WO2019131762A1 - Abrasive composition and method for adjusting abrasion rate - Google Patents
Abrasive composition and method for adjusting abrasion rate Download PDFInfo
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- WO2019131762A1 WO2019131762A1 PCT/JP2018/047847 JP2018047847W WO2019131762A1 WO 2019131762 A1 WO2019131762 A1 WO 2019131762A1 JP 2018047847 W JP2018047847 W JP 2018047847W WO 2019131762 A1 WO2019131762 A1 WO 2019131762A1
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- WIPO (PCT)
- Prior art keywords
- polishing
- copper
- polishing composition
- resin
- alumina
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims description 7
- 238000005299 abrasion Methods 0.000 title 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000010949 copper Substances 0.000 claims abstract description 45
- 229910052802 copper Inorganic materials 0.000 claims abstract description 45
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims abstract description 42
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 34
- 239000011347 resin Substances 0.000 claims abstract description 27
- 229920005989 resin Polymers 0.000 claims abstract description 27
- 239000004471 Glycine Substances 0.000 claims abstract description 21
- 239000006061 abrasive grain Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005498 polishing Methods 0.000 claims description 125
- 239000003945 anionic surfactant Substances 0.000 claims description 18
- 150000004996 alkyl benzenes Chemical group 0.000 claims description 8
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 5
- GNDACSNQMTVQHU-UHFFFAOYSA-N 2-aminoacetic acid;hydrogen peroxide Chemical compound OO.NCC(O)=O GNDACSNQMTVQHU-UHFFFAOYSA-N 0.000 claims 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 229920001721 polyimide Polymers 0.000 description 7
- 230000003746 surface roughness Effects 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
- 239000002518 antifoaming agent Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000009719 polyimide resin Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- -1 C20 alkyl benzene Chemical class 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000003082 abrasive agent Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- BTMZHHCFEOXAAN-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;2-dodecylbenzenesulfonic acid Chemical compound OCCN(CCO)CCO.CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O BTMZHHCFEOXAAN-UHFFFAOYSA-N 0.000 description 1
- UAZLASMTBCLJKO-UHFFFAOYSA-N 2-decylbenzenesulfonic acid Chemical compound CCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O UAZLASMTBCLJKO-UHFFFAOYSA-N 0.000 description 1
- PVXSFEGIHWMAOD-UHFFFAOYSA-N 2-tridecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O PVXSFEGIHWMAOD-UHFFFAOYSA-N 0.000 description 1
- UCDCOJNNUVYFKJ-UHFFFAOYSA-N 4-undecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCC1=CC=C(S(O)(=O)=O)C=C1 UCDCOJNNUVYFKJ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 238000001139 pH measurement Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- JZALLXAUNPOCEU-UHFFFAOYSA-N tetradecylbenzene Chemical compound CCCCCCCCCCCCCCC1=CC=CC=C1 JZALLXAUNPOCEU-UHFFFAOYSA-N 0.000 description 1
- 229910000597 tin-copper alloy Inorganic materials 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Images
Classifications
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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
- C09G1/02—Polishing compositions containing abrasives or grinding agents
-
- 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
-
- 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
- B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
- B24B37/042—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor
- B24B37/044—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor characterised by the composition of the lapping agent
-
- 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
-
- 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
- C09K3/1409—Abrasive particles per se
-
- 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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/26—Cleaning or polishing of the conductive pattern
Definitions
- the present invention relates to a polishing composition and a method of adjusting a polishing rate using the polishing composition.
- a conductive layer is formed by laminating a wiring made of copper or a copper alloy on an insulating substrate made of a resin.
- a polishing composition for polishing copper or a copper alloy for example, a polishing composition including abrasive grains such as colloidal silica, a copper complexing agent, triethanolamine alkylbenzene sulfonate, and water is known ( Patent Document 1).
- the present invention has been made in view of such a current situation, and an object of the present invention is to provide a polishing composition capable of adjusting the polishing rate of copper or copper alloy to the polishing rate of resin.
- the present inventors adjust the content of glycine when simultaneously polishing a copper or copper alloy and a resin using a polishing composition containing alumina abrasive grains, glycine, hydrogen peroxide water and water. It has been found that the polishing rate of copper or copper alloy can be adjusted relative to the polishing rate of the resin.
- the gist of the present invention is as follows.
- the polishing composition according to the present invention is a polishing composition for polishing a copper or copper alloy and a resin, and comprises alumina abrasive grains, glycine, a hydrogen peroxide solution, and water.
- the polishing composition according to the present invention preferably further contains an anionic surfactant.
- the anionic surfactant is preferably an alkylbenzene sulfonic acid.
- the polishing composition according to the present invention preferably has a pH of 7.0 or more and 11.0 or less.
- the method of adjusting the polishing rate according to the present invention adjusts the polishing rate of copper or copper alloy relative to the polishing rate of a resin by adjusting the content of glycine using the polishing composition according to the present invention.
- a polishing composition according to an embodiment of the present invention comprises alumina abrasive, glycine, hydrogen peroxide water and water.
- the polishing composition according to the present embodiment contains alumina abrasive grains.
- the alumina abrasive is not particularly limited, and can be appropriately selected from various known alumina particles. Examples of such known alumina particles include ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, ⁇ -alumina and the like.
- alumina called fumed alumina typically alumina fine particles produced when firing alumina salt at high temperature
- alumina called colloidal alumina or alumina sol eg boehmite etc.
- Alumina hydrate is also included in the examples of the known alumina particles. These alumina particles may be used alone or in combination of two or more.
- the content of the alumina abrasive in the polishing composition is preferably 0.3% by mass or more, and more preferably 5.0% by mass or less.
- the content of the alumina abrasive is more preferably 1.0% by mass or more, and more preferably 3.0% by mass or less.
- content of the said alumina abrasives be the total content of the said alumina abrasives.
- the polishing composition according to the present embodiment contains glycine. Since the polishing composition contains a hydrogen peroxide solution described later, the polishing rate of copper or copper alloy relative to the polishing rate of the resin can be adjusted by adjusting the content of glycine. Glycine can also reduce the surface roughness after polishing of copper or copper alloy.
- the content of glycine in the polishing composition is preferably 0.3% by mass or more, and more preferably 15.0% by mass or less.
- polishing of copper or copper alloy can be reduced more as content of the said glycine is the said range.
- content of the said glycine it is more preferable that it is 0.4 mass% or more, and it is more preferable that it is 5.0 mass% or less.
- the polishing composition according to the present embodiment contains a hydrogen peroxide solution.
- the content of the hydrogen peroxide solution in the polishing composition is preferably 0.1% by mass or more from the viewpoint of precisely adjusting the polishing rate of copper or copper alloy to the polishing rate of the resin, It is preferable that it is 0 mass% or less.
- the polishing composition according to the present embodiment may contain an anionic surfactant, if necessary.
- the anionic surfactant include polyacrylic acid, alkyl benzene sulfonic acid, alkane sulfonic acid and ⁇ -olefin sulfonic acid, and salts thereof. Among these, alkyl benzene sulfonic acid or a salt thereof is preferable. These anionic surfactants may be used alone or in combination of two or more.
