the content of the liquid medium may be the balance of the components.
- Examples of the liquid medium include water and organic solvents.
- the organic solvent used in the liquid medium there is no particular limitation on the organic solvent used in the liquid medium, but a solvent that can be arbitrarily mixed with water is preferable.
- the organic solvent is used as a solubilizing agent for components that are difficult to dissolve in water, or for the purpose of increasing the polishing rate for insulating materials by improving the wettability of the polishing liquid to the surface to be polished. You can do it.
- the organic solvent is selected from carbonates, lactones, glycols and derivatives thereof, ethers, alcohols, ketones, phenols, amides, and sulfolanes, particularly from the viewpoint of improving wettability to insulating materials. At least one is preferred. Specific examples of the organic solvent are described in detail in International Publication No. 2003/038883. These organic solvents can be used individually by 1 type or in mixture of 2 or more types.
- the content of the organic solvent is preferably 0.1 parts by mass or more, and more preferably 0.2 parts by mass or more with respect to 100 parts by mass of the polishing liquid in that the wettability of the polishing liquid with respect to the surface to be polished is sufficient. More preferably, it is 0.3 parts by mass or more. Moreover, 50 mass parts or less are preferable with respect to 100 mass parts of polishing liquid at the point which the fall of a dispersibility tends to be suppressed, 30 mass parts or less are more preferable, and it is still more preferable that it is 10 mass parts or less. .
- the metal polishing liquid in the present invention may further contain a metal anticorrosive (hereinafter referred to as “corrosion inhibitor”).
- a metal anticorrosive hereinafter referred to as “corrosion inhibitor”.
- the anticorrosive agent has a function of forming a protective material on the metal surface, and has an amount of water solubility effective for exhibiting this function.
- Known substances can be used without particular limitation. These may be used alone or in combination of two or more. Further, the anticorrosive is particularly effective when the wiring object is contained in the object to be polished.
- the wiring metal when the wiring metal is not included in the object to be polished or when it is not necessary to polish a large amount of the wiring metal, it is not necessary to add.
- the amount of polishing the wiring metal is small compared to the third embodiment, so that the effect of adding the anticorrosive agent is small.
- anticorrosive examples include quinaldic acid, anthonylic acid, salicylaldoxime, triazole compound, imidazole compound, tetrazole compound, pyrazole compound, and pyrimidine compound, among which triazole compound is preferable.
- the content of the anticorrosive agent is preferably 0.001 part by mass or more with respect to 100 parts by mass of the polishing liquid in that metal etching is easily suppressed and there is a tendency to suppress the occurrence of roughness on the surface to be polished.
- 0.005 parts by mass or more is more preferable, and 0.01 parts by mass or more is particularly preferable.
- 10 mass parts or less are preferable with respect to 100 mass parts of polishing liquid at the point which the metal polishing rate fall tends to be suppressed, 5 mass parts or less are more preferable, and it is especially 2 mass parts or less. preferable.
- triazole compound examples include: Triazole derivatives such as 2-mercaptobenzothiazole, 1,2,3-triazole, 1,2,4-triazole, 3-amino-1H-1,2,4-triazole; Benzotriazole, 1-hydroxybenzotriazole, 1-dihydroxypropylbenzotriazole, 2,3-dicarboxypropylbenzotriazole, 4-hydroxybenzotriazole, 4-carboxyl (-1H-) benzotriazole, 4-carboxyl (-1H- ) Benzotriazole methyl ester, 4-carboxyl (-1H-) benzotriazole butyl ester, 4-carboxyl (-1H-) benzotriazole octyl ester, 5-hexylbenzotriazole, [1,2,3-benzotriazolyl- 1-methyl] [1,2,4-triazolyl-1-methyl] [2-ethylhexyl] amine, tolyltriazole, naphth
- imidazole compound examples include 2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-propylimidazole, 2-butylimidazole, 4-methylimidazole, 2,4-dimethylimidazole, 2-ethyl-4- Examples include methylimidazole, 2-undecylimidazole, 2-aminoimidazole and the like.
- tetrazole compounds include 1H-tetrazole, 5-amino-1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 1- (2-diaminoethyl) -5-mercaptotetrazole and the like. It is done.
- Examples of the pyrazole compound include 3,5-dimethylpyrazole, 3-amino-5-methylpyrazole, 4-methylpyrazole, 3-amino-5-hydroxypyrazole and the like.
- pyrimidine compound examples include pyrimidine, 1,2,4-triazolo [1,5-a] pyrimidine, 1,3,4,6,7,8-hexahydro-2H-pyrimido [1,2-a] pyrimidine, 1,3-diphenyl-pyrimidine-2,4,6-trione, 1,4,5,6-tetrahydropyrimidine, 2,4,5,6-tetraaminopyrimidine sulfate, 2,4,5-trihydroxy Pyrimidine, 2,4,6-triaminopyrimidine, 2,4,6-trichloropyrimidine, 2,4,6-trimethoxypyrimidine, 2,4,6-triphenylpyrimidine, 2,4-diamino-6-hydroxyl Pyrimidine, 2,4-diaminopyrimidine, 2-acetamidopyrimidine, 2-aminopyrimidine, 2-methyl-5,7-diphenyl- (1,2,4) Riazolo (1,5-a) pyrimidine, 2-methylsulfany
- the pH of the polishing liquid in the present invention is 5.0 or less in that the stopper is positively charged and the component (A) is easily adsorbed on the stopper.
- the pH is preferably 4.5 or less, more preferably 4.0 or less, and even more preferably 3.5 or less.
- the pH is preferably 1.0 or more, more preferably 2.0 or more, further preferably 2.3 or more, and 2.5 or more. It is particularly preferred.
- the stopper when the pH is 4.0 or more, the stopper is effective in adsorbing the component (A) to the stopper in that the stopper is positively charged, and a high polishing rate of silicon oxide is obtained in a region smaller than pH 4.0. It is effective in. Taking these factors into account, the pH can be determined.
