JP2009191357A - Etching liquid - Google Patents
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- JP2009191357A JP2009191357A JP2008267719A JP2008267719A JP2009191357A JP 2009191357 A JP2009191357 A JP 2009191357A JP 2008267719 A JP2008267719 A JP 2008267719A JP 2008267719 A JP2008267719 A JP 2008267719A JP 2009191357 A JP2009191357 A JP 2009191357A
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- copper
- etching solution
- etching
- phenyltetrazole
- nitrobenzotriazole
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- 238000005530 etching Methods 0.000 title claims abstract description 72
- 239000007788 liquid Substances 0.000 title claims abstract description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 69
- 229910052802 copper Inorganic materials 0.000 claims abstract description 66
- 239000010949 copper Substances 0.000 claims abstract description 66
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 28
- UTMDJGPRCLQPBT-UHFFFAOYSA-N 4-nitro-1h-1,2,3-benzotriazole Chemical class [O-][N+](=O)C1=CC=CC2=NNN=C12 UTMDJGPRCLQPBT-UHFFFAOYSA-N 0.000 claims abstract description 25
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical class C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 claims abstract description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 8
- 150000008107 benzenesulfonic acids Chemical class 0.000 claims abstract description 3
- 235000002639 sodium chloride Nutrition 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- AOCDQWRMYHJTMY-UHFFFAOYSA-N 5-nitro-2h-benzotriazole Chemical compound C1=C([N+](=O)[O-])C=CC2=NNN=C21 AOCDQWRMYHJTMY-UHFFFAOYSA-N 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- IYPXPGSELZFFMI-UHFFFAOYSA-N 1-phenyltetrazole Chemical compound C1=NN=NN1C1=CC=CC=C1 IYPXPGSELZFFMI-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 235000011167 hydrochloric acid Nutrition 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 239000011810 insulating material Substances 0.000 abstract description 12
- 239000000463 material Substances 0.000 description 45
- 239000000243 solution Substances 0.000 description 38
- 239000000758 substrate Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 229910000679 solder Inorganic materials 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000007788 roughening Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910000881 Cu alloy Inorganic materials 0.000 description 3
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 3
- 229940092714 benzenesulfonic acid Drugs 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 239000005749 Copper compound Substances 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001880 copper compounds Chemical class 0.000 description 2
- 239000011889 copper foil Substances 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
- 230000000694 effects Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 150000003536 tetrazoles Chemical class 0.000 description 2
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 description 1
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Chemical compound C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 description 1
- CHZLVSBMXZSPNN-UHFFFAOYSA-N 2,4-dimethylbenzenesulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C(C)=C1 CHZLVSBMXZSPNN-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical group NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- BZOVBIIWPDQIHF-UHFFFAOYSA-N 3-hydroxy-2-methylbenzenesulfonic acid Chemical compound CC1=C(O)C=CC=C1S(O)(=O)=O BZOVBIIWPDQIHF-UHFFFAOYSA-N 0.000 description 1
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 1
- ONMOULMPIIOVTQ-UHFFFAOYSA-N 98-47-5 Chemical compound OS(=O)(=O)C1=CC=CC([N+]([O-])=O)=C1 ONMOULMPIIOVTQ-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical group [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229950000244 sulfanilic acid Drugs 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Classifications
-
- 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
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
Abstract
Description
本発明は、硫酸、過酸化水素及び水を含む銅のエッチング液に関する。 The present invention relates to a copper etching solution containing sulfuric acid, hydrogen peroxide and water.
銅または銅合金からなる層を含む配線層形成材（以下、単に「銅材」という）と、絶縁材とが積層された積層基材は、プリント配線板等の製造に使用される場合、銅層と絶縁層との密着性が要求される。そのため、銅材と絶縁材とを積層する前に、例えば、硫酸、過酸化水素及び水を含むエッチング液（硫酸／過酸化水素系マイクロエッチング液）で銅材表面を粗化（マイクロエッチング）して、銅層と絶縁層との密着性を向上させている。 A laminated base material in which a wiring layer forming material (hereinafter simply referred to as “copper material”) including a layer made of copper or a copper alloy and an insulating material is laminated is used when manufacturing a printed wiring board or the like. Adhesion between the layer and the insulating layer is required. Therefore, before laminating the copper material and the insulating material, for example, the surface of the copper material is roughened (microetching) with an etching solution (sulfuric acid / hydrogen peroxide microetching solution) containing sulfuric acid, hydrogen peroxide and water. Thus, the adhesion between the copper layer and the insulating layer is improved.
上記のような用途に使用されるエッチング液（マイクロエッチング液）においては、銅層と絶縁層との密着性を向上させるために、銅材表面に凹凸形状を均一に形成することが要求されていた。そのため、エッチング液にアゾール類等の種々の添加剤を添加することが従来から検討されていた（例えば、特許文献１〜１３参照）。 In the etching liquid (microetching liquid) used for the above-mentioned uses, in order to improve the adhesion between the copper layer and the insulating layer, it is required to form an uneven shape uniformly on the surface of the copper material. It was. Therefore, it has been conventionally studied to add various additives such as azoles to the etching solution (see, for example, Patent Documents 1 to 13).
