JP4069387B2 - Etching solution - Google Patents
Etching solution Download PDFInfo
- Publication number
- JP4069387B2 JP4069387B2 JP2003302997A JP2003302997A JP4069387B2 JP 4069387 B2 JP4069387 B2 JP 4069387B2 JP 2003302997 A JP2003302997 A JP 2003302997A JP 2003302997 A JP2003302997 A JP 2003302997A JP 4069387 B2 JP4069387 B2 JP 4069387B2
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- JP
- Japan
- Prior art keywords
- etching
- copper
- etching solution
- acid
- present
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000005530 etching Methods 0.000 title claims description 159
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 61
- 229910052802 copper Inorganic materials 0.000 claims description 60
- 239000010949 copper Substances 0.000 claims description 60
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 30
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 22
- -1 diol compound Chemical class 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 18
- 239000007800 oxidant agent Substances 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 12
- 150000007522 mineralic acids Chemical class 0.000 claims description 8
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 7
- 229910001431 copper ion Inorganic materials 0.000 claims description 7
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 description 60
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000003746 surface roughness Effects 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 229910017053 inorganic salt Inorganic materials 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 239000005749 Copper compound Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001880 copper compounds Chemical class 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000000059 patterning Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- ORTVZLZNOYNASJ-UPHRSURJSA-N (z)-but-2-ene-1,4-diol Chemical compound OC\C=C/CO ORTVZLZNOYNASJ-UPHRSURJSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- QPYKYDBKQYZEKG-UHFFFAOYSA-N 2,2-dimethylpropane-1,1-diol Chemical compound CC(C)(C)C(O)O QPYKYDBKQYZEKG-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 1
- NUYADIDKTLPDGG-UHFFFAOYSA-N 3,6-dimethyloct-4-yne-3,6-diol Chemical compound CCC(C)(O)C#CC(C)(O)CC NUYADIDKTLPDGG-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- BGRDGMRNKXEXQD-UHFFFAOYSA-N Maleic hydrazide Chemical compound OC1=CC=C(O)N=N1 BGRDGMRNKXEXQD-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- VRPUOTOZHIXZOB-UHFFFAOYSA-N [Cr].[Cu].[Sn] Chemical compound [Cr].[Cu].[Sn] VRPUOTOZHIXZOB-UHFFFAOYSA-N 0.000 description 1
- VBVIKCXWZZEILW-UHFFFAOYSA-N [Mg].[Si].[Ni].[Cu] Chemical compound [Mg].[Si].[Ni].[Cu] VBVIKCXWZZEILW-UHFFFAOYSA-N 0.000 description 1
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000000788 chromium alloy Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical class [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- MHIBEGOZTWERHF-UHFFFAOYSA-N heptane-1,1-diol Chemical compound CCCCCCC(O)O MHIBEGOZTWERHF-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- QRXWMOHMRWLFEY-UHFFFAOYSA-N isoniazide Chemical compound NNC(=O)C1=CC=NC=C1 QRXWMOHMRWLFEY-UHFFFAOYSA-N 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- BAQLNPIEFOYKNB-UHFFFAOYSA-N pyridine-2-carbohydrazide Chemical compound NNC(=O)C1=CC=CC=N1 BAQLNPIEFOYKNB-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Classifications
-
- 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
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/32—Alkaline compositions
- C23F1/34—Alkaline compositions for etching copper or alloys thereof
-
- 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
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/18—Acidic compositions for etching copper or alloys thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- ing And Chemical Polishing (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
Description
本発明は、銅又は銅合金、特に、ビルドアップ基板等のプリント配線板の製造において、導体として積層される銅のエッチングに用いられるエッチング液、とりわけ高低差を有する粗面となっている銅表面の平坦化に好適なエッチング液に関する。 The present invention relates to an etching solution used for etching copper or copper alloy, particularly copper laminated as a conductor in the manufacture of a printed wiring board such as a build-up board, particularly a roughened copper surface having a height difference. The present invention relates to an etching solution suitable for flattening.
銅又は銅合金をエッチングする技術は幅広い分野で使われており、装飾品、資源回収、半導体製造、プリント配線基板製造などの電子・電機部品製造の分野で不可欠な技術となっている。 The technique of etching copper or copper alloy is used in a wide range of fields, and has become an indispensable technique in the fields of electronic / electrical parts manufacturing such as decoration, resource recovery, semiconductor manufacturing, and printed wiring board manufacturing.