- the pH of the polishing liquid in the present invention can be adjusted to a desired pH by adjusting the acid content. Furthermore, it can also be adjusted by adding an alkaline component such as ammonia, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide. It can also be adjusted by adding amino acids. However, since the presence of amino groups induces a decrease in the polishing rate of silicon oxide and may reduce the effect of the present invention, it is preferable to adjust the pH only with the acid content.
- the pH of the polishing liquid is measured with a pH meter (for example, model number: PH81 manufactured by Yokogawa Electric Corporation). Two-point calibration was performed using a standard buffer solution (phthalate pH buffer solution pH: 4.01 (25 ° C.), neutral phosphate pH buffer solution pH 6.86 (25 ° C.)), and then the electrode was polished. The value after 3 minutes or more has passed and stabilized is adopted.
- a pH meter for example, model number: PH81 manufactured by Yokogawa Electric Corporation.
- the present invention will be described in more detail with reference to examples.
- the present invention is not limited to these examples without departing from the technical idea of the present invention.
- the material type and blending ratio of the polishing liquid may be other than the type and ratio described in this example, and the composition and structure of the polishing target may be other than the composition and structure described in this example.
- Polishing liquids (2) to (8) were obtained in the same manner as in Reference Example 1 except that the respective components and amounts of the polishing liquid were changed as shown in Table 1.
- colloidal silicas A to H shown in Table 1 commercially available abrasive grains prepared by a sol-gel method were used.
- the zeta potential of the abrasive grains in the polishing liquids (1) to (8) was measured using a product name: Delsa Nano C manufactured by Beckman Coulter, Inc. The measurement was performed three times, and the average value was taken as the zeta potential of the abrasive grains in the polishing liquid.
- the pH in the polishing liquids (1) to (8) was measured using a pH meter manufactured by Yokogawa Electric Corporation, trade name: PH81. After calibrating two points using a standard buffer solution (phthalate pH buffer solution pH: 4.01 (25 ° C.), neutral phosphate pH buffer solution pH 6.86 (25 ° C.)), the electrode was polished. The value after 3 minutes or more had elapsed and stabilized was taken as the pH of the polishing liquid.
- Polishing device Desktop small polishing machine (Nippon Engis Co., Ltd., trade name: IMPTECH 10 DVT)
- Abrasive cloth Suede-like polyurethane wet foam type abrasive cloth (made by Nitta Haas, trade name: Politex (registered trademark))
- Surface plate rotation speed 160 min -1
- Polishing pressure 30kPa
- Supply amount of polishing liquid 15 mL / min
- the blanket substrates (a) to (b) were subjected to CMP polishing with the polishing liquids (1) to (8) for 60 seconds under the polishing conditions.
- Polishing rate The polishing rate of the blanket substrates (a) to (b) polished under the above conditions was measured with an optical interference type material thickness gauge (Nanometrics Japan Co., Ltd., trade name: NanoSpec (registered trademark) 5100). It was determined using the material thickness difference before and after polishing.
- Selection ratio The ratio of the polishing rate of silicon oxide to the polishing rate of silicon nitride (the value obtained by dividing the polishing rate value of silicon oxide by the polishing rate value of silicon nitride) was taken as the selection ratio.
- Example 1 [Production of acrylic acid / methacrylic acid copolymer (copolymerization ratio: 30/70)] 75.00 parts by mass of deionized water and 75.00 parts by mass of isopropanol were charged into a 0.5 liter synthesis flask and heated to 80 ° C. with stirring in a nitrogen gas atmosphere.
- the weight average molecular weight was 9,000 (polyethylene glycol equivalent). Note that the copolymerization ratio is not particularly measured because the ratio of the blended components is the same as long as the reaction is completed. The same applies to the following copolymers.
- polishing liquid (9) Acrylic acid / methacrylic acid copolymer having a nonvolatile content of 40% (copolymerization ratio: 30/70): 0.13 parts by mass, malic acid: 0.20 parts by mass, water: 74.67 parts by mass After mixing, the dissolution of acrylic acid / methacrylic acid copolymer (copolymerization ratio: 30/70) and malic acid was visually confirmed. Thereafter, 20.00 parts by mass of commercially available colloidal silica having a silica content of 20% by mass and a primary particle diameter of 40 nm (the colloidal silica C) was added. Further, the mixture was stirred and mixed, and when the color of the polishing liquid became uniform, 30% hydrogen peroxide solution: 5.00 parts by mass was added, stirred and mixed to prepare a polishing liquid (9).
- the mixture was kept at 85 ° C. for 2 hours, completely polymerized, then cooled and taken out to obtain an acrylic acid / methacrylic acid copolymer.
- the nonvolatile content was measured and found to be 40% by mass.
- the weight average molecular weight was 8,900 (polyethylene glycol conversion value).
- the mixture was kept at 85 ° C. for 2 hours, completely polymerized, then cooled and taken out to obtain an acrylic acid / methacrylic acid copolymer.
- the nonvolatile content was measured and found to be 40% by mass. Further, when the molecular weight of the obtained acrylic acid / methacrylic acid copolymer was measured by the above method, the weight average molecular weight was 8,700 (polyethylene glycol equivalent).
- polishing liquids (10) to (12) Each component shown in Table 2 including each acrylic acid / methacrylic acid copolymer prepared above was mixed and operated in the same manner as in Example 1 to prepare polishing liquids (10) to (12).
- the mixture was kept at 85 ° C. for 2 hours, completely polymerized, then cooled and taken out to obtain an acrylic acid / methacrylic acid copolymer.
- the nonvolatile content was measured and found to be 40% by mass.
- the weight average molecular weight was 9,100 (polyethylene glycol equivalent).
- polishing liquid (13) Acrylic acid / methacrylic acid copolymer having a nonvolatile content of 40% (copolymerization ratio: 5/95): 0.13 parts by mass, malic acid: 0.20 parts by mass, water: 74.67 parts by mass After mixing and visually confirming the dissolution of acrylic acid / methacrylic acid copolymer (copolymerization ratio: 5/95) and malic acid, the silica content is 20% by mass and the primary particle size is 40 nm. Colloidal silica: 20.00 parts by mass are added. Further, the mixture was stirred and mixed, and when the color of the polishing liquid became uniform, 30% hydrogen peroxide solution: 5.00 parts by mass was added, stirred and mixed to prepare a polishing liquid (13).
