JP4750645B2 - Surface treatment agent and treatment method for copper or copper alloy surface - Google Patents
Surface treatment agent and treatment method for copper or copper alloy surface Download PDFInfo
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- JP4750645B2 JP4750645B2 JP2006220038A JP2006220038A JP4750645B2 JP 4750645 B2 JP4750645 B2 JP 4750645B2 JP 2006220038 A JP2006220038 A JP 2006220038A JP 2006220038 A JP2006220038 A JP 2006220038A JP 4750645 B2 JP4750645 B2 JP 4750645B2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 81
- 229910052802 copper Inorganic materials 0.000 title claims description 81
- 239000010949 copper Substances 0.000 title claims description 81
- 229910000881 Cu alloy Inorganic materials 0.000 title claims description 51
- 238000000034 method Methods 0.000 title claims description 12
- 239000012756 surface treatment agent Substances 0.000 title claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 36
- 239000007864 aqueous solution Substances 0.000 claims description 33
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 125000001424 substituent group Chemical group 0.000 claims description 9
- 125000000623 heterocyclic group Chemical group 0.000 claims description 7
- 150000007522 mineralic acids Chemical class 0.000 claims description 7
- 238000004381 surface treatment Methods 0.000 claims description 7
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000007772 electroless plating Methods 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
- 238000007740 vapor deposition Methods 0.000 claims description 5
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims description 4
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 4
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 3
- BAXOFTOLAUCFNW-UHFFFAOYSA-N 1H-indazole Chemical compound C1=CC=C2C=NNC2=C1 BAXOFTOLAUCFNW-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 3
- 239000012964 benzotriazole Substances 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims description 3
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 235000005985 organic acids Nutrition 0.000 claims description 3
- 150000003536 tetrazoles Chemical class 0.000 claims description 3
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 claims description 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 claims description 2
- SDXAWLJRERMRKF-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazole Chemical compound CC=1C=C(C)NN=1 SDXAWLJRERMRKF-UHFFFAOYSA-N 0.000 claims description 2
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 claims description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000000174 gluconic acid Substances 0.000 claims description 2
- 235000012208 gluconic acid Nutrition 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 claims description 2
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 2
- 229940044654 phenolsulfonic acid Drugs 0.000 claims description 2
- 150000003852 triazoles Chemical class 0.000 claims description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims 2
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 claims 1
- 150000002366 halogen compounds Chemical class 0.000 claims 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims 1
- 239000011347 resin Substances 0.000 description 30
- 229920005989 resin Polymers 0.000 description 30
- 229920002120 photoresistant polymer Polymers 0.000 description 26
- 239000000758 substrate Substances 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 20
- 238000011161 development Methods 0.000 description 14
- 238000007747 plating Methods 0.000 description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 12
- 238000005498 polishing Methods 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000005530 etching Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000000565 5-membered heterocyclic compounds Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- -1 imino hydrogen Chemical compound 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000000059 patterning Methods 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- FUOZJYASZOSONT-UHFFFAOYSA-N 2-propan-2-yl-1h-imidazole Chemical compound CC(C)C1=NC=CN1 FUOZJYASZOSONT-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000011962 puddings Nutrition 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- BUUPQKDIAURBJP-UHFFFAOYSA-N sulfinic acid Chemical compound OS=O BUUPQKDIAURBJP-UHFFFAOYSA-N 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Landscapes
- ing And Chemical Polishing (AREA)
- Manufacturing Of Printed Wiring (AREA)
Description
本発明は、プリント配線板などの銅又は銅合金表面の表面処理剤及び表面処理方法に関する。 The present invention relates to a surface treatment agent and a surface treatment method for the surface of copper or a copper alloy such as a printed wiring board.