しかし、高信頼性が要求されるプリント配線板においては、上記特許文献１〜１３に記載された技術を用いても、銅層と絶縁層との密着性が不充分であったため、さらなる改良が求められている。特に、近年、車載用などの耐熱性が要求されるプリント配線板などには、耐熱性の高い絶縁材が用いられるが、この場合には高温条件下でも銅層と絶縁層との密着性が維持される必要がある。また、はんだリフロー工程などのように高温条件下で基板が処理される工程においても、銅層と絶縁層との密着性が維持される必要がある。さらに、環境対策としてハロゲンフリー材が絶縁材として使用される場合もあるが、ハロゲンフリー材は、一般的に銅材との密着性が低いため、従来のマイクロエッチング液による処理では、銅層と絶縁層との密着性が不充分であった。 However, in printed wiring boards that require high reliability, even if the techniques described in Patent Documents 1 to 13 are used, the adhesion between the copper layer and the insulating layer is insufficient, so that further improvements can be made. It has been demanded. In particular, in recent years, insulating materials with high heat resistance are used for printed wiring boards and the like that are required for heat resistance such as in-vehicle use. In this case, the adhesion between the copper layer and the insulating layer is high even under high temperature conditions. Need to be maintained. In addition, the adhesion between the copper layer and the insulating layer needs to be maintained even in a process in which the substrate is processed under a high temperature condition such as a solder reflow process. In addition, halogen-free materials are sometimes used as insulating materials as environmental measures. However, since halogen-free materials generally have low adhesion to copper materials, conventional micro-etching solution treatments use a copper layer. Adhesion with the insulating layer was insufficient.
本発明は、上記実情に鑑みてなされたものであり、高温条件下においても銅層と絶縁層との密着性を確実に維持することができる上、広範な絶縁材に対して密着性を向上させることができるエッチング液を提供する。 The present invention has been made in view of the above circumstances, and can reliably maintain the adhesion between the copper layer and the insulating layer even under high temperature conditions, and also improves the adhesion to a wide range of insulating materials. An etching solution that can be applied is provided.
上記目的を達成するため、本発明のエッチング液は、硫酸、過酸化水素及び水を含む銅のエッチング液であって、フェニルテトラゾール類及びニトロベンゾトリアゾール類を含むことを特徴とする。 In order to achieve the above object, an etching solution of the present invention is a copper etching solution containing sulfuric acid, hydrogen peroxide and water, and includes phenyltetrazoles and nitrobenzotriazoles.
なお、上記本発明のエッチング液は、銅のエッチング液であるが、この「銅」には、純銅だけでなく銅合金も含まれる。また、本明細書において「銅」は、純銅又は銅合金をさす。 The above-described etching solution of the present invention is a copper etching solution, and this “copper” includes not only pure copper but also a copper alloy. In this specification, “copper” refers to pure copper or a copper alloy.
本発明のエッチング液によれば、高温条件下においても銅層と絶縁層との密着性を確実に維持することができる上、広範な絶縁材に対して密着性を向上させることができる。 According to the etching solution of the present invention, the adhesion between the copper layer and the insulating layer can be reliably maintained even under high temperature conditions, and the adhesion to a wide range of insulating materials can be improved.
本発明のエッチング液は、硫酸、過酸化水素及び水を含む銅のエッチング液であって、フェニルテトラゾール類及びニトロベンゾトリアゾール類を含む。本発明では、フェニルテトラゾール類とニトロベンゾトリアゾール類とを組み合わせることで、銅材表面を均一に粗化することができるため、はんだリフロー工程などの高温条件下においても銅層と絶縁層との密着性を確実に維持することができる上、ハロゲンフリー材を含む広範な絶縁材に対して密着性を向上させることができる。なお、本発明のエッチング液は、銅材表面を粗化することによって、アンカー効果で銅層と絶縁層との密着性を向上させる機能の他、化学的な作用で上記密着性を向上させる機能も有すると考えられる。この化学的な作用については、例えば、フェニルテトラゾール類及びニトロベンゾトリアゾール類が銅材表面に付着することによって、これらの成分と銅イオンとが皮膜を形成し、この皮膜が絶縁材に固着することにより、上記密着性が向上することが考えられる。 The etching solution of the present invention is a copper etching solution containing sulfuric acid, hydrogen peroxide and water, and contains phenyltetrazoles and nitrobenzotriazoles. In the present invention, the surface of the copper material can be uniformly roughened by combining phenyltetrazole and nitrobenzotriazole, so the adhesion between the copper layer and the insulating layer even under high temperature conditions such as a solder reflow process. In addition, the adhesion can be improved with respect to a wide range of insulating materials including halogen-free materials. The etching solution of the present invention has a function of improving the adhesion by a chemical action in addition to a function of improving the adhesion between the copper layer and the insulating layer by an anchor effect by roughening the surface of the copper material. Is also considered to have. Regarding this chemical action, for example, phenyltetrazole and nitrobenzotriazole adhere to the surface of the copper material, so that these components and copper ions form a film, and this film adheres to the insulating material. Thus, it is considered that the adhesion is improved.