- alkyl benzene sulfonic acid examples include C6 to C20 alkyl benzene sulfonic acid, and specifically, decyl benzene sulfonic acid, undecyl benzene sulfonic acid, dodecyl benzene sulfonic acid, tridecyl benzene sulfonic acid, tetradecyl benzene A sulfonic acid etc. are mentioned. Among these, dodecylbenzenesulfonic acid is preferable from the viewpoint of the adsorption rate to the surface of copper or copper alloy and the easiness of polishing. Further, as the alkylbenzene sulfonate, for example, sodium alkylbenzene sulfonate, triethanolamine alkylbenzene sulfonate and the like can be mentioned.
- the polishing composition according to the present embodiment may increase the polishing rate of the copper or copper alloy with respect to the polishing rate of the resin by including glycine.
- the polishing composition according to the present embodiment includes the anionic surfactant, whereby the anionic surfactant adsorbs to the surface of the copper or copper alloy during polishing to protect the copper or copper alloy. Do.
- the anionic surfactant adsorbs to the surface of the alumina abrasive grains to form clusters, thereby improving the dispersibility of the alumina abrasive grains.
- the polishing composition can be uniformly supplied on the polishing pad. Further, the particle diameter of the formed cluster is larger than the particle diameter of the alumina. Thereby, the polishing rate of resin can be improved.
- the content of the anionic surfactant in the polishing composition is preferably 0.3% by mass or more, and more preferably 3.0% by mass or less.
- content of the anionic surfactant it is more preferable that it is 0.5 mass% or more, and it is more preferable that it is 1.5 mass% or less.
- content of the said anionic surfactant be the total content of the said anionic surfactant.
- alumina abrasive grains, glycine and a surfactant are dissolved or suspended in water.
- water it is preferable to use water having few impurities such as ion-exchanged water so as not to inhibit various actions of alumina abrasive grains, glycine and surfactant.
- the polishing composition according to the present embodiment may contain an antifoaming agent, if necessary. According to such a configuration, foaming of the polishing composition can be suppressed, and copper or copper alloy and resin can be polished more uniformly.
- the antifoaming agent include silicone emulsions and nonionic surfactants.
- the content of the antifoaming agent in the polishing composition is preferably 0.05% by mass or more, and preferably 0.3% by mass or less.
- the polishing composition according to the present embodiment preferably has a pH of 7.0 or more and 11.0 or less. According to such a configuration, the mechanical polishing power to the resin can be improved, and the polishing rate of the resin can be improved. On the other hand, for copper or copper alloy, an increase in polishing rate of the copper or copper alloy can be suppressed by the adsorption of the anionic surfactant on the surface of the copper or copper alloy.
- the polishing composition according to the present embodiment may contain a pH adjuster, if necessary.
- the pH adjuster include acids such as organic acids and inorganic acids, inorganic bases such as ammonia and KOH, and organic bases such as tetramethyl ammonium hydroxide (TMAH).
- polishing composition according to the present invention is not limited to the above embodiment.
- the polishing composition according to the present invention is not limited to the above-described effects.
- the polishing composition according to the present invention can be variously modified without departing from the scope of the present invention.
- the polishing composition according to the present embodiment polishes copper or a copper alloy and a resin.
- the copper or copper alloy include copper, tin-copper alloy, nickel-copper alloy and the like.
- a resin an epoxy resin, a phenol resin, a polyimide resin etc. are mentioned, for example.
- Examples of the object to be polished by the polishing composition according to this embodiment include a printed circuit board containing copper or copper alloy and a resin, a module board, a package board, and the like.
- the method of adjusting the polishing rate according to the present embodiment adjusts the polishing rate of copper or copper alloy relative to the polishing rate of resin by adjusting the content of glycine using the above-mentioned polishing composition.
- Such a configuration makes it possible to easily adjust the polishing rate of copper or copper alloy to the polishing rate of resin.
- Polishing compositions A to I having the compositions shown in Table 1 and polishing compositions a to e (comparative examples) having the compositions shown in Table 2 were produced.
- the polishing compositions a to e having the compositions shown in Table 2 were the same as the polishing compositions A to E having the compositions shown in Table 1 except that the water content was increased instead of containing no hydrogen peroxide solution. It is. Details of each component are shown below.
- Alumina abrasive grain A9225 (manufactured by Saint-Gobain Co., Ltd.)
- Glycine manufactured by Sakai Chemical Industry Co., Ltd.
- LAS triethanolamine dodecylbenzenesulfonic acid (manufactured by Toho Chemical Industry Co., Ltd.) Silicone antifoaming agent: silicone emulsion (manufactured by Senka Co., Ltd.) KOH: Toagosei Co., Ltd. Hydrogen peroxide: Kanto Chemical Co., Ltd. Water: Ion-exchanged water
- the polishing rate of copper to the polishing rate of the polyimide resin can be adjusted according to the content of glycine.
- the increase of the polishing rate of copper with respect to the polishing rate of the polyimide resin can be suppressed by containing LAS.
- polishing compositions a to e containing no hydrogen peroxide solution can not adjust the polishing rate of copper to the polishing rate of the polyimide resin even if the content of glycine is changed. .
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Computer Hardware Design (AREA)
- Mechanical Engineering (AREA)
- Power Engineering (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
This abrasive composition for abrading a resin and copper or a copper alloy, comprises alumina abrasive grains, glycine, hydrogen peroxide water, and water.
Description
本願は、日本国特願２０１７－２５００５０号の優先権を主張し、引用によって本願明細書の記載に組み込まれる。
The present application claims the priority of Japanese Patent Application No. 2017-250050, and is incorporated by reference into the description of the present specification.
本発明は、研磨組成物、及び、該研磨組成物を用いた研磨速度を調整する方法に関する。
The present invention relates to a polishing composition and a method of adjusting a polishing rate using the polishing composition.
近年、プリント基板、モジュール基板、パッケージ基板等の小型化及び高集積化に伴い、配線の微細化及び高密度化が進められている。この配線は、幾重にも重ねられて凹凸が形成されることから、研磨により該凹凸を除去し、平坦にする必要がある。
In recent years, with the miniaturization and high integration of printed circuit boards, module substrates, package substrates and the like, miniaturization and high density of wiring have been promoted. Since this wiring is stacked several times to form asperities, it is necessary to remove the asperities by polishing and to make it flat.
従来、プリント基板等では、樹脂からなる絶縁基板上に銅又は銅合金からなる配線を積層させることにより導電層を形成する。銅又は銅合金を研磨する研磨組成物としては、例えば、コロイダルシリカ等の砥粒と、銅錯化剤と、アルキルベンゼンスルホン酸トリエタノールアミンと、水とを含む研磨組成物が知られている（特許文献１）。
Conventionally, in a printed circuit board or the like, a conductive layer is formed by laminating a wiring made of copper or a copper alloy on an insulating substrate made of a resin. As a polishing composition for polishing copper or a copper alloy, for example, a polishing composition including abrasive grains such as colloidal silica, a copper complexing agent, triethanolamine alkylbenzene sulfonate, and water is known ( Patent Document 1).