エッチングには、（１）銅又は銅合金の表面の汚れや酸化膜を除去するためのもの、（２）銅又は銅合金の表面の凹凸を平坦化するためのもの、（３）配線パターンを形成するときのような、銅又は銅合金の表面に保護膜を形成しておき、保護膜に覆われていない銅又は銅合金露出部分を溶解除去するためのもの、（４）素地上の銅又は銅合金を全て溶解させるためのもの、（５）レジスト等との密着性を得るため、銅又は銅合金の表面を粗面化するためのもの等があり、これらはいずれも銅を溶解するという点で共通の技術を用いるものであるが、現状では、エッチング対象やエッチング目的によって異なるエッチング液を使い分けねばならない。 Etching includes (1) for removing dirt and oxide film on the surface of copper or copper alloy, (2) for flattening unevenness on the surface of copper or copper alloy, and (3) wiring pattern. For forming a protective film on the surface of copper or copper alloy as in the case of forming and dissolving and removing the exposed copper or copper alloy part not covered with the protective film, (4) Copper on the ground Or for dissolving all copper alloys, (5) for obtaining adhesion with resists, etc., for roughening the surface of copper or copper alloys, etc., all of which dissolve copper In this respect, a common technique is used, but at present, different etching solutions must be used depending on the etching target and the etching purpose.
これまで種々の使用分野や用途に亘って共通して用いることができるエッチング液が得られていなかったのは、これまでエッチング液をその対象とする使用分野や用途と異なる使用分野や用途に用いると、例えば、銅表面を過剰に荒らしてしまう、エッチング液が安定でない、エッチング速度が遅すぎたり速すぎたりする、大量使用には安全上、環境上の問題があるなど、実用上問題となる欠点が少なくとも１つは発生してしまい、この欠点が解決できていなかったからである。 The reason why an etching solution that can be used in common in various usage fields and applications has not been obtained so far is that the etching solution is used in a usage field or usage that is different from the intended usage field or usage. For example, the copper surface is excessively roughened, the etching solution is not stable, the etching rate is too slow or too fast, and there are safety and environmental problems when used in large quantities. This is because at least one defect has occurred and this defect has not been solved.
例えば、特開平３−１９３８８６号公報（特許文献１）記載のリン酸やホウ酸を使用した過酸化水素エッチング剤は、エッチング処理後のＲａが０．０８μｍと非常に平滑に仕上がるとされている。しかし、エッチング速度が４０℃で０．０５μｍ／ｍｉｎと非常に遅く、例えば、配線パターン形成用にはエッチング速度が遅すぎて実用的でない上、リンやホウ素は排水規制があり環境面からも好ましくない。 For example, a hydrogen peroxide etchant using phosphoric acid or boric acid described in JP-A-3-193886 (Patent Document 1) is said to have an extremely smooth finish with an Ra of 0.08 μm after the etching treatment. . However, the etching rate is very slow as 0.05 μm / min at 40 ° C., and for example, the etching rate is too slow for wiring pattern formation and is not practical. Absent.
また、特開平２−６０１８９号公報（特許文献２）に記載のポリエチレングリコールのような界面活性剤を入れたエッチング液も銅表面を平滑にすることができるが、エッチング速度を抑制するという弊害がある。ジオール促進剤を用いればエッチング速度を速くする（特許文献３：特公平４−２９７４４号公報参照）こともできるが、銅表面が非常に荒れるというジレンマがある。 Further, an etching solution containing a surfactant such as polyethylene glycol described in JP-A-2-60189 (Patent Document 2) can also smooth the copper surface, but has the disadvantage of suppressing the etching rate. is there. If a diol accelerator is used, the etching rate can be increased (see Patent Document 3: Japanese Patent Publication No. 4-29744), but there is a dilemma that the copper surface becomes very rough.
プリント配線板の製造においては、異なる目的でエッチング処理する工程が多数存在する。例えば、レジストパターンを用いた銅の選択的エッチング、エッチングレジスト剥離後の銅表面処理のためのエッチング、基板の冶具などに付着した銅被膜を除去するためのエッチングなどがあり、同じ銅を溶解するものであっても、これらのエッチング各々に合ったエッチング液を管理しなければならないため、多くのコストを費やさねばならなかった。 In the production of a printed wiring board, there are many processes for performing an etching process for different purposes. For example, selective etching of copper using a resist pattern, etching for copper surface treatment after etching resist stripping, etching for removing a copper film attached to a jig on a substrate, etc., dissolve the same copper. Even if it is a thing, since the etching liquid suitable for each of these etching had to be managed, much cost had to be spent.
特に、エッチングレジスト剥離後の銅表面処理のためのエッチングにおいては、プリント配線板のビルドアップ基板製造工程を例にとると、レジストと内層銅との密着を得るため内層銅の表面が粗面となっており、レジストを剥離した後にその粗面が表面に出てくる。この粗面は表面積が大きいため酸化膜が厚く形成されており、このままめっきすることはできないため、酸化膜を除去する必要がある。しかし、実用的なエッチング速度でエッチングすることを考慮してエッチング液を選択すると、従来のエッチング液では過剰なエッチングが起こり、エッチングを制御できない。このような目的で使用できるエッチング液としては、例えば、特開平１１−６０８３号公報（特許文献４）に記載されたエッチング液があるが、このエッチング液では十分な平坦度を有する表面を得ることができない。 In particular, in the etching for copper surface treatment after peeling off the etching resist, when the build-up board manufacturing process of the printed wiring board is taken as an example, the surface of the inner layer copper is rough to obtain adhesion between the resist and the inner layer copper. The rough surface appears on the surface after the resist is peeled off. Since this rough surface has a large surface area, the oxide film is formed thick and cannot be plated as it is. Therefore, it is necessary to remove the oxide film. However, when an etching solution is selected in consideration of etching at a practical etching rate, excessive etching occurs in the conventional etching solution, and the etching cannot be controlled. As an etching solution that can be used for such a purpose, for example, there is an etching solution described in Japanese Patent Laid-Open No. 11-6083 (Patent Document 4). With this etching solution, a surface having sufficient flatness is obtained. I can't.