銅又は銅合金の上に感光性フィルムによるめっきレジスト又はエッチングレジストを形成しパターンニングを行うプリント配線板の製造過程において、感光性樹脂（フォトレジスト）を形成させるための銅又は銅合金の前処理として、バフ研磨などの物理研磨又はソフトエッチングなどの化学研磨が一般的に採り入れられている。これらの研磨の前処理は、銅又は銅合金の表面を活性化させるという目的のほかに、銅又は銅合金の表面を粗化することに因るアンカー作用で感光性樹脂（フォトレジスト）との密着性を向上させる効果を持っている。しかしながら絶縁層を有する基材自体の薄層化或いは感光性樹脂（フォトレジスト）を形成させる銅又は銅合金自体の薄膜化（蒸着層又は無電解めっき層）に伴い物理研磨や化学研磨が困難なケースが増えてきたため、銅又は銅合金の活性化処理を希硫酸による除錆に変更するケースが増えてきている。更に、近年では、形成されるパターンの細線、縮小化によって、希硫酸活性処理では感光性樹脂（フォトレジスト）によるめっきレジスト又はエッチングレジストの密着性に問題が生じ、生産性の低下が起きつつある状況である。より具体的には、銅又は銅合金上に形成された感光性樹脂（フォトレジスト）は、露光後に炭酸ナトリウムなどの水溶液で現像され、その現像パターンが次工程でめっきレジスト又はエッチングレジストとして利用されるが、めっき工程又はエッチング工程でレジスト密着性が確保できなければめっき工程処理剤又はエッチング工程処理剤の潜り込みが起きるため、所望しているパターンニングの形状が得られない。特に、絶縁層上に導電膜として形成される銅又は銅合金の蒸着層又は無電解めっき層は薄く研磨できないため、感光性樹脂（フォトレジスト）との密着性を化学的に向上させる手法の確立が求められている。 Pre-treatment of copper or copper alloy to form photosensitive resin (photoresist) in the manufacturing process of printed wiring board that forms plating resist or etching resist with photosensitive film on copper or copper alloy and performs patterning In general, physical polishing such as buff polishing or chemical polishing such as soft etching is generally adopted. In addition to the purpose of activating the surface of copper or a copper alloy, these pretreatments for polishing can be performed with a photosensitive resin (photoresist) by an anchor action caused by roughening the surface of the copper or copper alloy. Has the effect of improving adhesion. However, physical polishing and chemical polishing are difficult due to the thinning of the substrate itself having an insulating layer or the thinning of the copper or copper alloy itself (deposition layer or electroless plating layer) that forms a photosensitive resin (photoresist). Since the number of cases has increased, the number of cases where the activation treatment of copper or copper alloy is changed to rust removal with dilute sulfuric acid has increased. Further, in recent years, due to the fine lines and reduction of the pattern to be formed, the dilute sulfuric acid activation treatment has caused problems in the adhesion of the plating resist or the etching resist with the photosensitive resin (photoresist), and the productivity is decreasing. Is the situation. More specifically, a photosensitive resin (photoresist) formed on copper or a copper alloy is developed with an aqueous solution such as sodium carbonate after exposure, and the developed pattern is used as a plating resist or etching resist in the next step. However, if the resist adhesion cannot be ensured in the plating step or the etching step, the plating step treatment agent or the etching step treatment agent may be submerged, so that a desired patterning shape cannot be obtained. In particular, since a copper or copper alloy deposition layer or electroless plating layer formed as a conductive film on an insulating layer cannot be thinly polished, establishment of a method for chemically improving the adhesion to a photosensitive resin (photoresist) Is required.
特開平１１−４３７７８号公報には、アミノテトラゾール及びアミノテトラゾール誘導体から選ばれる化合物を含有する水溶液（第一の水溶液）又はアミノテトラゾール及びアミノテトラゾール誘導体から選ばれる化合物とアミノトリアゾール及びアミノトリアゾール誘導体から選ばれる化合物とを含有する水溶液（第二の水溶液）を、ガラス転移温度が１５０℃以上の樹脂が接着される銅の表面に塗布する銅の表面処理法が記載されている。しかしながら、当該文献には、ガラス転移温度が高い樹脂との密着性を保つためには、第一の水溶液又は第二の水溶液と接触付着させる前に、物理研磨又は化学研磨よって銅表面を粗化させることが好ましい旨の記載があり、物理研磨又は化学研磨による銅表面の粗化を行わなくても当該第一の水溶液又は第二の水溶液によって銅表面と樹脂との密着性が向上するかどうかについて明確に示されていない。
このように、従来技術においては、蒸着層又は無電解めっき層からなる銅又は銅合金は薄層のため物理研磨又は化学研磨ができないことから、当該銅又は銅合金の表面と感光性樹脂（フォトレジスト）によるめっきレジスト又はエッチングレジストとの十分な密着性を確保できないという問題があった。本発明はこのような状況を鑑みてなされたものであり、銅又は銅合金表面と感光性樹脂（フォトレジスト）との十分な密着性を確保できる銅又は銅合金用の処理剤及び銅又は銅合金の表面処理方法を提供することを課題とする。 As described above, in the prior art, copper or a copper alloy composed of a vapor deposition layer or an electroless plating layer cannot be physically polished or chemically polished because it is a thin layer. There has been a problem that sufficient adhesion to a plating resist or etching resist by resist) cannot be secured. This invention is made | formed in view of such a condition, The processing agent for copper or copper alloy which can ensure sufficient adhesiveness of the copper or copper alloy surface, and photosensitive resin (photoresist), and copper or copper It is an object of the present invention to provide an alloy surface treatment method.