- polishing liquids (14) to (18) Each component shown in Table 2 containing each polymer prepared above was mixed and operated in the same manner as in Comparative Example 1 to prepare polishing liquids (14) to (18).
- the polymers used in the polishing liquids (15), (17) and (18) were commercially available. Specifically, it is as follows.
- Acrylic acid / maleic acid copolymer (copolymerization ratio: 50/50): manufactured by BASF, product name Sokalan CP13S, weight average molecular weight 20,000 Polymaleic acid: manufactured by NOF Corporation, product name PMA-50W, weight average molecular weight 1,600 Polyacrylic acid: manufactured by Nippon Shokubai Co., Ltd., product name Aquaric (registered trademark) HL-415, weight average molecular weight 10,000
- polishing liquids (10), (12) and (13) were also measured as follows.
- Blanket substrate (c) A silicon substrate on which copper (thickness: 1000 nm) is formed by a plating method.
- Blanket substrate (d) A silicon substrate on which tantalum (thickness: 300 nm) is formed by the PVD method.
- Blanket substrate (e) A silicon substrate on which tantalum nitride (thickness: 200 nm) is formed by the PVD method.
- polishing device Desktop small polishing machine (Nippon Engis Co., Ltd., trade name: IMPTECH 10 DVT)
- Abrasive cloth Suede-like polyurethane wet foam type abrasive cloth (made by Nitta Haas, trade name: Politex)
- Surface plate rotation speed 160 min -1
- Polishing pressure 30kPa Supply amount of polishing liquid: 15 mL / min
- Polishing rate The polishing rate of the blanket substrates (c) to (f) was determined using a sheet resistance measuring instrument (trade name: RT-70 / RG-7B, manufactured by Napson Corporation). The results are shown in Table 3.
- the polishing liquid (15) containing an acrylic acid / maleic acid copolymer and the polishing liquid (17) containing polymaleic acid that is an anionic polymer have a high silicon nitride polishing rate of about 200 ⁇ / min, The selectivity was also low at 7.
- B It is considered that this is because a monomer containing a hydrophobic substituent is not contained in the copolymerization component.
- the polishing rate of silicon nitride is extremely suppressed to 26 ⁇ / min. As a result, the selectivity was greatly lowered.
- the polishing liquid (18) containing polyacrylic acid which is a homopolymer of acrylic acid (the copolymerization ratio of (a) and (b) is 100: 0) is subjected to polishing evaluation because the abrasive grains settled immediately after production. I could't.
- the polishing rate for silicon oxide is high, the polishing rate for silicon nitride can be suppressed, and the selectivity of silicon oxide to silicon nitride is high. Accordingly, for example, in the CMP process of the patterned substrate, silicon oxide can be preferentially polished, and polishing can be stopped when silicon nitride is exposed. Further, since the selection ratio is sufficiently high, the polishing end point can be detected by the end point detection device.
- the polishing liquids (10), (12) and (13) have a sufficient polishing rate for various metals such as copper, tantalum, tantalum nitride and titanium nitride. Thus, it can be seen that it can be applied as a polishing liquid for metal. Since the polishing liquids (9) and (11) have an acrylic acid / methacrylic acid copolymer copolymer ratio between the polishing liquids (12) and (13), the polishing liquids (10), (12) and It can be predicted that the metal polishing rate is the same as (13).
- polishing method of the present invention it is possible to provide a polishing method in which unnecessary portions such as a wiring metal, a barrier metal, and an insulating material are removed by polishing, and polishing is terminated using silicon nitride as a stopper. .
- the polishing method of the present invention it is possible to realize a high selection ratio in which polishing is stopped by a stopper while removing an insulating material such as a metal and an interlayer insulating material at a high polishing rate. Thereby, it is possible to shorten the process time while maintaining high processing accuracy.
- the CMP technique can be applied in addition to the wiring forming process and the metal embedding pattern forming process, and a semiconductor device with high dimensional accuracy can be designed and manufactured.