また、上述した過剰なエッチングは、エッチングする内層銅と内層銅が積層された樹脂等の絶縁体との間に隙間を生じさせることとなる。更に、表面をエッチングする内層銅の膜厚が薄い場合には、穴が開いてめっきがうまくつかないという問題、また、膜厚が十分ある場合であっても、過剰なエッチングにより形成された隙間にガスが取り残されてめっきがつかかない部分ができるため、その後の工程において積層基板をプレスすると、そのガスが原因で割れが生じることになり、導通が失われるという問題がある。 Moreover, the excessive etching mentioned above will produce a clearance gap between the inner layer copper to etch and insulators, such as resin in which the inner layer copper was laminated | stacked. Furthermore, when the thickness of the inner layer copper that etches the surface is thin, there is a problem that a hole is formed and plating does not work well, and even if the film thickness is sufficient, gaps formed by excessive etching Since there is a portion where gas is left behind and plating cannot be formed, if the laminated substrate is pressed in the subsequent process, cracking occurs due to the gas and there is a problem that conduction is lost.
本発明は、上記問題点を解決するためになされたものであり、銅又は銅合金のエッチングにおいて、（１）銅又は銅合金の表面の汚れや酸化膜を除去するため、（２）銅又は銅合金の表面の凹凸を平坦化するため、（３）配線パターンを形成するときのような、銅又は銅合金の表面に保護膜を形成しておき、保護膜に覆われていない銅又は銅合金露出部分を溶解除去するため、（４）素地上の銅又は銅合金を全て溶解させるために共通して用いることができるエッチング液、特に、異なる目的でエッチング処理する工程が多数存在するビルドアップ基板の製造工程等のプリント配線板を製造する工程において好適に用いることができるエッチング液を提供することを目的とする。 The present invention has been made to solve the above-mentioned problems. In etching of copper or copper alloy, (1) to remove dirt or oxide film on the surface of copper or copper alloy, (2) copper or copper In order to flatten the unevenness of the surface of the copper alloy, (3) a copper or copper that is not covered with the protective film, a protective film is formed on the surface of the copper or copper alloy as in the case of forming a wiring pattern In order to dissolve and remove the exposed portion of the alloy, (4) an etchant that can be used in common to dissolve all copper or copper alloy on the substrate, especially a build-up in which there are many processes for etching for different purposes. It aims at providing the etching liquid which can be used suitably in the process of manufacturing a printed wiring board, such as a manufacturing process of a board | substrate.
本発明者は、上記問題を解決するため鋭意検討を重ねた結果、銅又は銅合金用のエッチング液であって、酸化剤及び０．００００１〜０．０１ｍｏｌ／Ｌのヒドラジド化合物を含有するエッチング液が、異なる目的のエッチング処理、特に、異なる目的でエッチング処理する工程が多数存在するビルドアップ基板の製造工程等のプリント配線板を製造する工程において共通して用いることができるエッチング液であることを見出した。 As a result of intensive studies to solve the above problems, the present inventor is an etching solution for copper or a copper alloy, which contains an oxidizing agent and 0.00001 to 0.01 mol / L hydrazide compound. However, it is an etching solution that can be used in common in processes for manufacturing printed wiring boards, such as build-up board manufacturing processes where there are many processes for etching processes for different purposes, in particular, there are many processes for etching processes for different purposes. I found it.
また、上記本発明のエッチング液を、ビルドアップ基板等のプリント配線板の製造工程で導体として積層される銅又は銅合金に施されるエッチングにおいて、例えば、レジストを積層するために高低差を有する粗面とした銅又は銅合金の表面の粗化面を平坦化するためのエッチング液として用いれば、このような粗化面を、実用的なエッチング速度で効率的にエッチングでき、エッチング速度が速いにもかかわらず、荒れのない平坦な表面を与えることができるものであることを見出し、本発明をなすに至った。 In the etching applied to the copper or copper alloy laminated as a conductor in the manufacturing process of the printed wiring board such as a build-up board, the above-described etching solution of the present invention has, for example, a height difference for laminating resist When used as an etchant for flattening the roughened surface of copper or copper alloy, the roughened surface can be efficiently etched at a practical etching rate, and the etching rate is high. Nevertheless, the present inventors have found that a flat surface without roughness can be provided, and have reached the present invention.
即ち、本発明は、銅又は銅合金用のエッチング液であって、酸化剤及び０．００００１〜０．０１ｍｏｌ／Ｌのヒドラジド化合物を含有することを特徴とするエッチング液を提供する。 That is, the present invention provides an etching solution for copper or copper alloy, which contains an oxidizing agent and 0.00001 to 0.01 mol / L hydrazide compound.