上記エッチング液中の硫酸の濃度は、エッチング速度やエッチング液の銅溶解許容量に応じて調整されるが、６０〜２２０ｇ／Ｌが好ましく、９０〜１５０ｇ／Ｌがより好ましい。６０ｇ／Ｌ以上の場合は、エッチング速度が速くなるため、銅材表面を速やかに粗化することができる。一方、２２０ｇ／Ｌ以下の場合は、溶解した銅が硫酸銅として析出するのを防止できる。 Although the density | concentration of the sulfuric acid in the said etching liquid is adjusted according to an etching rate and the copper dissolution tolerance of an etching liquid, 60-220 g / L is preferable and 90-150 g / L is more preferable. In the case of 60 g / L or more, since the etching rate is increased, the surface of the copper material can be rapidly roughened. On the other hand, in the case of 220 g / L or less, it can prevent that the melt | dissolved copper precipitates as copper sulfate.
上記エッチング液中の過酸化水素の濃度は、エッチング速度や表面粗化能力に応じて調整されるが、５〜７０ｇ／Ｌが好ましく、７〜５６ｇ／Ｌがより好ましく、１０〜３０ｇ／Ｌがさらに好ましい。５ｇ／Ｌ以上の場合は、エッチング速度が速くなるため、銅材表面を速やかに粗化できる。一方、７０ｇ／Ｌ以下の場合は、銅材表面をより均一に粗化できる。 The concentration of hydrogen peroxide in the etching solution is adjusted according to the etching rate and surface roughening ability, but is preferably 5 to 70 g / L, more preferably 7 to 56 g / L, and more preferably 10 to 30 g / L. Further preferred. In the case of 5 g / L or more, since the etching rate is increased, the surface of the copper material can be rapidly roughened. On the other hand, in the case of 70 g / L or less, the copper material surface can be roughened more uniformly.
本発明のエッチング液には、フェニルテトラゾール類及びニトロベンゾトリアゾール類が配合されているため、フェニルテトラゾール類とニトロベンゾトリアゾール類との相乗効果により、従来のエッチング液に比べ銅材表面を均一に粗化できる。よって、高温条件下においても銅層と絶縁層との密着性を確実に維持することができる上、広範な絶縁材に対して密着性を向上させることができる。また、これらの成分を配合することにより、銅材表面の凹凸形状を、絶縁材との密着性を高めるのに適した形状にすることができる。 Since the etching solution of the present invention contains phenyltetrazole and nitrobenzotriazole, the copper material surface is more uniformly roughened than conventional etching solutions due to the synergistic effect of phenyltetrazole and nitrobenzotriazole. Can be Therefore, the adhesiveness between the copper layer and the insulating layer can be reliably maintained even under high temperature conditions, and the adhesiveness can be improved for a wide range of insulating materials. Moreover, by mix | blending these components, the uneven | corrugated shape of a copper material surface can be made into the shape suitable for improving adhesiveness with an insulating material.
また、上記フェニルテトラゾール類及びニトロベンゾトリアゾール類は、酸性溶液への溶解性が高いため、エッチング液中での安定性に優れている。よって、本発明のエッチング液は、連続してエッチング処理を行った場合でも、液中に析出物が生じることなく、銅材表面を均一に粗化できる。なお、従来の硫酸／過酸化水素系マイクロエッチング液に、ベンゾトリアゾールやテトラゾールなどを添加した場合、連続してエッチング処理を行うと、上記添加成分と銅とが結合した黒い析出物が生じ、これが銅材表面に付着して後工程に影響を及ぼすおそれがあった。具体的には、上記析出物が銅配線パターン間に残留した場合などは、ショートの原因になる可能性があった。従来は、このような析出物を除去するために、フィルターでマイクロエッチング液をろ過するなどの処理が必要であったため、製造工程が煩雑になりコスト高となっていた。本発明のエッチング液には、上記フェニルテトラゾール類及びニトロベンゾトリアゾール類が配合されているため、上記析出物の発生を効果的に抑制できる。 Moreover, since the said phenyltetrazole and nitrobenzotriazole are highly soluble in an acidic solution, they are excellent in stability in an etching solution. Therefore, the etching liquid of the present invention can uniformly roughen the surface of the copper material without causing precipitates in the liquid even when the etching process is continuously performed. In addition, when benzotriazole, tetrazole, or the like is added to the conventional sulfuric acid / hydrogen peroxide microetching solution, when the etching process is continuously performed, a black precipitate is formed in which the additive component and copper are combined. There was a risk of adhering to the copper material surface and affecting subsequent processes. Specifically, when the deposit remains between the copper wiring patterns, it may cause a short circuit. Conventionally, in order to remove such precipitates, a process such as filtering the microetching liquid with a filter has been required, which complicates the manufacturing process and increases the cost. Since the said phenyltetrazole and nitrobenzotriazole are mix | blended with the etching liquid of this invention, generation | occurrence | production of the said deposit can be suppressed effectively.