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Abstract
Description
(1) ストッパとしての窒化珪素と、配線金属及び絶縁材料とを有し、かつ、前記ストッパより被研磨面側に、前記配線金属の少なくとも一部及び前記絶縁材料の少なくとも一部を有する基板を用意する工程、
前記基板の被研磨面と研磨パッドとの間にCMP研磨液を供給して、前記窒化珪素より被研磨面側に位置する前記配線金属及び前記絶縁材料を研磨する工程及び
前記窒化珪素が露出し、かつ前記窒化珪素が完全に除去される前に、研磨を停止する工程、を有し、
前記CMP研磨液は、
(A)(a)アニオン性であって疎水性置換基を含まないモノマーと、(b)疎水性置換基を含むモノマーとの共重合体、
(B)砥粒、
(C)酸、
(D)酸化剤及び
(E)液状媒体を含有してなり、
前記(B)成分は、CMP研磨液中で+10mV以上のゼータ電位を有し、
前記(A)成分は、(a)と(b)の共重合比((a):(b))が、モル比で25:75~75:25であり、かつ、
pHが5.0以下である、
研磨方法。
前記基板の被研磨面と研磨パッドとの間にCMP研磨液を供給して、前記窒化珪素より被研磨面側に位置する前記配線金属、前記バリア金属及び前記絶縁材料を研磨する工程及び
前記窒化珪素が露出し、かつ前記窒化珪素が完全に除去される前に、研磨を停止する工程、を有し、
前記CMP研磨液は、
(A)(a)アニオン性であって疎水性置換基を含まないモノマーと、(b)疎水性置換基を含むモノマーとの共重合体、
(B)砥粒、
(C)酸、
(D)酸化剤及び
(E)液状媒体を含有してなり、
前記(B)成分は、CMP研磨液中で+10mV以上のゼータ電位を有し、
前記(A)成分は、(a)と(b)の共重合比((a):(b))が、モル比で25:75~75:25であり、かつ、
pHが5.0以下である、
研磨方法。
前記窒化珪素より被研磨面側に位置する、少なくとも配線金属の一部を除去して前記バリア金属の一部を露出させる第一の研磨工程及び
前記窒化珪素より被研磨面側に位置する、少なくとも、前記バリア金属の一部及び前記絶縁材料の一部をCMPにより除去して、前記窒化珪素を露出させ、かつ前記窒化珪素が完全に除去される前に研磨を停止する第二の研磨工程を含み、
少なくとも前記第二の研磨工程で前記基板の被研磨面と研磨パッドとの間にCMP研磨液を供給する研磨方法であって、
前記CMP研磨液は、
(A)(a)アニオン性であって疎水性置換基を含まないモノマーと、(b)疎水性置換基を含むモノマーとの共重合体、
(B)砥粒、
(C)酸、
(D)酸化剤及び
(E)液状媒体を含有してなり、
前記(B)成分は、CMP研磨液中で+10mV以上のゼータ電位を有し、
前記(A)成分は、(a)と(b)の共重合比((a):(b))が、モル比で25:75~75:25であり、かつ、
pHが5.0以下である、
研磨方法。
本発明の説明において、「物質Aを研磨する」及び「物質Aの研磨」とは、物質Aの少なくとも一部を研磨により除去することと定義される。「高いCMP速度」とは、研磨される物質がCMPにより除去される速度(例えば、時間あたりの厚みの低減量)が大きいことと定義される。
[研磨方法]
(第一の実施形態)
本発明の研磨方法の第一の実施形態は、ストッパとしての窒化珪素と、配線金属及び絶縁材料とを有し、かつ、前記ストッパより被研磨面側に、前記配線金属の少なくとも一部及び前記絶縁材料の少なくとも一部を有する基板を用意する工程、
前記基板の被研磨面と研磨パッドとの間にCMP研磨液を供給して、前記窒化珪素より被研磨面側に位置する前記配線金属及び前記絶縁材料を研磨する工程及び
前記窒化珪素が露出し、かつ前記窒化珪素が完全に除去される前に、研磨を停止する工程、を有し、
前記CMP研磨液は、
(A)(a)アニオン性であって疎水性置換基を含まないモノマーと、(b)疎水性置換基を含むモノマーとの共重合体、
(B)砥粒、
(C)酸、
(D)酸化剤及び
(E)液状媒体を含有してなり、
前記(B)成分は、CMP研磨液中で+10mV以上のゼータ電位を有し、
前記(A)成分は、(a)と(b)の共重合比((a):(b))が、モル比で25:75~75:25であり、かつ、
pHが5.0以下である、
研磨方法に関する。
本発明の研磨方法の第二の実施形態は、ストッパとしての窒化珪素と、配線金属、バリア金属及び絶縁材料とを有し、かつ、前記ストッパより被研磨面側に、前記配線金属の少なくとも一部、前記バリア金属の少なくとも一部及び前記絶縁材料の少なくとも一部を有する基板を用意する工程、
前記基板の被研磨面と研磨パッドとの間にCMP研磨液を供給して、前記窒化珪素より被研磨面側に位置する前記配線金属、前記バリア金属及び前記絶縁材料を研磨する工程及び
前記窒化珪素が露出し、かつ前記窒化珪素が完全に除去される前に、研磨を停止する工程、を有し、
前記CMP研磨液は、
(A)(a)アニオン性であって疎水性置換基を含まないモノマーと、(b)疎水性置換基を含むモノマーとの共重合体、
(B)砥粒、
(C)酸、
(D)酸化剤及び
(E)液状媒体を含有してなり、
前記(B)成分は、CMP研磨液中で+10mV以上のゼータ電位を有し、
前記(A)成分は、(a)と(b)の共重合比((a):(b))が、モル比で25:75~75:25であり、かつ、
pHが5.0以下である、
研磨方法に関する。
本発明の研磨方法の第三の実施形態は、ストッパとしての窒化珪素と、配線金属、バリア金属、及び絶縁材料とを有し、かつ、前記ストッパより被研磨面側に、前記配線金属の少なくとも一部、前記バリア金属の少なくとも一部及び前記絶縁材料の少なくとも一部を有し、更に、前記窒化珪素、前記絶縁材料、前記バリア金属、前記配線金属を、この順に被研磨面側に積層した部分を有する基板を用意する工程、
前記窒化珪素より被研磨面側に位置する、少なくとも配線金属の一部を除去して前記バリア金属の一部を露出させる第一の研磨工程及び