最近では、銅又は銅合金を研磨する際、絶縁基板を構成する樹脂も同時に研磨したいという要望がある。特に、樹脂の研磨速度に対する銅又は銅合金の研磨速度を調整しながら、銅又は銅合金と樹脂とを同時に研磨することが望まれている。しかしながら、銅又は銅合金と樹脂とを同時に研磨する研磨組成物について、これまで何ら検討がされていなかった。
Recently, when polishing copper or copper alloy, there is a demand for simultaneously polishing the resin constituting the insulating substrate. In particular, it is desirable to simultaneously polish copper or copper alloy and resin while adjusting the polishing speed of copper or copper alloy to the polishing speed of resin. However, no study has been made on polishing compositions for simultaneously polishing copper or copper alloy and resin.
本発明は、このような現状に鑑みてなされたものであり、樹脂の研磨速度に対する銅又は銅合金の研磨速度を調整することが可能な研磨組成物を提供することを課題とする。
The present invention has been made in view of such a current situation, and an object of the present invention is to provide a polishing composition capable of adjusting the polishing rate of copper or copper alloy to the polishing rate of resin.
本発明者らは、アルミナ砥粒、グリシン、過酸化水素水及び水を含む研磨組成物を用いて銅又は銅合金と樹脂とを同時に研磨する際、前記グリシンの含有量を調整することにより、樹脂の研磨速度に対する銅又は銅合金の研磨速度を調整することができることを見出した。本発明の要旨は、以下の通りである。
The present inventors adjust the content of glycine when simultaneously polishing a copper or copper alloy and a resin using a polishing composition containing alumina abrasive grains, glycine, hydrogen peroxide water and water. It has been found that the polishing rate of copper or copper alloy can be adjusted relative to the polishing rate of the resin. The gist of the present invention is as follows.
本発明に係る研磨組成物は、銅又は銅合金と樹脂とを研磨する研磨組成物であって、アルミナ砥粒と、グリシンと、過酸化水素水と、水と、を含む。
The polishing composition according to the present invention is a polishing composition for polishing a copper or copper alloy and a resin, and comprises alumina abrasive grains, glycine, a hydrogen peroxide solution, and water.
本発明に係る研磨組成物は、さらに、アニオン界面活性剤を含有することが好ましい。
The polishing composition according to the present invention preferably further contains an anionic surfactant.
本発明に係る研磨組成物は、前記アニオン界面活性剤が、アルキルベンゼンスルホン酸であることが好ましい。
In the polishing composition according to the present invention, the anionic surfactant is preferably an alkylbenzene sulfonic acid.
本発明に係る研磨組成物は、ｐＨが、７．０以上１１．０以下であることが好ましい。
The polishing composition according to the present invention preferably has a pH of 7.0 or more and 11.0 or less.
本発明に係る研磨速度を調整する方法は、本発明に係る研磨組成物を用いて、前記グリシンの含有量を調整することにより、樹脂の研磨速度に対する銅又は銅合金の研磨速度を調整する。
The method of adjusting the polishing rate according to the present invention adjusts the polishing rate of copper or copper alloy relative to the polishing rate of a resin by adjusting the content of glycine using the polishing composition according to the present invention.
以下、本発明の実施形態に係る研磨組成物について説明する。
Hereinafter, a polishing composition according to an embodiment of the present invention will be described.
＜研磨組成物＞
本発明の実施形態に係る研磨組成物は、アルミナ砥粒、グリシン、過酸化水素水及び水を含む。 <Abrasive composition>
A polishing composition according to an embodiment of the present invention comprises alumina abrasive, glycine, hydrogen peroxide water and water.
本発明の実施形態に係る研磨組成物は、アルミナ砥粒、グリシン、過酸化水素水及び水を含む。 <Abrasive composition>
A polishing composition according to an embodiment of the present invention comprises alumina abrasive, glycine, hydrogen peroxide water and water.
（アルミナ砥粒）
本実施形態に係る研磨組成物は、アルミナ砥粒を含有する。前記アルミナ砥粒としては、特に限定されるものではなく、公知の各種アルミナ粒子の中から適宜選択して用いることができる。このような公知のアルミナ粒子としては、例えば、α－アルミナ、γ－アルミナ、δ－アルミナ、θ－アルミナ、η－アルミナ、κ－アルミナ、χ－アルミナ等が挙げられる。また、製法による分類に基づき、ヒュームドアルミナと称されるアルミナ（典型的にはアルミナ塩を高温焼成する際に生産されるアルミナ微粒子）、コロイダルアルミナ又はアルミナゾルと称されるアルミナ（例えばベーマイト等のアルミナ水和物）も、前記公知のアルミナ粒子の例に含まれる。これらのアルミナ粒子は、単独で用いても、２種以上を組み合わせて用いてもよい。 (Alumina abrasive grains)
The polishing composition according to the present embodiment contains alumina abrasive grains. The alumina abrasive is not particularly limited, and can be appropriately selected from various known alumina particles. Examples of such known alumina particles include α-alumina, γ-alumina, δ-alumina, θ-alumina, η-alumina, κ-alumina, χ-alumina and the like. Also, based on classification according to production method, alumina called fumed alumina (typically alumina fine particles produced when firing alumina salt at high temperature), alumina called colloidal alumina or alumina sol (eg boehmite etc.) Alumina hydrate) is also included in the examples of the known alumina particles. These alumina particles may be used alone or in combination of two or more.
本実施形態に係る研磨組成物は、アルミナ砥粒を含有する。前記アルミナ砥粒としては、特に限定されるものではなく、公知の各種アルミナ粒子の中から適宜選択して用いることができる。このような公知のアルミナ粒子としては、例えば、α－アルミナ、γ－アルミナ、δ－アルミナ、θ－アルミナ、η－アルミナ、κ－アルミナ、χ－アルミナ等が挙げられる。また、製法による分類に基づき、ヒュームドアルミナと称されるアルミナ（典型的にはアルミナ塩を高温焼成する際に生産されるアルミナ微粒子）、コロイダルアルミナ又はアルミナゾルと称されるアルミナ（例えばベーマイト等のアルミナ水和物）も、前記公知のアルミナ粒子の例に含まれる。これらのアルミナ粒子は、単独で用いても、２種以上を組み合わせて用いてもよい。 (Alumina abrasive grains)
The polishing composition according to the present embodiment contains alumina abrasive grains. The alumina abrasive is not particularly limited, and can be appropriately selected from various known alumina particles. Examples of such known alumina particles include α-alumina, γ-alumina, δ-alumina, θ-alumina, η-alumina, κ-alumina, χ-alumina and the like. Also, based on classification according to production method, alumina called fumed alumina (typically alumina fine particles produced when firing alumina salt at high temperature), alumina called colloidal alumina or alumina sol (eg boehmite etc.) Alumina hydrate) is also included in the examples of the known alumina particles. These alumina particles may be used alone or in combination of two or more.
前記研磨組成物における、前記アルミナ砥粒の含有量は、０．３質量％以上であることが好ましく、５．０質量％以下であることが好ましい。前記アルミナ砥粒の含有量が前記範囲であると、高い研磨性を維持しつつ、保存安定性の低下を抑制することができる。前記アルミナ砥粒の含有量は、１．０質量％以上であることがより好ましく、３．０質量％以下であることがより好ましい。なお、前記アルミナ砥粒が２種以上含まれる場合、前記アルミナ砥粒の含有量は、前記アルミナ砥粒の合計含有量とする。
The content of the alumina abrasive in the polishing composition is preferably 0.3% by mass or more, and more preferably 5.0% by mass or less. When the content of the alumina abrasive grains is in the above range, it is possible to suppress a decrease in storage stability while maintaining high polishing properties. The content of the alumina abrasive is more preferably 1.0% by mass or more, and more preferably 3.0% by mass or less. In addition, when 2 or more types of said alumina abrasives are contained, let content of the said alumina abrasives be the total content of the said alumina abrasives.