上記フェニルテトラゾール類としては、１−フェニルテトラゾール及びその誘導体、５−フェニルテトラゾール及びその誘導体等が挙げられる。なかでも、ニトロベンゾトリアゾール類との相乗効果により銅層と絶縁層との密着性を高めるには、上記フェニルテトラゾール類が、５−フェニルテトラゾールであることが特に好ましい。フェニルテトラゾール類の誘導体としては、−ＳＨ基が導入された化合物（例えば、１−フェニル−５−メルカプト−１Ｈテトラゾール）や、−ＮＨ２基が導入された化合物（例えば、５（３−アミノフェニル）１Ｈテトラゾール）等が例示できる。また、１−フェニルテトラゾールの金属塩や５−フェニルテトラゾールの金属塩を使用してもよく、これらの金属塩のカウンターカチオンとしては、カルシウムイオン、第一銅イオン、第二銅イオン、リチウムイオン、マグネシウムイオン、ナトリウムイオン等が例示できる。 Examples of the phenyltetrazole include 1-phenyltetrazole and derivatives thereof, 5-phenyltetrazole and derivatives thereof, and the like. Especially, in order to improve the adhesiveness of a copper layer and an insulating layer by a synergistic effect with nitrobenzotriazole, it is especially preferable that the said phenyltetrazole is 5-phenyltetrazole. Examples of the derivatives of phenyltetrazole include a compound in which a —SH group is introduced (for example, 1-phenyl-5-mercapto-1Htetrazole) and a compound in which a —NH 2 group is introduced (for example, 5 (3-aminophenyl). ) 1H tetrazole) and the like. In addition, a metal salt of 1-phenyltetrazole or a metal salt of 5-phenyltetrazole may be used. Counter ions of these metal salts include calcium ions, cuprous ions, cupric ions, lithium ions, Examples thereof include magnesium ions and sodium ions.
上記フェニルテトラゾール類の濃度は、粗化形状やエッチング液の銅溶解許容量に応じて調整されるが、０．０１〜０．７ｇ／Ｌが好ましく、０．０３〜０．６ｇ／Ｌがより好ましく、０．０５〜０．４ｇ／Ｌがさらに好ましい。０．０１ｇ／Ｌ以上の場合は、エッチング速度が速くなるため、銅材表面を速やかに粗化できる。一方、０．７ｇ／Ｌ以下の場合は、エッチング液中で析出するのを防止できる。 The concentration of the phenyltetrazole is adjusted according to the roughened shape and the copper dissolution tolerance of the etching solution, but is preferably 0.01 to 0.7 g / L, more preferably 0.03 to 0.6 g / L. 0.05 to 0.4 g / L is more preferable. In the case of 0.01 g / L or more, since the etching rate is increased, the surface of the copper material can be rapidly roughened. On the other hand, in the case of 0.7 g / L or less, precipitation in the etching solution can be prevented.
上記ニトロベンゾトリアゾール類としては、４−ニトロベンゾトリアゾール及びその誘導体、５−ニトロベンゾトリアゾール及びその誘導体等が挙げられる。なかでも、フェニルテトラゾール類との相乗効果により銅層と絶縁層との密着性を高めるには、上記ニトロベンゾトリアゾール類が、４−ニトロベンゾトリアゾール又は５−ニトロベンゾトリアゾール、あるいは４−ニトロベンゾトリアゾールと５−ニトロベンゾトリアゾールの混合物であることが好ましい。特に、４−ニトロベンゾトリアゾールを使用した場合には、酸性溶液への溶解性が高く、エッチング液中で析出物が生じにくいため好ましい。 Examples of the nitrobenzotriazoles include 4-nitrobenzotriazole and derivatives thereof, 5-nitrobenzotriazole and derivatives thereof, and the like. Among these, in order to enhance the adhesion between the copper layer and the insulating layer by a synergistic effect with phenyltetrazoles, the above nitrobenzotriazoles are 4-nitrobenzotriazole, 5-nitrobenzotriazole, or 4-nitrobenzotriazole. And a mixture of 5-nitrobenzotriazole. In particular, when 4-nitrobenzotriazole is used, it is preferable because the solubility in an acidic solution is high and precipitates are hardly generated in the etching solution.