本発明のエッチング液は、異なる目的のエッチング処理、特に、異なる目的でエッチング処理する工程が多数存在するビルドアップ基板の製造工程等のプリント配線板を製造する工程において共通して用いることができ、特に、ビルドアップ基板等のプリント配線板の製造工程で導体として積層される銅又は銅合金に施されるエッチング用のエッチング液として優れたエッチング特性を有しており、例えば、レジストを積層するために高低差を有する粗面とした銅又は銅合金の表面の粗化面を平坦化するためのエッチング液として用いれば、このような粗化面を、実用的なエッチング速度で効率的にエッチングしつつ、優れた平坦面を形成できるものであり、無電解めっき等のめっき処理の前処理として施されるソフトエッチング用として特に好適である。 The etching solution of the present invention can be used in common in a process for producing a printed wiring board such as a build-up board production process in which there are many processes for etching processes for different purposes, in particular, processes for etching processes for different purposes, In particular, it has excellent etching characteristics as an etching solution for etching applied to copper or copper alloy that is laminated as a conductor in a manufacturing process of a printed wiring board such as a build-up board, for example, for laminating a resist When used as an etchant for flattening the roughened surface of copper or copper alloy with a rough surface having a height difference, the roughened surface can be efficiently etched at a practical etching rate. However, it can form an excellent flat surface and is specially used for soft etching applied as a pretreatment for electroless plating. It is preferred.
以下、本発明について更に詳述する。
本発明のエッチング液は、銅又は銅合金用のエッチング液であって、酸化剤及びヒドラジド化合物を含有するものである。
The present invention will be described in detail below.
The etching solution of the present invention is an etching solution for copper or a copper alloy, and contains an oxidizing agent and a hydrazide compound.
本発明のエッチング液は、銅又は銅合金のエッチングに用いるものであり、対象とする銅合金としては、特に限定されないが、銅−錫合金、銅−錫−クロム合金、銅−錫−ケイ素−ニッケル合金、銅−ニッケル−ケイ素−マグネシウム合金等を挙げることができる。 The etching solution of the present invention is used for etching copper or a copper alloy, and is not particularly limited as a target copper alloy, but a copper-tin alloy, a copper-tin-chromium alloy, a copper-tin-silicon- A nickel alloy, a copper-nickel-silicon-magnesium alloy, etc. can be mentioned.
本発明のエッチング液は酸化剤を含有する。この酸化剤としては、過酸化水素、過硫酸塩等が挙げられる。過酸化水素又は過硫酸塩を用いたエッチング液は、安全性が高く、環境負荷が低いなどの点で優れた特性をもつ。酸化剤として過酸化水素を用いる場合、無機酸を併用することが好ましい。無機酸としては、硝酸、塩酸、硫酸等が挙げられるが、特に硫酸が好ましい。この場合、エッチング液中の過酸化水素の濃度は５〜１００ｇ／Ｌ、特に１０〜８０ｇ／Ｌであることが好ましく、過酸化水素を用いる場合の無機酸の濃度は１０〜５００ｇ／Ｌ、特に５０〜２００ｇ／Ｌであることが好ましい。過酸化水素は、特に、銅表面が粗くなることが抑えられると共に、通常、過酸化水素水として水溶液で取り扱われ、エッチング液調整時の溶解操作が不要であることから特に好ましい。 The etching solution of the present invention contains an oxidizing agent. Examples of the oxidizing agent include hydrogen peroxide and persulfate. An etching solution using hydrogen peroxide or persulfate has excellent characteristics such as high safety and low environmental load. When hydrogen peroxide is used as the oxidizing agent, it is preferable to use an inorganic acid in combination. Examples of the inorganic acid include nitric acid, hydrochloric acid, sulfuric acid and the like, and sulfuric acid is particularly preferable. In this case, the concentration of hydrogen peroxide in the etching solution is preferably 5 to 100 g / L, particularly 10 to 80 g / L. When hydrogen peroxide is used, the concentration of inorganic acid is 10 to 500 g / L, particularly It is preferable that it is 50-200 g / L. Hydrogen peroxide is particularly preferable because it can suppress the copper surface from becoming rough, and is usually handled as an aqueous solution of hydrogen peroxide as an aqueous solution, and does not require a dissolving operation when adjusting the etching solution.