前記窒化珪素より被研磨面側に位置する、少なくとも、前記バリア金属の一部及び前記絶縁材料の一部をCMPにより除去して、前記窒化珪素を露出させ、かつ前記窒化珪素が完全に除去される前に研磨を停止する第二の研磨工程を含み、
少なくとも前記第二の研磨工程で前記基板の被研磨面と研磨パッドとの間にCMP研磨液を供給する研磨方法であって、
前記CMP研磨液は、
(A)(a)アニオン性であって疎水性置換基を含まないモノマーと、(b)疎水性置換基を含むモノマーとの共重合体、
(B)砥粒、
(C)酸、
(D)酸化剤及び
(E)液状媒体を含有してなり、
前記(B)成分は、CMP研磨液中で+10mV以上のゼータ電位を有し、
前記(A)成分は、(a)と(b)の共重合比((a):(b))が、モル比で25:75~75:25であり、かつ、
pHが5.0以下である、
研磨方法に関する。
本発明における研磨液は、(A)(a)アニオン性モノマーと(b)疎水性置換基を含むモノマーとの共重合体を含有する。これにより、(a)アニオン性モノマーに由来するアニオン性部分の作用でストッパに吸着し、かつ(b)疎水性置換基を含むモノマーに由来する疎水性の作用で、砥粒のストッパへの接近を抑制しうる。このため、金属と絶縁材料を高研磨速度で除去しつつ、絶縁材料/ストッパの選択比を高くすることができる。
試料:10μL(Lは「リットル」を表す。以下同じ)
標準ポリスチレン:東ソー株式会社製標準ポリスチレン(分子量:190,000、17,900、9,100、2,980、578、474、370、266)
検出器:株式会社日立製作所製、RI-モニター、商品名:L-3000
インテグレーター:株式会社日立製作所製、GPCインテグレーター、商品名:D-2200
ポンプ:株式会社日立製作所製、商品名:L-6000
デガス装置:昭和電工株式会社製、商品名:Shodex DEGAS
カラム:日立化成株式会社製、商品名:GL-R440、GL-R430、GL-R420をこの順番で連結して使用
溶離液:テトラヒドロフラン(THF)
測定温度:23℃
流速:1.75mL/min
測定時間:45min
本発明における研磨液は砥粒を含有する。砥粒としては、特に制限はないが、シリカ、アルミナ、ジルコニア、セリア、チタニア、ゲルマニア及びこれらの変性物からなる群から選択される少なくとも一種であることが好ましい。前記変性物としては、砥粒粒子の表面をアルキル基で変性したものが挙げられる。砥粒の中でも、入手が容易な点でシリカが好ましく、更に研磨傷の発生を抑制する点でコロイダルシリカがより好ましい。
例えば、選択した砥粒が真球でない形状であった場合、砥粒に外接し、その長径が最も長くなるように配置した外接長方形を導く。そして、その外接長方形の長径をX、短径をYとして、(X+Y)/2として二軸平均一次粒子径を算出する。この作業を任意の20個の砥粒に対して実施し、得られた値の平均値を二軸平均一次粒子径と定義し、一次粒子径という。
本発明における研磨液は、酸を含有する。研磨対象物が絶縁材料及びストッパ以外に金属を含む場合、酸を含有することによって、金属を良好な研磨速度で除去することができる。
本発明における研磨液は、酸化剤を更に含有する。酸化剤を含有した場合、金属に対し良好な研磨速度を得ることができる。酸化剤としては、特に制限はないが、例えば、過酸化水素、過ヨウ素酸カリウム等の過ヨウ素酸塩、過硫酸塩(ペルオキソ硫酸塩)、次亜塩素酸塩、オゾン水等が挙げられ、その中でも過酸化水素が好ましい。これら酸化剤は、一種類単独で又は二種類以上を混合して用いることができる。適用対象の基板が集積回路用素子を含むシリコン基板である場合、アルカリ金属、アルカリ土類金属、ハロゲン化物等による汚染が好ましくないため、不揮発成分を含まない酸化剤が好ましい。なお、適用対象の基板が半導体素子を含まないガラス基板等である場合は、不揮発成分を含む酸化剤を用いても差し支えない。
本発明における研磨液は、液状媒体を含むことにより、液体(固体砥粒が分散した液体)となっている。液状媒体の含有量は前記含有成分の残部でよい。前記液状媒体としては、水、有機溶媒等を挙げることができる。
研磨対象物に含まれる金属の表面を腐食から保護するために、本発明における金属用研磨液は、金属防食剤(以下「防食剤」という)を更に含有することができる。本発明の金属用研磨液において防食剤とは、金属表面に対して保護材料を形成する作用を有し、かつこの作用を発揮するのに有効な量の水溶性を有していれば、従来公知の物質を特に制限なく使用できる。これらは一種類単独で、もしくは二種類以上を混合して用いることができる。また、防食剤は、研磨対象に配線金属が含まれている場合に特に有効である。このため、研磨対象に配線金属含まれない又は配線金属を多量に研磨する必要がない場合は、添加する必要がない。例えば、前記第一の実施形態及び第二の実施形態は、第三の実施形態と比較して、配線金属を研磨する量が少ないため、防食剤の添加効果は小さい。このため、前記第一の実施形態及び第二の実施形態では、防食剤を含まないことが好ましい。
2-メルカプトベンゾチアゾール、1,2,3-トリアゾール、1,2,4-トリアゾール、3-アミノ-1H-1,2,4-トリアゾール等のトリアゾール誘導体;
ベンゾトリアゾール、1-ヒドロキシベンゾトリアゾール、1-ジヒドロキシプロピルベンゾトリアゾール、2,3-ジカルボキシプロピルベンゾトリアゾール、4-ヒドロキシベンゾトリアゾール、4-カルボキシル(-1H-)ベンゾトリアゾール、4-カルボキシル(-1H-)ベンゾトリアゾールメチルエステル、4-カルボキシル(-1H-)ベンゾトリアゾールブチルエステル、4-カルボキシル(-1H-)ベンゾトリアゾールオクチルエステル、5-ヘキシルベンゾトリアゾール、[1,2,3-ベンゾトリアゾリル-1-メチル][1,2,4-トリアゾリル-1-メチル][2-エチルヘキシル]アミン、トリルトリアゾール、ナフトトリアゾール、1-アセチル-1H-1,2,3-トリアゾロ[4,5-b]ピリジン、1H-1,2,3-トリアゾロ[4,5-b]ピリジン、1,2,4-トリアゾロ[4,3-a]ピリジン-3(2H)-オン、3H-1,2,3-トリアゾロ[4,5-b]ピリジン-3-オール、ビス[(1-ベンゾトリアゾリル)メチル]ホスホン酸、3-アミノトリアゾール等のベンゾトリアゾール誘導体;