上記ニトロベンゾトリアゾール類の濃度は、粗化形状やエッチング液の銅溶解許容量に応じて調整されるが、０．０１〜１．５ｇ／Ｌが好ましく、０．１〜１．０ｇ／Ｌがより好ましく、０．２〜０．８ｇ／Ｌがさらに好ましい。０．０１ｇ／Ｌ以上の場合は、銅材表面をより均一に粗化できる。一方、１．５ｇ／Ｌ以下の場合は、エッチング液中で析出するのを防止できる。 The concentration of the nitrobenzotriazoles is adjusted according to the roughened shape and the copper dissolution tolerance of the etching solution, but is preferably 0.01 to 1.5 g / L, more preferably 0.1 to 1.0 g / L. More preferred is 0.2 to 0.8 g / L. In the case of 0.01 g / L or more, the copper material surface can be roughened more uniformly. On the other hand, in the case of 1.5 g / L or less, precipitation in the etching solution can be prevented.
また、高温条件下における銅層と絶縁層との密着性をより向上させるには、上記フェニルテトラゾール類の濃度をＡｇ／Ｌとし、上記ニトロベンゾトリアゾール類の濃度をＢｇ／Ｌとした場合に、Ｂ／Ａが１．０〜３．０であることが好ましい。特に、Ｂ／Ａが１．５〜３．０の場合は、銅材表面をより均一に粗化できるため、より好ましい。 Further, in order to further improve the adhesion between the copper layer and the insulating layer under high temperature conditions, when the concentration of the phenyltetrazole is Ag / L and the concentration of the nitrobenzotriazole is Bg / L, B / A is preferably 1.0 to 3.0. In particular, B / A of 1.5 to 3.0 is more preferable because the surface of the copper material can be more uniformly roughened.
本発明のエッチング液には、上述した成分以外にも、本発明の効果を妨げない程度に他の成分を添加してもよい。例えば、過酸化水素の安定剤として、クレゾールスルホン酸、ベンゼンスルホン酸、トルエンスルホン酸、ｍ−キシレンスルホン酸、フェノールスルホン酸、スルホサリチル酸、ｍ−ニトロベンゼンスルホン酸、ｐ−アミノベンゼンスルホン酸などのベンゼンスルホン酸類を添加してもよい。この場合、ベンゼンスルホン酸類の濃度は、過酸化水素の安定性の観点から、１０ｇ／Ｌ以下が好ましく、２〜４ｇ／Ｌがより好ましい。なお、従来の硫酸／過酸化水素系マイクロエッチング液にベンゼンスルホン酸類を添加すると、銅とベンゼンスルホン酸類とが結合した析出物が生じる事があったが、本発明のエッチング液には、上記フェニルテトラゾール類及びニトロベンゾトリアゾール類が配合されているため、上記析出物の発生を効果的に抑制できる。 In addition to the components described above, other components may be added to the etching solution of the present invention to the extent that the effects of the present invention are not hindered. For example, as a hydrogen peroxide stabilizer, benzene such as cresol sulfonic acid, benzene sulfonic acid, toluene sulfonic acid, m-xylene sulfonic acid, phenol sulfonic acid, sulfosalicylic acid, m-nitrobenzene sulfonic acid, p-aminobenzene sulfonic acid, etc. Sulfonic acids may be added. In this case, the concentration of benzenesulfonic acids is preferably 10 g / L or less, more preferably 2 to 4 g / L, from the viewpoint of hydrogen peroxide stability. In addition, when benzenesulfonic acid was added to the conventional sulfuric acid / hydrogen peroxide microetching solution, a precipitate in which copper and benzenesulfonic acid were combined was sometimes generated. Since tetrazole and nitrobenzotriazole are blended, generation of the precipitate can be effectively suppressed.
また、本発明のエッチング液には、粗化後の銅材表面の凹みを深くするために、塩化物イオン源を配合してもよい。塩化物イオン源としては、例えば塩化ナトリウム、塩化カリウム、塩化アンモニウム、塩酸等が挙げられる。塩化物イオン源の濃度は、粗化形状やエッチング速度に応じて調整されるが、塩化物イオンとして１〜６０ｐｐｍが好ましく、２〜３０ｐｐｍがより好ましい。この範囲内であれば、銅材表面を充分に粗化できる。また、安定したエッチング速度を得るために、硫酸銅、塩化銅、酢酸銅などの銅化合物を溶解させてもよい。これらの銅化合物の濃度は、通常、銅濃度として５〜６０ｇ／Ｌ程度である。 Moreover, you may mix | blend a chloride ion source with the etching liquid of this invention in order to deepen the dent of the copper material surface after roughening. Examples of the chloride ion source include sodium chloride, potassium chloride, ammonium chloride, hydrochloric acid and the like. Although the density | concentration of a chloride ion source is adjusted according to a roughening shape and an etching rate, 1-60 ppm is preferable as a chloride ion, and 2-30 ppm is more preferable. Within this range, the copper material surface can be sufficiently roughened. In order to obtain a stable etching rate, a copper compound such as copper sulfate, copper chloride, or copper acetate may be dissolved. The concentration of these copper compounds is usually about 5 to 60 g / L as the copper concentration.