一方、酸化剤として過硫酸塩を用いる場合、ヒドラジド化合物との相乗効果によりエッチング液の安定性が増す点、エッチング速度を速められる点から無機酸を併用することが好ましい。過硫酸塩としては、過硫酸ナトリウム、過硫酸アンモニウム等が挙げられる。また、無機酸としては、硝酸、塩酸、硫酸等が挙げられるが、特に硫酸が好ましい。この場合、エッチング液中の過硫酸塩の濃度は１０〜２５０ｇ／Ｌ、特に５０〜２００ｇ／Ｌであることが好ましく、過硫酸塩を用いる場合の無機酸の濃度は１００ｇ／Ｌ以下、特に５０ｇ／Ｌ以下であることが好ましい。 On the other hand, when persulfate is used as the oxidizing agent, it is preferable to use an inorganic acid in combination from the viewpoint that the stability of the etching solution is increased by a synergistic effect with the hydrazide compound and the etching rate can be increased. Examples of the persulfate include sodium persulfate and ammonium persulfate. Examples of the inorganic acid include nitric acid, hydrochloric acid, sulfuric acid and the like, and sulfuric acid is particularly preferable. In this case, the concentration of persulfate in the etching solution is preferably 10 to 250 g / L, particularly 50 to 200 g / L, and the concentration of the inorganic acid when using the persulfate is 100 g / L or less, particularly 50 g. / L or less is preferable.
また、本発明のエッチング液はヒドラジド化合物を含有する。ヒドラジド化合物を含有させた本発明のエッチング液は、上記した酸化剤を含有し、適宜無機塩を含有するエッチング液において、上記酸化剤及び無機塩が与えるエッチング速度を低下させることなく、被エッチング面の凹凸の特に凸部を優先的にエッチングしてエッチング面を平坦化することができるものである。従って、ヒドラジド化合物を含有する本発明のエッチング液を用いれば、被エッチング表面の凹凸、例えば、算術平均表面粗さＲａが０．３〜１．０μｍ、特に０．５〜０．８μｍ程度の粗さを有する銅表面又は銅合金表面の効率的な平坦化が可能である。 The etching solution of the present invention contains a hydrazide compound. The etching solution of the present invention containing the hydrazide compound contains the above-described oxidizing agent, and in the etching solution containing the appropriate inorganic salt, the etching target surface without reducing the etching rate given by the oxidizing agent and the inorganic salt. The etching surface can be flattened by preferentially etching the projections of the projections and depressions. Therefore, when the etching solution of the present invention containing a hydrazide compound is used, the roughness of the surface to be etched, for example, the arithmetic average surface roughness Ra is 0.3 to 1.0 μm, particularly about 0.5 to 0.8 μm. It is possible to efficiently planarize the copper surface or copper alloy surface having a thickness.
ヒドラジド化合物としては、イソニコチン酸ヒドラジド等のピリジンカルボン酸ヒドラジド、マレイン酸ヒドラジド、アジピン酸ジヒドラジド等の脂肪族カルボン酸ヒドラジド、イソフタノインジヒドラジド、テレフタル酸ジヒドラジド等の芳香族カルボン酸ヒドラジドなどが挙げられる。エッチング液中のヒドラジド化合物の濃度は０．００００１〜０．０１ｍｏｌ／Ｌ、特に０．０００１〜０．００１ｍｏｌ／Ｌである。 Examples of the hydrazide compound include pyridinecarboxylic acid hydrazide such as isonicotinic acid hydrazide, aliphatic carboxylic acid hydrazide such as maleic acid hydrazide and adipic acid dihydrazide, aromatic carboxylic acid hydrazide such as isophthalanoin dihydrazide and the like. . The concentration of the hydrazide compound in the etching solution is 0.00001~0.01mol / L, Ru particular 0.0001~0.001mol / L der.
本発明のエッチング液は、ジオール化合物を含有していることが好ましい。一般に、酸化剤、又は酸化剤及び無機塩を含有するエッチング液にジオール化合物を添加した場合、エッチング速度は速くなる傾向にあることが知られているが、ジオール化合物のみを添加してエッチング速度を速くした場合、被エッチング表面が粗くなってしまう。 The etching solution of the present invention preferably contains a diol compound. In general, when a diol compound is added to an etching solution containing an oxidizing agent or an oxidizing agent and an inorganic salt, it is known that the etching rate tends to increase. However, the etching rate is increased by adding only the diol compound. When the speed is increased, the surface to be etched becomes rough.
また、プリント配線板の導体である銅のエッチングには、上述したような防錆剤や油分の除去、又は密着性の向上を目的とするソフトエッチング以外に、レジストによって保護されていない部分の銅を完全に溶かすパターニング用のエッチングがある。このようなエッチングにおいては、ソフトエッチングに比べてエッチング速度が速いエッチング液を用いるが、特公平４−２９７４４号公報記載のジオール促進剤を用いたエッチング速度の速いエッチング液を用いると、レジストに保護されていない部分が溶けるだけでなく、更にレジストで保護された銅部分をも基板面方向に浸食してしまうため、パターン同士の間隔が広く、太いパターンのエッチングには使用できても、高密度の細線パターンのパターンエッチングには使用できない。 Etching of copper, which is a conductor of a printed wiring board, includes portions of copper that are not protected by a resist, other than the above-described soft etching for the purpose of removing rust inhibitors and oils, or improving adhesion. There is an etching for patterning that completely dissolves. In such etching, an etching solution having a higher etching rate than soft etching is used. However, when an etching solution having a high etching rate using a diol accelerator described in Japanese Patent Publication No. 4-29744 is used, the resist is protected. Not only is the part that is not melted, but also the copper part protected by the resist also erodes in the direction of the substrate surface, so the distance between patterns is wide, and even if it can be used for etching thick patterns, it has a high density It cannot be used for pattern etching of thin line patterns.