などが挙げられ、中でもベンゾトリアゾール誘導体を使用することがより好ましい。
本発明における研磨液のpHは、ストッパが正電荷を帯び、(A)成分がストッパに吸着しやすくなる点で、5.0以下である。砥粒の分散性を考慮すると、前記pHは4.5以下であることが好ましく、4.0以下であることがより好ましく、3.5以下であることが更に好ましい。一方で、研磨液の取り扱い性を考慮するとpHは1.0以上であることが好ましく、2.0以上であることがより好ましく、2.3以上であることが更に好ましく、2.5以上であることが特に好ましい。
<参考例1>
リンゴ酸0.20質量部、水73.80質量部を混合及び攪拌し、目視にてリンゴ酸の溶解を確認した。次いで、コロイダルシリカA(シリカ含有量20質量%)25.00質量部を添加し、撹拌した。研磨液の色が均一となったところで30質量%過酸化水素水1.00質量部を添加し、撹拌した。これにより、研磨液(1)を得た。
[研磨液(2)~(8)の作製]
研磨液の各成分及び量を、表1に示すとおりに変更した以外は、参考例1と同様に操作して、研磨液(2)~(8)を得た。なお、表1に示すコロイダルシリカA~Hは、ゾルゲル法にて作製された市販の砥粒を用いた。
(一次粒子径の評価)
銅膜付きシリコン基板上に付着させた砥粒の大きさを、株式会社日立ハイテクノロジーズ製、商品名:高分解能電界放出形走査電子顕微鏡 S-4800を用いて、前記の方法にて観察した。観察試料の作製は、約100mLの研磨液が入った容器に銅膜付きウエハを2cm角に切ったチップを30秒浸した後、約100mLの純水が入った容器に移して30秒間すすぎをし、そのチップを窒素ブロー乾燥して得た。
ベックマン・コールター株式会社製、商品名:デルサナノCを用いて、研磨液(1)~(8)における砥粒のゼータ電位を測定した。測定は3回実施し、その平均値を研磨液中の砥粒のゼータ電位とした。
横河電機株式会社製pH測定器、商品名:PH81を用いて研磨液(1)~(8)におけるpHを測定した。標準緩衝液(フタル酸塩pH緩衝液pH:4.01(25℃)、中性りん酸塩pH緩衝液pH6.86(25℃))を用いて、2点校正した後、電極を研磨液に入れて、3分以上経過して安定した後の値を研磨液のpHとした。
以下の基板を2cm×2cmの小片に切断し、下記の研磨に使用した。
ブランケット基板(b):CVD法で窒化珪素(厚さ:200nm)を形成したシリコン基板。
研磨装置:卓上小型研磨機(日本エンギス株式会社製、商品名:IMPTECH 10 DVT)
研磨布:スウェード状ポリウレタン湿式発泡タイプ研磨布(ニッタ・ハース社製、商品名:Politex(登録商標))
定盤回転数:160min-1
研磨圧力:30kPa
研磨液の供給量:15mL/min
前記ブランケット基板(a)~(b)を前記研磨液(1)~(8)で、前記研磨条件で60秒間CMP研磨した。
研磨速度:前記条件で研磨したブランケット基板(a)~(b)の研磨速度を、光干渉式材料厚計(ナノメトリクス ジャパン株式会社製、商品名:NanoSpec(登録商標)5100)にて測定した研磨前後の材料厚差を使用して求めた。
<実施例1>
[アクリル酸/メタクリル酸共重合体(共重合比:30/70)の作製]
脱イオン水75.00質量部とイソプロパノール75.00質量部を、0.5リットルの合成用フラスコに投入し、窒素ガス雰囲気下で撹拌しながら80℃に昇温した。
その後、アクリル酸32.05質量部とメタクリル酸89.34質量部を混合したもの及び、2,2´-アゾビス〔2-(2-イミダゾリン-2-イル)プロパン〕14.84質量部と濃硫酸11.63質量部を脱イオン水80.00質量部に溶解させたものを、同時に60分間かけてフラスコ中に注入した。85℃で2時間保温し、完全に重合反応させた後に冷却して取り出し、アクリル酸/メタクリル酸共重合体を得た。その不揮発分を測定したところ、40質量%であった。また、得られたアクリル酸/メタクリル酸共重合体の分子量を前記の方法にて測定を行ったところ、その重量平均分子量は9,000(ポリエチレングリコール換算値)であった。なお、共重合比は、反応が完全に終わっていれば配合成分の比率通りとなるため、特に測定は実施していない。以下の共重合体についても同様である。
不揮発分が40%の前記アクリル酸/メタクリル酸共重合体(共重合比:30/70):0.13質量部、リンゴ酸:0.20質量部、水:74.67質量部を撹拌・混合し、目視にてアクリル酸/メタクリル酸共重合体(共重合比:30/70)とリンゴ酸の溶解を確認した。その後、シリカ含有量が20質量%で1次粒子径が40nmである市販のコロイダルシリカ:20.00質量部(前記のコロイダルシリカC)を添加した。さらに撹拌・混合し、研磨液の色が均一となったところで30%過酸化水素水:5.00質量部を添加、撹拌・混合し、研磨液(9)を作製した。
[アクリル酸/メタクリル酸共重合体(共重合比:50/50)の作製]
脱イオン水75.00質量部とイソプロパノール75.00質量部を、0.5リットルの合成用フラスコに投入し、窒素ガス雰囲気下で撹拌しながら80℃に昇温した。
その後、アクリル酸54.94質量部とメタクリル酸65.63質量部を混合したもの及び、2,2´-アゾビス〔2-(2-イミダゾリン-2-イル)プロパン〕15.27質量部と濃硫酸11.96質量部を脱イオン水80.00質量部に溶解させたものを、同時に60分間かけてフラスコ中に注入した。85℃で2時間保温し、完全に重合反応させた後に冷却して取り出し、アクリル酸/メタクリル酸共重合体を得た。その不揮発分を測定したところ、40質量%であった。また、得られたアクリル酸/メタクリル酸共重合体の分子量を前記の方法にて測定を行ったところ、その重量平均分子量は9,300(ポリエチレングリコール換算値)であった。