上記エッチング液は、上記の各成分を水に溶解させることにより、容易に調製することができる。上記水としては、イオン性物質や不純物を除去した水が好ましく、例えばイオン交換水、純水、超純水などが好ましい。 The etching solution can be easily prepared by dissolving the above components in water. As the water, water from which ionic substances and impurities have been removed is preferable. For example, ion exchange water, pure water, ultrapure water, and the like are preferable.
上記エッチング液は、各成分を使用時に所定の濃度になるように配合してもよく、濃縮液を調製しておき使用直前に希釈して使用してもよい。上記エッチング液の使用方法は、特に限定されず、浸漬処理、スプレー処理等の方法を採用できるが、銅材表面をより均一に粗化するには、浸漬処理が好ましい。また、使用時のエッチング液の温度は、特に制限はないが、銅材表面をより均一に粗化するには２０〜４０℃で使用することが好ましい。 The etching solution may be blended so that each component has a predetermined concentration when used, or a concentrated solution may be prepared and diluted immediately before use. The method of using the etching solution is not particularly limited, and methods such as immersion treatment and spray treatment can be adopted. However, immersion treatment is preferable in order to more uniformly roughen the copper material surface. Further, the temperature of the etching solution at the time of use is not particularly limited, but it is preferably used at 20 to 40 ° C. in order to roughen the copper material surface more uniformly.
次に、本発明に係るエッチング液の実施例について比較例と併せて説明する。なお、本発明は下記の実施例に限定して解釈されるものではない。 Next, examples of the etching solution according to the present invention will be described together with comparative examples. In addition, this invention is limited to a following example and is not interpreted.
表１（実施例）及び表２（比較例）に示す組成の各エッチング液を用いて、下記に示す測定方法により各項目について評価した。各エッチング液は、まず、硫酸及び過酸化水素をイオン交換水に溶解させた後、残りの成分を添加して調製した。なお、各エッチング液の塩化物イオン源としては、塩化ナトリウムを用いた。 Each item was evaluated by the measuring method shown below using each etching solution having the composition shown in Table 1 (Example) and Table 2 (Comparative Example). Each etching solution was prepared by first dissolving sulfuric acid and hydrogen peroxide in ion exchange water, and then adding the remaining components. In addition, sodium chloride was used as a chloride ion source of each etching solution.
＜エッチング時間＞
厚み35μｍの銅箔を絶縁基材の両面に張り合わせた厚み0.2mmのガラス布エポキシ樹脂含浸銅張積層板を、試験基板として２種類用意した。具体的には、１０ｃｍ×１０ｃｍに裁断したＦＲ−４材（日立化成社製、製品名：ＭＣＬ−Ｅ−６７）と、同じく１０ｃｍ×１０ｃｍに裁断したハロゲンフリー材（日立化成社製、製品名：ＭＣＬ−ＢＥ−６７Ｇ）を試験基板として用意した。次に、表１及び表２に示す各エッチング液（２５℃）を満たした１Ｌビーカー中に、各試験基板を立てて投入し、６０秒間浸漬して銅表面をエッチングした。そして、処理前後の各試験基板の重量から、下式によりエッチング速度（μm/秒）を算出し、このエッチング速度に基づき、銅表面から平均１．０μｍの深さまでエッチングする時間と、銅表面から平均１．５μｍの深さまでエッチングする時間とを算出した。なお、エッチング速度は、ＦＲ−４材及びハロゲンフリー材の間で相違はなかった。
エッチング速度（μm/秒）＝（処理前の重量(g)−処理後の重量(g)）÷基板面積（ｍ2）÷銅の密度（g/cｍ3）÷浸漬時間（秒）
<Etching time>
Two types of glass cloth epoxy resin-impregnated copper clad laminates each having a thickness of 0.2 mm obtained by bonding a copper foil having a thickness of 35 μm to both surfaces of an insulating substrate were prepared as test substrates. Specifically, FR-4 material (product name: MCL-E-67 manufactured by Hitachi Chemical Co., Ltd.) cut to 10 cm × 10 cm and halogen-free material (product name manufactured by Hitachi Chemical Co., Ltd., product cut to 10 cm × 10 cm). : MCL-BE-67G) was prepared as a test substrate. Next, each test substrate was put up in a 1 L beaker filled with each etching solution (25 ° C.) shown in Table 1 and Table 2, and immersed for 60 seconds to etch the copper surface. Then, the etching rate (μm / second) is calculated from the weight of each test substrate before and after the treatment by the following equation, and based on this etching rate, the time for etching from the copper surface to an average depth of 1.0 μm is calculated from the copper surface. The etching time to an average depth of 1.5 μm was calculated. The etching rate was not different between the FR-4 material and the halogen-free material.