（グリシン）
本実施形態に係る研磨組成物は、グリシンを含有する。前記研磨組成物は、後述する過酸化水素水を含むため、グリシンの含有量を調整することにより、樹脂の研磨速度に対する銅又は銅合金の研磨速度を調整することができる。また、グリシンは、銅又は銅合金の研磨後の表面粗さを低減することができる。 (glycine)
The polishing composition according to the present embodiment contains glycine. Since the polishing composition contains a hydrogen peroxide solution described later, the polishing rate of copper or copper alloy relative to the polishing rate of the resin can be adjusted by adjusting the content of glycine. Glycine can also reduce the surface roughness after polishing of copper or copper alloy.
本実施形態に係る研磨組成物は、グリシンを含有する。前記研磨組成物は、後述する過酸化水素水を含むため、グリシンの含有量を調整することにより、樹脂の研磨速度に対する銅又は銅合金の研磨速度を調整することができる。また、グリシンは、銅又は銅合金の研磨後の表面粗さを低減することができる。 (glycine)
The polishing composition according to the present embodiment contains glycine. Since the polishing composition contains a hydrogen peroxide solution described later, the polishing rate of copper or copper alloy relative to the polishing rate of the resin can be adjusted by adjusting the content of glycine. Glycine can also reduce the surface roughness after polishing of copper or copper alloy.
前記研磨組成物における、前記グリシンの含有量は、０．３質量％以上であることが好ましく、１５．０質量％以下であることが好ましい。前記グリシンの含有量が前記範囲であると、銅又は銅合金の研磨後の表面粗さをより低減することができる。前記グリシンの含有量は、０．４質量％以上であることがより好ましく、５．０質量％以下であることがより好ましい。
The content of glycine in the polishing composition is preferably 0.3% by mass or more, and more preferably 15.0% by mass or less. The surface roughness after grinding | polishing of copper or copper alloy can be reduced more as content of the said glycine is the said range. As for content of the said glycine, it is more preferable that it is 0.4 mass% or more, and it is more preferable that it is 5.0 mass% or less.
（過酸化水素水）
本実施形態に係る研磨組成物は、過酸化水素水を含有する。前記研磨組成物における、前記過酸化水素水の含有量は、樹脂の研磨速度に対する銅又は銅合金の研磨速度を精度良く調整する観点から、０．１質量％以上であることが好ましく、３．０質量％以下であることが好ましい。 (Hydrogen peroxide water)
The polishing composition according to the present embodiment contains a hydrogen peroxide solution. The content of the hydrogen peroxide solution in the polishing composition is preferably 0.1% by mass or more from the viewpoint of precisely adjusting the polishing rate of copper or copper alloy to the polishing rate of the resin, It is preferable that it is 0 mass% or less.
本実施形態に係る研磨組成物は、過酸化水素水を含有する。前記研磨組成物における、前記過酸化水素水の含有量は、樹脂の研磨速度に対する銅又は銅合金の研磨速度を精度良く調整する観点から、０．１質量％以上であることが好ましく、３．０質量％以下であることが好ましい。 (Hydrogen peroxide water)
The polishing composition according to the present embodiment contains a hydrogen peroxide solution. The content of the hydrogen peroxide solution in the polishing composition is preferably 0.1% by mass or more from the viewpoint of precisely adjusting the polishing rate of copper or copper alloy to the polishing rate of the resin, It is preferable that it is 0 mass% or less.
（アニオン界面活性剤）
本実施形態に係る研磨組成物は、必要に応じて、アニオン界面活性剤を含んでいてもよい。前記アニオン界面活性剤としては、例えば、ポリアクリル酸、アルキルベンゼンスルホン酸、アルカンスルホン酸及びα－オレフィンスルホン酸、並びに、これらの塩等が挙げられる。これらの中でも、アルキルベンゼンスルホン酸又はその塩であることが好ましい。なお、これらのアニオン界面活性剤は、単独で用いても、２種以上を組み合わせて用いてもよい。 (Anionic surfactant)
The polishing composition according to the present embodiment may contain an anionic surfactant, if necessary. Examples of the anionic surfactant include polyacrylic acid, alkyl benzene sulfonic acid, alkane sulfonic acid and α-olefin sulfonic acid, and salts thereof. Among these, alkyl benzene sulfonic acid or a salt thereof is preferable. These anionic surfactants may be used alone or in combination of two or more.
本実施形態に係る研磨組成物は、必要に応じて、アニオン界面活性剤を含んでいてもよい。前記アニオン界面活性剤としては、例えば、ポリアクリル酸、アルキルベンゼンスルホン酸、アルカンスルホン酸及びα－オレフィンスルホン酸、並びに、これらの塩等が挙げられる。これらの中でも、アルキルベンゼンスルホン酸又はその塩であることが好ましい。なお、これらのアニオン界面活性剤は、単独で用いても、２種以上を組み合わせて用いてもよい。 (Anionic surfactant)
The polishing composition according to the present embodiment may contain an anionic surfactant, if necessary. Examples of the anionic surfactant include polyacrylic acid, alkyl benzene sulfonic acid, alkane sulfonic acid and α-olefin sulfonic acid, and salts thereof. Among these, alkyl benzene sulfonic acid or a salt thereof is preferable. These anionic surfactants may be used alone or in combination of two or more.
前記アルキルベンゼンスルホン酸としては、例えば、Ｃ６からＣ２０のアルキルベンゼンスルホン酸が挙げられ、具体的には、デシルベンゼンスルホン酸、ウンデシルベンゼンスルホン酸、ドデシルベンゼンスルホン酸、トリデシルベンゼンスルホン酸、テトラデシルベンゼンスルホン酸等が挙げられる。これらの中でも、銅又は銅合金の表面への吸着速度及び研磨の容易性の観点から、ドデシルベンゼンスルホン酸であることが好ましい。また、アルキルベンゼンスルホン酸塩としては、例えば、アルキルベンゼンスルホン酸ナトリウム、アルキルベンゼンスルホン酸トリエタノールアミン等が挙げられる。
Examples of the alkyl benzene sulfonic acid include C6 to C20 alkyl benzene sulfonic acid, and specifically, decyl benzene sulfonic acid, undecyl benzene sulfonic acid, dodecyl benzene sulfonic acid, tridecyl benzene sulfonic acid, tetradecyl benzene A sulfonic acid etc. are mentioned. Among these, dodecylbenzenesulfonic acid is preferable from the viewpoint of the adsorption rate to the surface of copper or copper alloy and the easiness of polishing. Further, as the alkylbenzene sulfonate, for example, sodium alkylbenzene sulfonate, triethanolamine alkylbenzene sulfonate and the like can be mentioned.