これに対して、本発明のエッチング液は、ヒドラジド化合物を含有しているため、ジオール化合物を添加してエッチング速度が速くなってもヒドラジド化合物の併用により被エッチング表面の粗化が起こらず、エッチング後の被エッチング表面に平坦性を与えることができ、またパターニング用のエッチングにおいてもレジストで保護された銅部分が過度に浸食されることがない。特に、酸化剤として過酸化水素を用いる場合、一般に過酸化水素ベースのエッチング液は過酸化水素の分解が起こり易く不安定であるが、ヒドラジド化合物とジオール化合物との併用は、この安定化にも効果があるため特に効果的である。 On the other hand, since the etching solution of the present invention contains a hydrazide compound, even if the diol compound is added to increase the etching rate, the hydrazide compound is not used to roughen the surface to be etched and etching is performed. Flatness can be imparted to the surface to be etched later, and the copper portion protected by the resist is not excessively eroded in patterning etching. In particular, when hydrogen peroxide is used as an oxidizing agent, an etching solution based on hydrogen peroxide is generally unstable because hydrogen peroxide is likely to be decomposed. However, the combined use of a hydrazide compound and a diol compound is also effective for this stabilization. It is particularly effective because it is effective.
ジオール化合物としては、例えば、ブタンジオール、ペンタンジオール、ヘキサンジオール、ヘプタンジオール、ジメチルプロパンジオール等の飽和炭化水素系ジオール、ジメチルオクチンジオール、ブテンジオール、ブチンジオール等の不飽和炭化水素系ジオールなどの脂肪族炭化水素系ジオールが挙げられる。エッチング液中のジオール化合物の濃度は０．０１〜０．５ｍｏｌ／Ｌ、特に０．０２〜０．２ｍｏｌ／Ｌであることが好ましい。 Examples of the diol compound include fats such as saturated hydrocarbon diols such as butanediol, pentanediol, hexanediol, heptanediol, and dimethylpropanediol, and unsaturated hydrocarbon diols such as dimethyloctynediol, butenediol, and butynediol. Group hydrocarbon diol. The concentration of the diol compound in the etching solution is preferably 0.01 to 0.5 mol / L, particularly 0.02 to 0.2 mol / L.
また、本発明のエッチング液には、上記したジオール化合物と共に塩化物イオンを含有させることができる。一般に、銅又は銅合金用のエッチング液、特に酸化剤として過酸化水素を用いたエッチング液は、市水などから混入する塩化物イオンにより銅表面に塩化第１銅の皮膜が形成されてエッチング速度が急激に低下する場合がある。これに対して、本発明のエッチング液において、ヒドラジド化合物と共にジオール化合物を用いる場合には、塩化物イオンによりエッチング速度が低下する影響があっても、上述したように、エッチング速度を維持しつつ、被エッチング表面の平坦性を制御することが可能である。従って、本発明のエッチング液においては、上記したジオール化合物と共に塩化物イオンを予め添加しておくことも好適である。この場合、建浴時から予め塩化物イオンが存在する状態とし、エッチング速度を安定化した状態で所望のエッチング速度を確保しつつ、被エッチング表面の平坦性を制御することができる。 In addition, the etching solution of the present invention can contain chloride ions together with the diol compound described above. In general, an etching solution for copper or a copper alloy, particularly an etching solution using hydrogen peroxide as an oxidizing agent, forms a cuprous chloride film on the copper surface by chloride ions mixed from city water, etc., and etching rate. May drop sharply. On the other hand, in the etching solution of the present invention, when a diol compound is used together with a hydrazide compound, as described above, while maintaining the etching rate, even if there is an effect that the etching rate is reduced by chloride ions, It is possible to control the flatness of the surface to be etched. Therefore, in the etching solution of the present invention, it is also preferable to add chloride ions together with the above-described diol compound. In this case, it is possible to control the flatness of the surface to be etched while maintaining a desired etching rate in a state where chloride ions are present in advance from the time of bathing and the etching rate is stabilized.
この場合、塩化物イオンを供給する塩化物としては、塩化ナトリウム、塩化アンモニウム等の塩化物塩が挙げられるが、無機酸として塩酸を用いることで塩化物イオンを添加することも可能である。本発明のエッチング液は、塩化物イオンを含まないものであってもよいが、上述したとおり、エッチング速度の安定化の点からすれば、塩化物イオンを含んでいることが好ましく、この場合、エッチング液中の塩化物イオンの濃度は１０〜１０００ｐｐｍ、特に２０〜６０ｐｐｍであることが好ましい。 In this case, chlorides supplying chloride ions include chloride salts such as sodium chloride and ammonium chloride, but chloride ions can be added by using hydrochloric acid as an inorganic acid. The etching solution of the present invention may not contain chloride ions, but as described above, it is preferable to contain chloride ions from the viewpoint of stabilization of the etching rate. The concentration of chloride ions in the etching solution is preferably 10 to 1000 ppm, particularly 20 to 60 ppm.