この課題を解決するために、次式：
によって表される１種以上の複素環式化合物を含有し、しかもｐＨが４以下である水溶液からなる銅又は銅合金用表面処理剤を提供する。
To solve this problem, the following formula:
The surface treatment agent for copper or copper alloy which consists of the aqueous solution which contains 1 or more types of heterocyclic compounds represented by these, and is pH 4 or less is provided.
また、本発明は、銅又は銅合金用表面処理剤と銅又は銅合金の表面とを接触させ、その後に該表面上に感光性フィルムによるレジスト層を形成させることを特徴とする、銅又は銅合金の表面処理方法も提供する。 Further, the present invention is characterized in that the surface treatment agent for copper or copper alloy and the surface of copper or copper alloy are brought into contact with each other, and then a resist layer made of a photosensitive film is formed on the surface. An alloy surface treatment method is also provided.
本発明の表面処理剤又は表面処理方法によれば、４以下のｐＨにより蒸着層又は無電解めっき層からなる銅又は銅合金であってもエッチングすることなく銅又は銅合金表面が活性化され、そして当該処理剤に含まれる１種以上の複素環式化合物が当該活性化された銅又は銅合金の表面に付着するため、当該銅又は銅合金の表面と感光性樹脂（フォトレジスト）との十分な密着性が確保できる。 According to the surface treatment agent or the surface treatment method of the present invention, the copper or copper alloy surface is activated without etching even if it is copper or a copper alloy comprising a vapor deposition layer or an electroless plating layer at a pH of 4 or less, And since the 1 or more types of heterocyclic compound contained in the said processing agent adheres to the surface of the said activated copper or copper alloy, sufficient of the surface of the said copper or copper alloy, and photosensitive resin (photoresist) Good adhesion can be secured.
本発明によれば、物理研磨や化学研磨が行なえない銅又は銅合金であっても、当該銅又は銅合金の表面と感光性樹脂（フォトレジスト）との密着性を向上できる。本発明の銅又は銅合金の処理剤及び処理方法は、感光性樹脂（フォトレジスト）の細線密着性が要求されるプリント配線板の製造に好適である。 According to this invention, even if it is copper or a copper alloy which cannot perform physical polishing and chemical polishing, the adhesiveness of the surface of the said copper or copper alloy and photosensitive resin (photoresist) can be improved. The treatment agent and treatment method for copper or copper alloy of the present invention are suitable for the production of a printed wiring board in which fine wire adhesion of a photosensitive resin (photoresist) is required.