本実施形態に係る研磨組成物は、グリシンを含むことにより、樹脂の研磨速度に対する前記銅又は銅合金の研磨速度が上昇する場合がある。しかしながら、本実施形態に係る研磨組成物は、アニオン界面活性剤を含むことにより、該アニオン界面活性剤が、研磨の際、銅又は銅合金の表面に吸着して、前記銅又は銅合金を保護する。その結果、樹脂の研磨速度に対する前記銅又は銅合金の研磨速度の上昇を抑制することができる。さらに、前記研磨組成物において、アニオン界面活性剤は、前記アルミナ砥粒表面に吸着することによりクラスターを形成し、前記アルミナ砥粒の分散性を向上させる。これにより、前記アルミナ砥粒の沈降を防ぐことができるため、研磨組成物を研磨パッド上に均一に供給することができる。また、形成された前記クラスターの粒子径は、前記アルミナの粒子径よりも大きくなる。これにより、樹脂の研磨速度を向上させることができる。
The polishing composition according to the present embodiment may increase the polishing rate of the copper or copper alloy with respect to the polishing rate of the resin by including glycine. However, the polishing composition according to the present embodiment includes the anionic surfactant, whereby the anionic surfactant adsorbs to the surface of the copper or copper alloy during polishing to protect the copper or copper alloy. Do. As a result, it is possible to suppress an increase in the polishing rate of the copper or copper alloy with respect to the polishing rate of the resin. Furthermore, in the polishing composition, the anionic surfactant adsorbs to the surface of the alumina abrasive grains to form clusters, thereby improving the dispersibility of the alumina abrasive grains. Thereby, since the sedimentation of the alumina abrasive can be prevented, the polishing composition can be uniformly supplied on the polishing pad. Further, the particle diameter of the formed cluster is larger than the particle diameter of the alumina. Thereby, the polishing rate of resin can be improved.
前記研磨組成物における、前記アニオン界面活性剤の含有量は、０．３質量％以上であることが好ましく、３．０質量％以下であることが好ましい。前記アニオン界面活性剤の含有量が前記範囲であると、樹脂の研磨速度に対する銅又は銅合金の研磨速度の上昇をより抑制することができる。前記アニオン界面活性剤の含有量は、０．５質量％以上であることがより好ましく、１．５質量％以下であることがより好ましい。なお、前記アニオン界面活性剤が２種以上含まれる場合、前記アニオン界面活性剤の含有量は、前記アニオン界面活性剤の合計含有量とする。
The content of the anionic surfactant in the polishing composition is preferably 0.3% by mass or more, and more preferably 3.0% by mass or less. When the content of the anionic surfactant is in the above range, it is possible to further suppress an increase in the polishing rate of the copper or copper alloy with respect to the polishing rate of the resin. As for content of the said anionic surfactant, it is more preferable that it is 0.5 mass% or more, and it is more preferable that it is 1.5 mass% or less. In addition, when 2 or more types of said anionic surfactant are contained, let content of the said anionic surfactant be the total content of the said anionic surfactant.
（水）
本実施形態に係る研磨組成物は、アルミナ砥粒、グリシン及び界面活性剤が水に溶解又は懸濁されている。前記水は、アルミナ砥粒、グリシン及び界面活性剤の各種作用を阻害しないように、イオン交換水等の不純物が少ないものを用いることが好ましい。 (water)
In the polishing composition according to this embodiment, alumina abrasive grains, glycine and a surfactant are dissolved or suspended in water. As the water, it is preferable to use water having few impurities such as ion-exchanged water so as not to inhibit various actions of alumina abrasive grains, glycine and surfactant.
本実施形態に係る研磨組成物は、アルミナ砥粒、グリシン及び界面活性剤が水に溶解又は懸濁されている。前記水は、アルミナ砥粒、グリシン及び界面活性剤の各種作用を阻害しないように、イオン交換水等の不純物が少ないものを用いることが好ましい。 (water)
In the polishing composition according to this embodiment, alumina abrasive grains, glycine and a surfactant are dissolved or suspended in water. As the water, it is preferable to use water having few impurities such as ion-exchanged water so as not to inhibit various actions of alumina abrasive grains, glycine and surfactant.
（消泡剤）
本実施形態に係る研磨組成物は、必要に応じて、消泡剤を含んでいてもよい。斯かる構成により、研磨組成物の泡立ちを抑制し、銅又は銅合金及び樹脂をより均一に研磨することができる。前記消泡剤としては、例えば、シリコーンエマルジョン、ノニオン系界面活性剤等が挙げられる。前記研磨組成物における、前記消泡剤の含有量は、０．０５質量％以上であることが好ましく、０．３質量％以下であることが好ましい。 (Defoamer)
The polishing composition according to the present embodiment may contain an antifoaming agent, if necessary. According to such a configuration, foaming of the polishing composition can be suppressed, and copper or copper alloy and resin can be polished more uniformly. Examples of the antifoaming agent include silicone emulsions and nonionic surfactants. The content of the antifoaming agent in the polishing composition is preferably 0.05% by mass or more, and preferably 0.3% by mass or less.
本実施形態に係る研磨組成物は、必要に応じて、消泡剤を含んでいてもよい。斯かる構成により、研磨組成物の泡立ちを抑制し、銅又は銅合金及び樹脂をより均一に研磨することができる。前記消泡剤としては、例えば、シリコーンエマルジョン、ノニオン系界面活性剤等が挙げられる。前記研磨組成物における、前記消泡剤の含有量は、０．０５質量％以上であることが好ましく、０．３質量％以下であることが好ましい。 (Defoamer)
The polishing composition according to the present embodiment may contain an antifoaming agent, if necessary. According to such a configuration, foaming of the polishing composition can be suppressed, and copper or copper alloy and resin can be polished more uniformly. Examples of the antifoaming agent include silicone emulsions and nonionic surfactants. The content of the antifoaming agent in the polishing composition is preferably 0.05% by mass or more, and preferably 0.3% by mass or less.
（ｐＨ調整剤）
本実施形態に係る研磨組成物は、ｐＨが、７．０以上１１．０以下であることが好ましい。斯かる構成により、樹脂に対する機械的研磨力が向上し、樹脂の研磨速度を向上させることができる。一方、銅又は銅合金に対しては、前記銅又は銅合金の表面にアニオン界面活性剤が吸着することにより、前記銅又は銅合金の研磨速度の上昇を抑制することができる。ｐＨを前記範囲に調整するため、本実施形態に係る研磨組成物は、必要に応じて、ｐＨ調整剤を含んでいてもよい。前記ｐＨ調整剤としては、例えば、有機酸、無機酸等の酸、アンモニア、ＫＯＨ等の無機塩基、水酸化テトラメチルアンモニウム（ＴＭＡＨ）等の有機塩基等が挙げられる。 (PH adjuster)
The polishing composition according to the present embodiment preferably has a pH of 7.0 or more and 11.0 or less. According to such a configuration, the mechanical polishing power to the resin can be improved, and the polishing rate of the resin can be improved. On the other hand, for copper or copper alloy, an increase in polishing rate of the copper or copper alloy can be suppressed by the adsorption of the anionic surfactant on the surface of the copper or copper alloy. In order to adjust the pH to the above-mentioned range, the polishing composition according to the present embodiment may contain a pH adjuster, if necessary. Examples of the pH adjuster include acids such as organic acids and inorganic acids, inorganic bases such as ammonia and KOH, and organic bases such as tetramethyl ammonium hydroxide (TMAH).