Etching rate (μm / second) = (weight before processing (g) −weight after processing (g)) ÷ substrate area (m 2 ) ÷ copper density (g / cm 3 ) ÷ dipping time (seconds)
＜均一性＞
表１及び表２に示す各エッチング液（２５℃）を満たした１Ｌビーカー中に、上記試験基板と同様の試験基板を立てて投入し、上記算出したエッチング時間だけ浸漬して銅表面をエッチングした。これにより、銅表面から平均１．０μｍの深さまでエッチングしたＦＲ−４材及びハロゲンフリー材と、銅表面から平均１．５μｍの深さまでエッチングしたＦＲ−４材及びハロゲンフリー材とを得た。そして、これら処理後の試験基板（４種類）を目視にて観察して、粗化状態の均一性について、いずれの基板にもムラが全くなかったものを◎、いずれの基板にもムラはなかったが、少なくとも１種類の基板に薄いスジやテカリがあったものを○、少なくとも１種類の基板にムラがあったものを×として評価した。なお、均一性にムラがある場合は、通常、密着性にもムラができ、密着不良をおこすおそれがある。
<Uniformity>
In a 1 L beaker filled with each etching solution (25 ° C.) shown in Table 1 and Table 2, a test substrate similar to the above test substrate was placed upright and immersed for the calculated etching time to etch the copper surface. . As a result, an FR-4 material and a halogen-free material etched to an average depth of 1.0 μm from the copper surface, and an FR-4 material and a halogen-free material etched to an average depth of 1.5 μm from the copper surface were obtained. And after visually observing the test substrates (4 types) after these treatments, the uniformity in the roughened state is ◎, which is not uneven at all, and there is no unevenness at any of the substrates However, the case where thin streaks and shine were found on at least one type of substrate was evaluated as “◯”, and the case where at least one type of substrate was uneven was evaluated as “x”. In addition, when there is unevenness in uniformity, there is usually a possibility of unevenness in adhesion, which may cause poor adhesion.
＜ピール強度（引き剥がし強さ）＞
厚み35μｍの電解銅箔を１０ｃｍ×１０ｃｍに裁断し、上記均一性の評価の場合と同様の方法で光沢面をエッチングした。そして、エッチングを行った光沢面に、ガラス布エポキシ樹脂含浸プリプレグを積層プレス（プレス圧：３０ＭＰａ、温度：１７０℃、時間：６０分）により張り合わせた。この際のガラス布エポキシ樹脂含浸プリプレグには、ＦＲ−４材（日立化成社製、製品名：ＧＥＡ−６７Ｎ、厚さ０．１５ｍｍ）と、ハロゲンフリー材（日立化成社製、製品名：ＧＥＡ−６７ＢＥ、厚さ０．１ｍｍ）の２種類を使用した。次いで、上記ＦＲ−４材又は上記ハロゲンフリー材が張り合わされた基板をＪＩＳ Ｃ ６４８１に準じて１ｃｍ幅にサンプリングし、ピール強度を求めた。
<Peel strength (peeling strength)>
An electrolytic copper foil having a thickness of 35 μm was cut into 10 cm × 10 cm, and the glossy surface was etched by the same method as in the evaluation of the uniformity. Then, a glass cloth epoxy resin-impregnated prepreg was laminated on the etched glossy surface by a lamination press (press pressure: 30 MPa, temperature: 170 ° C., time: 60 minutes). In this case, the glass cloth epoxy resin-impregnated prepreg includes FR-4 material (manufactured by Hitachi Chemical Co., Ltd., product name: GEA-67N, thickness 0.15 mm) and halogen-free material (manufactured by Hitachi Chemical Co., Ltd., product name: GEA). -67BE, thickness 0.1 mm) were used. Subsequently, the substrate on which the FR-4 material or the halogen-free material was bonded was sampled to a width of 1 cm in accordance with JIS C 6481 to determine the peel strength.
＜はんだ耐熱性＞
上記均一性の評価を行った後の各試験基板の両面に、ガラス布エポキシ樹脂含浸プリプレグを上記ピール強度の評価の場合と同様に積層プレスにより張り合わせた。この際、ＦＲ−４材（ＭＣＬ−Ｅ−６７）を用いた試験基板に対しては、ＦＲ−４材（日立化成社製、製品名：ＧＥＡ−６７Ｎ、厚さ０．１５ｍｍ）を使用し、ハロゲンフリー材（ＭＣＬ−ＢＥ−６７Ｇ）を用いた試験基板に対しては、ハロゲンフリー材（日立化成社製、製品名：ＧＥＡ−６７ＢＥ、厚さ０．１ｍｍ）を使用した。次いで、積層した基板の周辺部を切り取ってテストピースを作製した。このテストピースを１００℃（湿度：１００％）中に４時間放置した後、ＪＩＳ Ｃ ６４８１に準じて２７０℃の溶融はんだ浴中に３０秒間浸漬した。そして、浸漬後の各試験基板を目視にて観察して、剥がれ・膨れが全く見られなかったものを◎、小さな膨れがあったものを○、大きな剥がれや膨れがあったものを×として評価した。
<Solder heat resistance>
A glass cloth epoxy resin-impregnated prepreg was bonded to both surfaces of each test substrate after the evaluation of the uniformity by a lamination press in the same manner as in the evaluation of the peel strength. At this time, FR-4 material (manufactured by Hitachi Chemical Co., Ltd., product name: GEA-67N, thickness 0.15 mm) is used for the test substrate using FR-4 material (MCL-E-67). A halogen-free material (manufactured by Hitachi Chemical Co., Ltd., product name: GEA-67BE, thickness 0.1 mm) was used for a test substrate using a halogen-free material (MCL-BE-67G). Next, a test piece was produced by cutting off the peripheral portion of the laminated substrate. This test piece was allowed to stand at 100 ° C. (humidity: 100%) for 4 hours, and then immersed in a molten solder bath at 270 ° C. for 30 seconds in accordance with JIS C 6481. Then, each test substrate after immersion was visually observed and evaluated as ◎ if there was no peeling or swelling, ○ if there was a small swelling, and × if there was a large peeling or swelling. did.