脱イオン水75.00質量部とイソプロパノール75.00質量部を、0.5リットルの合成用フラスコに投入し、窒素ガス雰囲気下で撹拌しながら80℃に昇温した。
その後、アクリル酸66.88質量部とメタクリル酸53.27質量部を混合したもの及び、2,2´-アゾビス〔2-(2-イミダゾリン-2-イル)プロパン〕15.49質量部と濃硫酸12.14質量部を脱イオン水80.00質量部に溶解させたものを、同時に60分間かけてフラスコ中に注入した。85℃で2時間保温し、完全に重合反応させた後に冷却して取り出し、アクリル酸/メタクリル酸共重合体を得た。その不揮発分を測定したところ、40質量%であった。また、得られたアクリル酸/メタクリル酸共重合体の分子量を前記の方法にて測定を行ったところ、その重量平均分子量は8,900(ポリエチレングリコール換算値)であった。
脱イオン水75.00質量部とイソプロパノール75.00質量部を、0.5リットルの合成用フラスコに投入し、窒素ガス雰囲気下で撹拌しながら80℃に昇温した。
その後、アクリル酸79.17質量部とメタクリル酸40.54質量部を混合したもの及び、2,2´-アゾビス〔2-(2-イミダゾリン-2-イル)プロパン〕15.71質量部と濃硫酸12.31質量部を脱イオン水80.00質量部に溶解させたものを、同時に60分間かけてフラスコ中に注入した。85℃で2時間保温し、完全に重合反応させた後に冷却して取り出し、アクリル酸/メタクリル酸共重合体を得た。その不揮発分を測定したところ、40質量%であった。また、得られたアクリル酸/メタクリル酸共重合体の分子量を前記の方法にて測定を行ったところ、その重量平均分子量は8,700(ポリエチレングリコール換算値)であった。
前記で作製した各アクリル酸/メタクリル酸共重合体を含む表2に示す各成分を混合し、実施例1と同様に操作して研磨液(10)~(12)を作製した。
[アクリル酸/メタクリル酸共重合体(共重合比:5/95)の作製]
脱イオン水75.00質量部とイソプロパノール75.00質量部を、0.5リットルの合成用フラスコに投入し、窒素ガス雰囲気下で撹拌しながら80℃に昇温した。その後、アクリル酸5.16質量部とメタクリル酸117.18質量部を混合したもの及び、2,2´-アゾビス〔2-(2-イミダゾリン-2-イル)プロパン〕14.34質量部と濃硫酸11.24質量部を脱イオン水80.00質量部に溶解させたものを、同時に60分間かけてフラスコ中に注入した。85℃で2時間保温し、完全に重合反応させた後に冷却して取り出し、アクリル酸/メタクリル酸共重合体を得た。その不揮発分を測定したところ、40質量%であった。
また、得られたアクリル酸/メタクリル酸共重合体の分子量を前記の方法にて測定を行ったところ、その重量平均分子量は9,100(ポリエチレングリコール換算値)であった。
不揮発分が40%の前記アクリル酸/メタクリル酸共重合体(共重合比:5/95):0.13質量部、リンゴ酸:0.20質量部、水:74.67質量部を撹拌・混合し、目視にてアクリル酸/メタクリル酸共重合体(共重合比:5/95)とリンゴ酸の溶解を確認した後、シリカ含有量が20質量%で1次粒子径が40nmである市販のコロイダルシリカ:20.00質量部を添加する。さらに撹拌・混合し、研磨液の色が均一となったところで30%過酸化水素水:5.00質量部を添加、撹拌・混合し、研磨液(13)を作製した。
[アクリル酸/メタクリル酸共重合体(共重合比:10/90)の作製]
脱イオン水75.00質量部とイソプロパノール75.00質量部を、0.5リットルの合成用フラスコに投入し、窒素ガス雰囲気下で撹拌しながら80℃に昇温した。
その後、アクリル酸10.39質量部とメタクリル酸111.76質量部を混合したもの及び、2,2´-アゾビス〔2-(2-イミダゾリン-2-イル)プロパン〕14.44質量部と濃硫酸11.32質量部を脱イオン水80.00質量部に溶解させたものを、同時に60分間かけてフラスコ中に注入した。85℃で2時間保温し、完全に重合反応させた後に冷却して取り出し、アクリル酸/メタクリル酸共重合体を得た。その不揮発分を測定したところ、40質量%であった。
また、得られたアクリル酸/メタクリル酸共重合体の分子量を前記の方法にて測定を行ったところ、その重量平均分子量は9,200(ポリエチレングリコール換算値)であった。
脱イオン水115.00質量部とイソプロパノール115.00質量部を0.5リットルの合成用フラスコに投入し、窒素ガス雰囲気下で撹拌しながら80℃に昇温した。
前記で作製した各重合体を含む表2に示す各成分を混合し、比較例1と同様に操作して研磨液(14)~(18)を作製した。なお、研磨液(15)、(17)及び(18)で用いた重合体は市販のものを使用した。具体的には下記の通りである。
アクリル酸/マレイン酸共重合体(共重合比:50/50):BASF社製、製品名Sokalan CP13S、重量平均分子量20,000
ポリマレイン酸:日本油脂株式会社製、製品名PMA-50W、重量平均分子量1,600
ポリアクリル酸:株式会社日本触媒製、製品名アクアリック(登録商標)HL-415、重量平均分子量10,000
実施例1~4及び比較例1~6の研磨液について、参考例1~8と同様に評価を行なった。これら評価結果を表2に示す。
実施例2及び4並びに比較例1の研磨液について、配線金属(銅)及びバリア部(タンタル類)の研磨速度も以下のように測定した。
以下の基板を2cm×2cmの小片に切断した。
ブランケット基板(d):PVD法でタンタル(厚さ:300nm)を形成したシリコン基板。
ブランケット基板(e):PVD法で窒化タンタル(厚さ:200nm)を形成したシリコン基板。
ブランケット基板(f):PVD法で窒化チタン(厚さ:300nm)を形成したシリコン基板。
前記ブランケット基板(c)~(f)を下記条件で研磨した。
(研磨条件)
研磨装置:卓上小型研磨機(日本エンギス株式会社製、商品名:IMPTECH 10 DVT)
研磨布:スウェード状ポリウレタン湿式発泡タイプ研磨布(ニッタ・ハース社製、商品名:Politex)