更に、本発明のエッチング液には、銅イオンを含有させることができる。一般に銅又は銅合金のエッチング液は、建浴直後は反応性が低く、銅の溶解に伴い反応性が上がるため、エッチング速度が不安定である。予め銅イオンを含有させておくことにより、建浴直後から安定した反応性でエッチングすることができる。 Furthermore, the etching solution of the present invention can contain copper ions. In general, an etching solution of copper or a copper alloy has a low reactivity immediately after the building bath, and the reactivity increases with the dissolution of copper, so that the etching rate is unstable. By containing copper ions in advance, etching can be performed with stable reactivity immediately after the bath.
この場合、銅イオンを供給する銅化合物としては、硫酸銅、塩化銅、硝酸銅等が挙げられるが、特に硫酸銅が好ましい。本発明のエッチング液は、銅イオンを含まないものであってもよいが、上述したとおり、エッチング反応性の安定化の点からすれば、銅イオンを含んでいることが好ましく、この場合、エッチング液中の銅イオンの濃度は５ｇ／Ｌ以上特に１０ｇ／Ｌ以上でエッチング機能を損なわない範囲で含有させることができる。例えば、銅化合物として硫酸銅５水塩を用いる場合、エッチング液への添加量を２０〜４０ｇ／Ｌ程度とすればよい。 In this case, examples of the copper compound for supplying copper ions include copper sulfate, copper chloride, and copper nitrate, and copper sulfate is particularly preferable. The etching solution of the present invention may not contain copper ions, but as described above, from the viewpoint of stabilization of etching reactivity, it is preferable to contain copper ions. The concentration of copper ions in the liquid is 5 g / L or more, particularly 10 g / L or more, and can be contained in a range that does not impair the etching function. For example, when copper sulfate pentahydrate is used as the copper compound, the amount added to the etching solution may be about 20 to 40 g / L.
本発明のエッチング液には、メタノールやエタノール等の（モノ）アルコール類、上述のジオール化合物以外のグリコール類、エチレングリコールモノメチルエーテル等のグリコールエーテル類、フェノール類等を添加することが可能である。また、浴寿命の長寿命化を図るため、ギ酸、酢酸、酪酸、シュウ酸、コハク酸、グルタル酸、リンゴ酸、酒石酸、クエン酸等の脂肪族カルボン酸、ＥＤＴＡ、ＨＥＤＴＡ、ＴＥＴＡ、ＥＤＡ、ＤＥＴＡ、ＴＥＡ、ＤＥＡ、ＭＥＡ等のアミン化合物を添加することも可能である。 To the etching solution of the present invention, (mono) alcohols such as methanol and ethanol, glycols other than the above diol compounds, glycol ethers such as ethylene glycol monomethyl ether, phenols and the like can be added. In order to prolong bath life, aliphatic carboxylic acids such as formic acid, acetic acid, butyric acid, oxalic acid, succinic acid, glutaric acid, malic acid, tartaric acid, citric acid, EDTA, HEDTA, TETA, EDA, DETA It is also possible to add amine compounds such as TEA, DEA and MEA.
本発明のエッチング液は、ビルドアップ基板の製造工程等のプリント配線板を製造する工程において用いるエッチング液、特に、銅と樹脂等の絶縁体とを交互に積層してビルドアップ基板を製造する工程において、銅上に積層された樹脂等の絶縁体を除去することにより形成したビアホール内に露呈した銅表面を処理するためのエッチング液として好適である。本発明のエッチング液を用いることにより、このようなビアホール内の内層銅の表面を、効率よく、また内層銅に欠陥を生じさせることなく平坦化することが可能であり、例えば、算術平均表面粗さＲａが０．１５〜０．３μｍ、特に０．１５〜０．２μｍ程度の粗さの銅表面又は銅合金表面を得ることが可能である。 The etching solution of the present invention is a process for producing a build-up substrate by alternately laminating an insulating material such as copper and a resin, which is used in a process for producing a printed wiring board such as a build-up substrate production process. In the above, it is suitable as an etching solution for treating the copper surface exposed in the via hole formed by removing the insulator such as resin laminated on the copper. By using the etching solution of the present invention, it is possible to planarize the surface of the inner layer copper in such a via hole efficiently and without causing defects in the inner layer copper, for example, arithmetic mean surface roughness. It is possible to obtain a copper surface or a copper alloy surface having a roughness Ra of about 0.15 to 0.3 μm, particularly about 0.15 to 0.2 μm.
以下、実施例及び比較例を挙げて本発明を具体的に説明するが、本発明は下記実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not limited to the following Example.