＜析出物の有無＞
表１及び表２に示す各エッチング液を５０℃の恒温槽に１６８時間放置し、析出物の有無を目視にて確認した。
<Presence / absence of precipitate>
Each etching solution shown in Table 1 and Table 2 was left in a thermostatic bath at 50 ° C. for 168 hours, and the presence or absence of precipitates was confirmed visually.
表１及び表２に示すように、本発明の実施例１〜８は、いずれの評価項目についても良好な結果が得られた。特に、ニトロベンゾトリアゾール類の濃度が、フェニルテトラゾール類の濃度の１．０〜３．０倍である実施例１，２，６，７は、銅表面から平均１．０μｍの深さまでエッチングしたハロゲンフリー材を用いても、はんだ耐熱性が◎の評価となった。一方、比較例１〜５については、実施例１〜８と比較していずれの評価項目についても劣る結果となった。特に、ハロゲンフリー材を用いた場合に、ピール強度及びはんだ耐熱性の少なくとも一方が実施例１〜８に比べ極端に劣る結果となった。このことから、本発明によれば、高温条件下においても銅層と絶縁層との密着性を確実に維持することができる上、広範な絶縁材に対して密着性を向上させ得ることが分かった。 As shown in Table 1 and Table 2, in Examples 1 to 8 of the present invention, good results were obtained for any of the evaluation items. In particular, Examples 1, 2, 6, and 7 in which the concentration of nitrobenzotriazoles is 1.0 to 3.0 times the concentration of phenyltetrazoles are halogen etched to an average depth of 1.0 μm from the copper surface. Even when a free material was used, the solder heat resistance was evaluated as ◎. On the other hand, about Comparative Examples 1-5, it became a result inferior also about any evaluation item compared with Examples 1-8. In particular, when a halogen-free material was used, at least one of peel strength and solder heat resistance was extremely inferior to Examples 1-8. Thus, according to the present invention, it is found that the adhesion between the copper layer and the insulating layer can be reliably maintained even under high temperature conditions, and the adhesion can be improved with respect to a wide range of insulating materials. It was.
Claims (10)
フェニルテトラゾール類及びニトロベンゾトリアゾール類を含むことを特徴とするエッチング液。 An etching solution for copper containing sulfuric acid, hydrogen peroxide and water,
An etching solution comprising phenyltetrazole and nitrobenzotriazole.
前記過酸化水素の濃度が、５〜７０ｇ／Ｌである請求項１〜６のいずれか一項に記載のエッチング液。 The concentration of the sulfuric acid is 60 to 220 g / L,
The etching solution according to any one of claims 1 to 6, wherein a concentration of the hydrogen peroxide is 5 to 70 g / L.
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| JP2008267719A JP4278705B1 (en) | 2008-01-16 | 2008-10-16 | Etching solution |
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| CN2008101877176A CN101487122B (en) | 2008-01-16 | 2008-12-31 | Etching solution |
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| WO2011093445A1 (en) * | 2010-01-28 | 2011-08-04 | 三菱瓦斯化学株式会社 | Etching liquid for a copper/titanium multilayer thin film |
| KR20110108252A (en) * | 2010-03-26 | 2011-10-05 | 멕크 가부시키가이샤 | Etching solution for copper and substrate manufacturing method |
| CN115404480A (en) * | 2022-08-30 | 2022-11-29 | 昆山市板明电子科技有限公司 | Recyclable copper surface roughening micro-etching solution and use method thereof |
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| JP2000282265A (en) | 1999-03-31 | 2000-10-10 | Mec Kk | Microetching agent for copper or copper alloy and surface treating method using the same |
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| Publication number | Publication date |
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| CN101487122B (en) | 2011-04-06 |
| KR101550069B1 (en) | 2015-09-03 |
| JP4278705B1 (en) | 2009-06-17 |
| KR20090079172A (en) | 2009-07-21 |
| TW200932955A (en) | 2009-08-01 |
| CN101487122A (en) | 2009-07-22 |
| TWI398552B (en) | 2013-06-11 |
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