本実施形態に係る研磨組成物は、ｐＨが、７．０以上１１．０以下であることが好ましい。斯かる構成により、樹脂に対する機械的研磨力が向上し、樹脂の研磨速度を向上させることができる。一方、銅又は銅合金に対しては、前記銅又は銅合金の表面にアニオン界面活性剤が吸着することにより、前記銅又は銅合金の研磨速度の上昇を抑制することができる。ｐＨを前記範囲に調整するため、本実施形態に係る研磨組成物は、必要に応じて、ｐＨ調整剤を含んでいてもよい。前記ｐＨ調整剤としては、例えば、有機酸、無機酸等の酸、アンモニア、ＫＯＨ等の無機塩基、水酸化テトラメチルアンモニウム（ＴＭＡＨ）等の有機塩基等が挙げられる。 (PH adjuster)
The polishing composition according to the present embodiment preferably has a pH of 7.0 or more and 11.0 or less. According to such a configuration, the mechanical polishing power to the resin can be improved, and the polishing rate of the resin can be improved. On the other hand, for copper or copper alloy, an increase in polishing rate of the copper or copper alloy can be suppressed by the adsorption of the anionic surfactant on the surface of the copper or copper alloy. In order to adjust the pH to the above-mentioned range, the polishing composition according to the present embodiment may contain a pH adjuster, if necessary. Examples of the pH adjuster include acids such as organic acids and inorganic acids, inorganic bases such as ammonia and KOH, and organic bases such as tetramethyl ammonium hydroxide (TMAH).
なお、本発明に係る研磨組成物は、前記実施形態に限定されるものではない。また、本発明に係る研磨組成物は、上述の作用効果に限定されるものでもない。本発明に係る研磨組成物は、本発明の要旨を逸脱しない範囲で種々の変更が可能である。
The polishing composition according to the present invention is not limited to the above embodiment. In addition, the polishing composition according to the present invention is not limited to the above-described effects. The polishing composition according to the present invention can be variously modified without departing from the scope of the present invention.
＜研磨対象物＞
本実施形態に係る研磨組成物は、銅又は銅合金と樹脂とを研磨する。前記銅又は銅合金としては、例えば、銅、錫－銅合金、ニッケル－銅合金等が挙げられる。また、前記樹脂としては、例えば、エポキシ樹脂、フェノール樹脂、ポリイミド樹脂等が挙げられる。 <Polished object>
The polishing composition according to the present embodiment polishes copper or a copper alloy and a resin. Examples of the copper or copper alloy include copper, tin-copper alloy, nickel-copper alloy and the like. Moreover, as said resin, an epoxy resin, a phenol resin, a polyimide resin etc. are mentioned, for example.
本実施形態に係る研磨組成物は、銅又は銅合金と樹脂とを研磨する。前記銅又は銅合金としては、例えば、銅、錫－銅合金、ニッケル－銅合金等が挙げられる。また、前記樹脂としては、例えば、エポキシ樹脂、フェノール樹脂、ポリイミド樹脂等が挙げられる。 <Polished object>
The polishing composition according to the present embodiment polishes copper or a copper alloy and a resin. Examples of the copper or copper alloy include copper, tin-copper alloy, nickel-copper alloy and the like. Moreover, as said resin, an epoxy resin, a phenol resin, a polyimide resin etc. are mentioned, for example.
本実施形態に係る研磨組成物で研磨する研磨対象物としては、銅又は銅合金と樹脂とを含むプリント基板、モジュール基板、パッケージ基板等が挙げられる。
Examples of the object to be polished by the polishing composition according to this embodiment include a printed circuit board containing copper or copper alloy and a resin, a module board, a package board, and the like.
＜研磨速度を調整する方法＞
本実施形態に係る研磨速度を調整する方法は、上述の研磨組成物を用いて、グリシンの含有量を調整することにより、樹脂の研磨速度に対する銅又は銅合金の研磨速度を調整する。斯かる構成により、樹脂の研磨速度に対する銅又は銅合金の研磨速度を容易に調整することができる。 <Method to adjust the polishing rate>
The method of adjusting the polishing rate according to the present embodiment adjusts the polishing rate of copper or copper alloy relative to the polishing rate of resin by adjusting the content of glycine using the above-mentioned polishing composition. Such a configuration makes it possible to easily adjust the polishing rate of copper or copper alloy to the polishing rate of resin.
本実施形態に係る研磨速度を調整する方法は、上述の研磨組成物を用いて、グリシンの含有量を調整することにより、樹脂の研磨速度に対する銅又は銅合金の研磨速度を調整する。斯かる構成により、樹脂の研磨速度に対する銅又は銅合金の研磨速度を容易に調整することができる。 <Method to adjust the polishing rate>
The method of adjusting the polishing rate according to the present embodiment adjusts the polishing rate of copper or copper alloy relative to the polishing rate of resin by adjusting the content of glycine using the above-mentioned polishing composition. Such a configuration makes it possible to easily adjust the polishing rate of copper or copper alloy to the polishing rate of resin.
以下、本発明の実施例について説明するが、本発明は、以下の実施例に限定されるものではない。
Examples of the present invention will be described below, but the present invention is not limited to the following examples.
＜研磨組成物の調整＞
表１に示す組成の研磨組成物Ａ～Ｉ（実施例）、及び、表２に示す組成の研磨組成物ａ～ｅ（比較例）を作製した。表２に示す組成の研磨組成物ａ～ｅは、過酸化水素水を含まない代わりに水の含有量を増やしたこと以外は、それぞれ、表１に示す組成の研磨組成物Ａ～Ｅと同様である。各成分の詳細を以下に示す。
アルミナ砥粒：Ａ９２２５（サンゴバン（株）製）
グリシン：扶桑化学工業（株）製
ＬＡＳ：ドデシルベンゼンスルホン酸トリエタノールアミン（東邦化学工業（株）製）
シリコーン系消泡剤：シリコーンエマルジョン（センカ（株）製）
ＫＯＨ：東亞合成（株）製
過酸化水素水：関東化学（株）製
水：イオン交換水 <Preparation of Abrasive Composition>
Polishing compositions A to I (examples) having the compositions shown in Table 1 and polishing compositions a to e (comparative examples) having the compositions shown in Table 2 were produced. The polishing compositions a to e having the compositions shown in Table 2 were the same as the polishing compositions A to E having the compositions shown in Table 1 except that the water content was increased instead of containing no hydrogen peroxide solution. It is. Details of each component are shown below.
Alumina abrasive grain: A9225 (manufactured by Saint-Gobain Co., Ltd.)
Glycine: manufactured by Sakai Chemical Industry Co., Ltd. LAS: triethanolamine dodecylbenzenesulfonic acid (manufactured by Toho Chemical Industry Co., Ltd.)
Silicone antifoaming agent: silicone emulsion (manufactured by Senka Co., Ltd.)