［実施例１〜１３、比較例１〜３］
基材として製面研磨を施していないＦＲ−４銅張り積層板を使用し、この基材を表１〜３に示す組成のエッチング液に浸漬することにより銅表面にエッチング処理を施した。その後、基材を水洗、乾燥し、処理前後の重量差からエッチング量を算出し、また、レーザー顕微鏡（キーエンス社製）により算術平均表面粗さＲａ及び最大高さＲｙを測定した。結果を表１〜３に示す。
[Examples 1 to 13, Comparative Examples 1 to 3]
An FR-4 copper-clad laminate without surface polishing was used as a substrate, and the copper surface was etched by immersing this substrate in an etching solution having the composition shown in Tables 1 to 3. Thereafter, the substrate was washed with water, dried, the etching amount was calculated from the weight difference before and after the treatment, and the arithmetic average surface roughness Ra and the maximum height Ry were measured with a laser microscope (manufactured by Keyence Corporation). The results are shown in Tables 1-3.
表１，２によれば、ヒドラジド化合物を含有するエッチング液を用いた実施例１〜４又は実施例５〜８の場合、ヒドラジド化合物を含有しないエッチング液を用いた比較例１又は比較例２の場合に比べ、酸化剤として過酸化水素、過硫酸ナトリウムのいずれを用いた場合においてもエッチング量（エッチング速度）を実質的に減少（低下）させずに、エッチング面の表面粗さを小さくすることができることがわかる。 According to Tables 1 and 2, in the case of Examples 1 to 4 or Examples 5 to 8 using an etching solution containing a hydrazide compound, Comparative Example 1 or Comparative Example 2 using an etching solution containing no hydrazide compound was used. Compared to the case, when using either hydrogen peroxide or sodium persulfate as the oxidizing agent, the surface roughness of the etched surface should be reduced without substantially reducing (decreasing) the etching amount (etching rate). You can see that
また、表３によれば、酸化剤が過酸化水素の場合、エッチング液中に塩素イオンが存在するとエッチング量（エッチング速度）が減少（低下）する（比較例１，３参照）が、ヒドラジド化合物と共にジオール化合物を含有させる（実施例９〜１３）ことにより、エッチング液中に塩素イオンが存在していても、エッチング量（エッチング速度）を、塩素イオンを含まない場合と同等に調整することができ、この場合、エッチング量（エッチング速度）が塩素イオンを含まない場合と同等であっても、エッチング面の表面粗さが大きくならないことがわかる。 Further, according to Table 3, when the oxidizing agent is hydrogen peroxide, the etching amount (etching rate) decreases (decreases) when chlorine ions are present in the etching solution (see Comparative Examples 1 and 3), but the hydrazide compound In addition, by including a diol compound (Examples 9 to 13), even when chlorine ions are present in the etching solution, the etching amount (etching rate) can be adjusted to the same level as when chlorine ions are not included. In this case, it can be seen that even if the etching amount (etching rate) is equal to that in the case of not containing chlorine ions, the surface roughness of the etched surface does not increase.
［実施例１４、比較例４，５］
基材として製面研磨を施していないＦＲ−４銅張り積層板の銅表面を、レジストと内層銅との密着を得るため粗化面とした基材を表４に示す組成のエッチング液に浸漬することによりこの粗化面にエッチング処理を施した。その後、基材を水洗、乾燥し、処理前後の重量差からエッチング量を算出し、また、レーザー顕微鏡（キーエンス社製）により算術平均表面粗さＲａ及び最大高さＲｙを測定した。結果を表４に示す。
[Example 14, comparative examples 4 and 5]
As a base material, the surface of the FR-4 copper-clad laminate not subjected to surface polishing is immersed in an etching solution having the composition shown in Table 4 as a roughened surface in order to obtain adhesion between the resist and the inner layer copper. Thus, the roughened surface was etched. Thereafter, the substrate was washed with water, dried, the etching amount was calculated from the weight difference before and after the treatment, and the arithmetic average surface roughness Ra and the maximum height Ry were measured with a laser microscope (manufactured by Keyence Corporation). The results are shown in Table 4.
表面粗化処理した銅表面のエッチングは、表面粗化処理していない銅表面をエッチングする場合に比べてエッチング量（エッチング速度）が増大（上昇）し、表面粗さが大きくなってしまう（比較例３，４、又は比較例２，５参照）。これに対して、ヒドラジド化合物と共に、塩化物イオン及びジオール化合物を含有させる（実施例１４）ことにより、エッチング量（エッチング速度）を、実用的なエッチング量（エッチング速度）としつつ、エッチング面の表面粗さを抑えることができることがわかる。
Etching of a copper surface that has undergone surface roughening increases (increases) the etching amount (etching rate) and increases the surface roughness compared to etching a copper surface that has not been surface roughened (comparison). See Examples 3 and 4 or Comparative Examples 2 and 5). On the other hand, a chloride ion and a diol compound are contained together with the hydrazide compound (Example 14), so that the etching amount (etching rate) is set to a practical etching amount (etching rate), and the surface of the etching surface. It can be seen that the roughness can be suppressed.
Claims (8)
8. The etching solution according to claim 7, wherein the process is a manufacturing process of a build-up substrate.
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