定盤回転数:160min-1
研磨圧力:30kPa
研磨液の供給量:15mL/min
研磨速度:ブランケット基板(c)~(f)の研磨速度を、シート抵抗測定器(ナプソン株式会社製、商品名:RT-70/RG-7B)を使用して求めた。結果を表3に示す。
2、6 ストッパ
3、9 配線金属
4 シリコン基板
8 バリア金属
5、7 層間絶縁材料
Claims (10)
- ストッパとしての窒化珪素と、配線金属及び絶縁材料とを有し、かつ、前記ストッパより被研磨面側に、前記配線金属の少なくとも一部及び前記絶縁材料の少なくとも一部を有する基板を用意する工程、
前記基板の被研磨面と研磨パッドとの間にCMP研磨液を供給して、前記窒化珪素より被研磨面側に位置する前記配線金属及び前記絶縁材料を研磨する工程及び
前記窒化珪素が露出し、かつ前記窒化珪素が完全に除去される前に、研磨を停止する工程、を有し、
前記CMP研磨液は、
(A)(a)アニオン性であって疎水性置換基を含まないモノマーと、(b)疎水性置換基を含むモノマーとの共重合体、
(B)砥粒、
(C)酸、
(D)酸化剤及び
(E)液状媒体を含有してなり、
前記(B)成分は、CMP研磨液中で+10mV以上のゼータ電位を有し、
前記(A)成分は、(a)と(b)の共重合比((a):(b))が、モル比で25:75~75:25であり、かつ、
pHが5.0以下である、
研磨方法。 - ストッパとしての窒化珪素と、配線金属、バリア金属及び絶縁材料とを有し、かつ、前記ストッパより被研磨面側に、前記配線金属の少なくとも一部、前記バリア金属の少なくとも一部及び前記絶縁材料の少なくとも一部を有する基板を用意する工程、
前記基板の被研磨面と研磨パッドとの間にCMP研磨液を供給して、前記窒化珪素より被研磨面側に位置する前記配線金属、前記バリア金属及び前記絶縁材料を研磨する工程及び
前記窒化珪素が露出し、かつ前記窒化珪素が完全に除去される前に、研磨を停止する工程、を有し、
前記CMP研磨液は、
(A)(a)アニオン性であって疎水性置換基を含まないモノマーと、(b)疎水性置換基を含むモノマーとの共重合体、
(B)砥粒、
(C)酸、
(D)酸化剤及び
(E)液状媒体を含有してなり、
前記(B)成分は、CMP研磨液中で+10mV以上のゼータ電位を有し、
前記(A)成分は、(a)と(b)の共重合比((a):(b))が、モル比で25:75~75:25であり、かつ、
pHが5.0以下である、
研磨方法。 - ストッパとしての窒化珪素と、配線金属、バリア金属、及び絶縁材料とを有し、かつ、前記ストッパより被研磨面側に、前記配線金属の少なくとも一部、前記バリア金属の少なくとも一部及び前記絶縁材料の少なくとも一部を有し、更に、前記窒化珪素、前記絶縁材料、前記バリア金属、前記配線金属を、この順に被研磨面側に積層した部分を有する基板を用意する工程、
前記窒化珪素より被研磨面側に位置する、少なくとも配線金属の一部を除去して前記バリア金属の一部を露出させる第一の研磨工程及び
前記窒化珪素より被研磨面側に位置する、少なくとも、前記バリア金属の一部及び前記絶縁材料の一部をCMPにより除去して、前記窒化珪素を露出させ、かつ前記窒化珪素が完全に除去される前に研磨を停止する第二の研磨工程を含み、
少なくとも前記第二の研磨工程で前記基板の被研磨面と研磨パッドとの間にCMP研磨液を供給する研磨方法であり、
前記CMP研磨液は、
(A)(a)アニオン性であって疎水性置換基を含まないモノマーと、(b)疎水性置換基を含むモノマーとの共重合体、
(B)砥粒、
(C)酸、
(D)酸化剤及び
(E)液状媒体を含有してなり、
前記(B)成分は、CMP研磨液中で+10mV以上のゼータ電位を有し、
前記(A)成分は、(a)と(b)の共重合比((a):(b))が、モル比で25:75~75:25であり、かつ、
pHが5.0以下である、
研磨方法。 - 前記CMP研磨液は、前記窒化珪素の研磨速度に対する前記絶縁材料の研磨速度の比(絶縁材料に対する研磨速度/窒化珪素に対する研磨速度)が、20以上である、請求項1~3のいずれかに記載の研磨方法。
- 前記(a)アニオン性であって疎水性置換基を含まないモノマーがアクリル酸及びマレイン酸からなる群から選択される少なくとも一種である請求項1~3のいずれかに記載の研磨方法。
- 前記(b)疎水性置換基を含むモノマーが、メタクリル酸、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ブチル、2-エチルアクリル酸、2-プロピルアクリル酸及び2-ブチルアクリル酸からなる群から選択される少なくとも一種である請求項1~3のいずれかに記載の研磨方法。
- 前記(A)成分が、アクリル酸とメタクリル酸との共重合体である請求項1~3のいずれかに記載の研磨方法。
- (B)成分が、シリカ、アルミナ、セリア、チタニア、ジルコニア、ゲルマニア及びこれらの変性物からなる群から選択される少なくとも一種である請求項1~3のいずれかに記載の研磨方法。
- (C)成分が有機酸である請求項1~3のいずれかに記載の研磨方法。
- 前記CMP研磨液が、(F)成分として、金属防食剤をさらに含有する請求項1~3のいずれかに記載の研磨方法。
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US9299573B2 (en) | 2016-03-29 |
CN104170065A (zh) | 2014-11-26 |
US20150031205A1 (en) | 2015-01-29 |
CN104170065B (zh) | 2016-09-07 |
SG11201405708VA (en) | 2014-11-27 |
KR20140135743A (ko) | 2014-11-26 |
JPWO2013137220A1 (ja) | 2015-08-03 |
TW201343886A (zh) | 2013-11-01 |
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