KOH: Toagosei Co., Ltd. Hydrogen peroxide: Kanto Chemical Co., Ltd. Water: Ion-exchanged water
表１に示す組成の研磨組成物Ａ～Ｉ（実施例）、及び、表２に示す組成の研磨組成物ａ～ｅ（比較例）を作製した。表２に示す組成の研磨組成物ａ～ｅは、過酸化水素水を含まない代わりに水の含有量を増やしたこと以外は、それぞれ、表１に示す組成の研磨組成物Ａ～Ｅと同様である。各成分の詳細を以下に示す。
アルミナ砥粒：Ａ９２２５（サンゴバン（株）製）
グリシン：扶桑化学工業（株）製
ＬＡＳ：ドデシルベンゼンスルホン酸トリエタノールアミン（東邦化学工業（株）製）
シリコーン系消泡剤：シリコーンエマルジョン（センカ（株）製）
ＫＯＨ：東亞合成（株）製
過酸化水素水：関東化学（株）製
水：イオン交換水 <Preparation of Abrasive Composition>
Polishing compositions A to I (examples) having the compositions shown in Table 1 and polishing compositions a to e (comparative examples) having the compositions shown in Table 2 were produced. The polishing compositions a to e having the compositions shown in Table 2 were the same as the polishing compositions A to E having the compositions shown in Table 1 except that the water content was increased instead of containing no hydrogen peroxide solution. It is. Details of each component are shown below.
Alumina abrasive grain: A9225 (manufactured by Saint-Gobain Co., Ltd.)
Glycine: manufactured by Sakai Chemical Industry Co., Ltd. LAS: triethanolamine dodecylbenzenesulfonic acid (manufactured by Toho Chemical Industry Co., Ltd.)
Silicone antifoaming agent: silicone emulsion (manufactured by Senka Co., Ltd.)
KOH: Toagosei Co., Ltd. Hydrogen peroxide: Kanto Chemical Co., Ltd. Water: Ion-exchanged water
＜ｐＨの測定＞
各研磨組成物のｐＨは、ｐＨメーターを用いて測定した。 <Measurement of pH>
The pH of each polishing composition was measured using a pH meter.
各研磨組成物のｐＨは、ｐＨメーターを用いて測定した。 <Measurement of pH>
The pH of each polishing composition was measured using a pH meter.
＜研磨速度の測定＞
各研磨組成物を用いて、下記条件で被研磨物を研磨し、研磨速度を求めた。結果を表１及び２、並びに、図１及び２に示す。
被研磨物：ポリイミド（シリコンウェハに成膜）、銅（シリコンウェハにメッキ）
研磨機：ＦＲＥＸ（（株）荏原製作所製）
研磨圧：３ｐｓｉ
スラリー流量：３００ｍＬ／ｍｉｎ
プラテン回転数／キャリア回転数：１０３ｒｐｍ／９７ｒｐｍ
研磨時間：１ｍｉｎ
研磨パッド：ＩＣ１０００（ニッタ・ハース（株）製） <Measurement of polishing rate>
An object to be polished was polished using the respective polishing compositions under the following conditions, and the polishing rate was determined. The results are shown in Tables 1 and 2 and in FIGS.
Object to be polished: polyimide (deposited on silicon wafer), copper (plated on silicon wafer)
Polishing machine: FREX (manufactured by Ebara Corporation)
Polishing pressure: 3 psi
Slurry flow rate: 300 mL / min
Platen rotation speed / Carrier rotation speed: 103rpm / 97rpm
Polishing time: 1 min
Polishing pad: IC 1000 (manufactured by Nitta Haas Co., Ltd.)
各研磨組成物を用いて、下記条件で被研磨物を研磨し、研磨速度を求めた。結果を表１及び２、並びに、図１及び２に示す。
被研磨物：ポリイミド（シリコンウェハに成膜）、銅（シリコンウェハにメッキ）
研磨機：ＦＲＥＸ（（株）荏原製作所製）
研磨圧：３ｐｓｉ
スラリー流量：３００ｍＬ／ｍｉｎ
プラテン回転数／キャリア回転数：１０３ｒｐｍ／９７ｒｐｍ
研磨時間：１ｍｉｎ
研磨パッド：ＩＣ１０００（ニッタ・ハース（株）製） <Measurement of polishing rate>
An object to be polished was polished using the respective polishing compositions under the following conditions, and the polishing rate was determined. The results are shown in Tables 1 and 2 and in FIGS.
Object to be polished: polyimide (deposited on silicon wafer), copper (plated on silicon wafer)
Polishing machine: FREX (manufactured by Ebara Corporation)
Polishing pressure: 3 psi
Slurry flow rate: 300 mL / min
Platen rotation speed / Carrier rotation speed: 103rpm / 97rpm
Polishing time: 1 min
Polishing pad: IC 1000 (manufactured by Nitta Haas Co., Ltd.)
＜表面粗さの測定＞
各研磨組成物を用いて銅を研磨した後、非接触表面粗さ測定器（Ｗｙｋｏ ＮＴ９３００、Ｖｅｅｃｏ社製）を用いて、銅の表面粗さＲａを測定した。測定結果を表１及び２、並びに、図１及び２に示す。 <Measurement of surface roughness>
After copper was polished using each polishing composition, the surface roughness Ra of copper was measured using a noncontact surface roughness tester (Wyko NT9300, manufactured by Veeco). The measurement results are shown in Tables 1 and 2 and FIGS. 1 and 2.
各研磨組成物を用いて銅を研磨した後、非接触表面粗さ測定器（Ｗｙｋｏ ＮＴ９３００、Ｖｅｅｃｏ社製）を用いて、銅の表面粗さＲａを測定した。測定結果を表１及び２、並びに、図１及び２に示す。 <Measurement of surface roughness>
After copper was polished using each polishing composition, the surface roughness Ra of copper was measured using a noncontact surface roughness tester (Wyko NT9300, manufactured by Veeco). The measurement results are shown in Tables 1 and 2 and FIGS. 1 and 2.
＜分散安定性の評価＞
各研磨組成物１００ｍｌを、側面が透明又は半透明であるプラスチック容器に取り分けて充分に撹拌した後、室温で１０分間静置することにより、各研磨組成物のスラリーを得た。そして、各スラリーを目視観察することにより、分散安定性の評価を行った。評価基準は以下の通りである。評価結果を表１に示す。
○：砥粒が容器下部に沈降した様子が観察されない。
×：砥粒が容器下部に沈降している様子が観察される。 <Evaluation of dispersion stability>
The slurry of each polishing composition was obtained by dividing 100 ml of each polishing composition into a plastic container whose side is transparent or translucent and sufficiently stirring, and then standing at room temperature for 10 minutes. And evaluation of dispersion stability was performed by visually observing each slurry. Evaluation criteria are as follows. The evaluation results are shown in Table 1.
:: Abrasive grains are not observed to settle in the lower part of the container.
X: Abrasive grains are observed to settle in the lower part of the container.
各研磨組成物１００ｍｌを、側面が透明又は半透明であるプラスチック容器に取り分けて充分に撹拌した後、室温で１０分間静置することにより、各研磨組成物のスラリーを得た。そして、各スラリーを目視観察することにより、分散安定性の評価を行った。評価基準は以下の通りである。評価結果を表１に示す。
○：砥粒が容器下部に沈降した様子が観察されない。
×：砥粒が容器下部に沈降している様子が観察される。 <Evaluation of dispersion stability>
The slurry of each polishing composition was obtained by dividing 100 ml of each polishing composition into a plastic container whose side is transparent or translucent and sufficiently stirring, and then standing at room temperature for 10 minutes. And evaluation of dispersion stability was performed by visually observing each slurry. Evaluation criteria are as follows. The evaluation results are shown in Table 1.
:: Abrasive grains are not observed to settle in the lower part of the container.
X: Abrasive grains are observed to settle in the lower part of the container.
表１に示すように、本発明の要件をすべて満たす研磨組成物Ａ～Ｅでは、グリシンの含有量に応じて、ポリイミド樹脂の研磨速度に対する銅の研磨速度を調整することができる。また、本発明の要件をすべて満たす研磨組成物Ｃ，Ｆ，Ｇ，Ｈ及びＩでは、ＬＡＳを含有することにより、ポリイミド樹脂の研磨速度に対する銅の研磨速度の上昇を抑制することができる。
As shown in Table 1, in the polishing compositions A to E satisfying all the requirements of the present invention, the polishing rate of copper to the polishing rate of the polyimide resin can be adjusted according to the content of glycine. In addition, in the polishing compositions C, F, G, H and I satisfying all the requirements of the present invention, the increase of the polishing rate of copper with respect to the polishing rate of the polyimide resin can be suppressed by containing LAS.
一方、表２に示すように、過酸化水素水を含まない研磨組成物ａ～ｅは、グリシンの含有量を変化させても、ポリイミド樹脂の研磨速度に対する銅の研磨速度を調整することができない。
On the other hand, as shown in Table 2, polishing compositions a to e containing no hydrogen peroxide solution can not adjust the polishing rate of copper to the polishing rate of the polyimide resin even if the content of glycine is changed. .
On the other hand, as shown in Table 2, polishing compositions a to e containing no hydrogen peroxide solution can not adjust the polishing rate of copper to the polishing rate of the polyimide resin even if the content of glycine is changed. .
Claims (5)
- 銅又は銅合金と樹脂とを研磨する研磨組成物であって、
アルミナ砥粒と、
グリシンと、
過酸化水素水と、
水と、
を含む、研磨組成物。 A polishing composition for polishing copper or copper alloy and resin, comprising:
Alumina abrasive grains,
With glycine
Hydrogen peroxide solution,
water and,
And polishing composition. - さらに、アニオン界面活性剤を含有する、請求項１に記載の研磨組成物。 The polishing composition according to claim 1, further comprising an anionic surfactant.
- 前記アニオン界面活性剤が、アルキルベンゼンスルホン酸である、請求項２に記載の研磨組成物。 The polishing composition according to claim 2, wherein the anionic surfactant is an alkyl benzene sulfonic acid.
- ｐＨが、７．０以上１１．０以下である、請求項１～３のいずれか一つに記載の研磨組成物。 The polishing composition according to any one of claims 1 to 3, wherein the pH is 7.0 or more and 11.0 or less.
- 請求項１～４のいずれか一つに記載の研磨組成物を用いて研磨速度を調整する方法であって、
前記グリシンの含有量を調整することにより、樹脂の研磨速度に対する銅又は銅合金の研磨速度を調整する方法。
A method of adjusting a polishing rate using the polishing composition according to any one of claims 1 to 4, comprising:
A method of adjusting the polishing rate of copper or copper alloy to the polishing rate of resin by adjusting the content of glycine.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
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| SG11202005997WA SG11202005997WA (en) | 2017-12-26 | 2018-12-26 | Polishing composition and method for adjusting polishing speed |
| KR1020207017310A KR20200093578A (en) | 2017-12-26 | 2018-12-26 | Polishing composition and method of adjusting the polishing rate |
| CN201880080958.2A CN111511869A (en) | 2017-12-26 | 2018-12-26 | Polishing composition and method for adjusting polishing rate |
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| JP2017250050A JP7057662B2 (en) | 2017-12-26 | 2017-12-26 | Polishing composition and method for adjusting polishing speed |
| JP2017-250050 | 2017-12-26 |
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| JP (1) | JP7057662B2 (en) |
| KR (1) | KR20200093578A (en) |
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| JP2002164308A (en) * | 2000-11-24 | 2002-06-07 | Nec Corp | Slurry for chemical-mechanical polishing |
| JP2005268666A (en) * | 2004-03-19 | 2005-09-29 | Fujimi Inc | Abrasive composition |
| JP2009129977A (en) * | 2007-11-20 | 2009-06-11 | Jsr Corp | Method of polishing multi-layer circuit board, and multi-layer circuit board |
| JP2015090922A (en) * | 2013-11-06 | 2015-05-11 | ニッタ・ハース株式会社 | Polishing composition |
| JP2015528031A (en) * | 2012-07-05 | 2015-09-24 | ジェネラル エンジニアリング アンド リサーチ，エル．エル．シー． | Contact release capsules useful for chemical mechanical flattening slurries |
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| US6432828B2 (en) * | 1998-03-18 | 2002-08-13 | Cabot Microelectronics Corporation | Chemical mechanical polishing slurry useful for copper substrates |
| DE102007005291A1 (en) * | 2007-02-02 | 2008-08-07 | Evonik Degussa Gmbh | Aqueous dispersion useful for chemical-mechanical polishing of conductive metal films contains an abrasive in the form of fumed alumina |
| JPWO2009014191A1 (en) * | 2007-07-24 | 2010-10-07 | ニッタ・ハース株式会社 | Polishing composition |
| US20100207057A1 (en) * | 2007-08-23 | 2010-08-19 | Hiroshi Nitta | Polishing composition |
| JP5459466B2 (en) * | 2008-06-05 | 2014-04-02 | Ｊｓｒ株式会社 | Chemical mechanical polishing aqueous dispersion for use in circuit board production, circuit board production method, circuit board, and multilayer circuit board |
| CN102604542A (en) * | 2012-02-21 | 2012-07-25 | 复旦大学 | Polishing solution used in polishing process with metal ruthenium as adhesive barrier layer in copper interconnection |
-
2017
- 2017-12-26 JP JP2017250050A patent/JP7057662B2/en active Active
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2018
- 2018-12-26 WO PCT/JP2018/047847 patent/WO2019131762A1/en active Application Filing
- 2018-12-26 KR KR1020207017310A patent/KR20200093578A/en not_active IP Right Cessation
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002164308A (en) * | 2000-11-24 | 2002-06-07 | Nec Corp | Slurry for chemical-mechanical polishing |
| JP2005268666A (en) * | 2004-03-19 | 2005-09-29 | Fujimi Inc | Abrasive composition |
| JP2009129977A (en) * | 2007-11-20 | 2009-06-11 | Jsr Corp | Method of polishing multi-layer circuit board, and multi-layer circuit board |
| JP2015528031A (en) * | 2012-07-05 | 2015-09-24 | ジェネラル エンジニアリング アンド リサーチ，エル．エル．シー． | Contact release capsules useful for chemical mechanical flattening slurries |
| JP2015090922A (en) * | 2013-11-06 | 2015-05-11 | ニッタ・ハース株式会社 | Polishing composition |
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| KR20200093578A (en) | 2020-08-05 |
| JP2019116529A (en) | 2019-07-18 |
| JP7057662B2 (en) | 2022-04-20 |
| SG11202005997WA (en) | 2020-07-29 |
| TW201930539A (en) | 2019-08-01 |
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