本発明の銅又は銅合金用表面処理剤は、以下に説明する１種以上の複素環式化合物を含有し、しかもｐＨが４以下である水溶液からなることに大きな特徴がある。すなわち、この４以下のｐＨにより、当該複素環式化合物の銅又は銅合金への付着が促進され、その結果として当該銅又は銅合金の表面と感光性樹脂（フォトレジスト）との密着性が向上し得る。ｐＨ４以下の場合に当該複素環式化合物の銅又は銅合金表面への付着が進行する明確な理由は定かではないが、通常数〜十数オングストームの酸化層膜（一価銅及び二価銅層）に覆われている銅又は銅合金をｐＨ４以下の処理液に浸漬した場合、当該酸化膜が僅かに還元される過程で当該複素環式化合物のイミノ水素が当該一価銅と反応して付着するためであると考えられる。なお、当該水溶液のｐＨは、３．５以下、さらには３．０以下がさらに好ましい。 The surface treatment agent for copper or copper alloy of the present invention is characterized by comprising an aqueous solution containing one or more heterocyclic compounds described below and having a pH of 4 or less. That is, the pH of 4 or less promotes the adhesion of the heterocyclic compound to copper or a copper alloy, and as a result, the adhesion between the surface of the copper or copper alloy and the photosensitive resin (photoresist) is improved. Can do. Although it is not clear why the heterocyclic compound adheres to the copper or copper alloy surface when the pH is 4 or less, it is usually an oxide layer film (monovalent copper and divalent copper) of several to tens of angstroms. When copper or a copper alloy covered with a layer is immersed in a treatment solution having a pH of 4 or less, imino hydrogen of the heterocyclic compound reacts with the monovalent copper in the process of slightly reducing the oxide film. This is thought to be due to adhesion. In addition, the pH of the aqueous solution is 3.5 or less, more preferably 3.0 or less.
一方、当該水溶液のｐＨが４を越えると、複素環式化合物の溶解性が低下したり、複素環式化合物の銅又は銅合金表面への付着性が低下したりするため、十分な密着性が得られない。また、ｐＨ４を超える水溶液では、銅及び銅合金の活性化ができず、これらの付着反応が著しく抑制されるため、十分な効果が得られない。
On the other hand, if the pH of the aqueous solution exceeds 4, the solubility of the heterocyclic compound is lowered, or the adhesion of the heterocyclic compound to the copper or copper alloy surface is lowered. I can't get it. Moreover, in the aqueous solution exceeding pH 4, copper and a copper alloy cannot be activated, and since these adhesion reactions are remarkably suppressed, sufficient effects cannot be obtained.
４以下のｐＨは、無機酸及び有機酸から選択される１種以上の酸により達成できる。ここで、用語「無機酸」とは、Ｓ、Ｎ、Ｐ、Ｂなどの、ハロゲン以外の非金属を含む酸基が水素と結合してできた酸をいい、具体的には硫酸、亜硫酸、硝酸、亜硝酸、オルト燐酸、亜燐酸、ピロ燐酸、メタ燐酸、ホウ酸などが挙げられる。本発明の銅又は銅合金用表面処理剤に使用できる無機酸としては、硝酸、硫酸、燐酸、ホウ酸などが好ましい。これらの無機酸は、複素環式化合物の銅への付着反応を特に促進させるからである。また、本発明において用語「有機酸」とは、有機化合物のうち酸性の性質を有するものをいい、具体的にはカルボン酸、スルホン酸、スルフィン酸などが挙げられる。本発明においては、特に、カルボン酸及びスルホン酸が使用できる。ここで、用語「カルボン酸」とは、炭化水素の水素原子が「−ＣＯＯＨ」で置換された化合物をいい、用語「スルホン酸」とは、炭化水素の水素原子がスルホン基（−ＳＯ3Ｈ）で置換された化合物をいう。使用できるカルボン酸に特に制限はないが、酢酸、グリコール酸、クエン酸、グルコン酸などが好ましい。また、使用できるスルホン酸も特に制限はないが、メタンスルホン酸、エタノールスルホン酸、フェノールスルホン酸、トルエンスルホン酸などが好ましい。なお、当該水溶液に、ｐＨ調整のために水酸化ナトリウム、水酸化カリウム、アンモニア水など、或いはこれら無機酸又は有機酸の塩を適宜添加することも可能である。 A pH of 4 or less can be achieved with one or more acids selected from inorganic and organic acids. Here, the term "inorganic acid", S, N, P, such as B, acid group containing non-metallic non-halogen refers to acid Deki combined with hydrogen, in particular sulfuric acid, sulfurous , Nitric acid, nitrous acid, orthophosphoric acid, phosphorous acid, pyrophosphoric acid, metaphosphoric acid, boric acid and the like. Inorganic acids that can be used for copper or copper alloy surface treatment agent of the present invention, nitric acid, sulfuric acid, phosphoric acid, and boric acid. This is because these inorganic acids particularly promote the adhesion reaction of the heterocyclic compound to copper. In the present invention, the term “organic acid” refers to an organic compound having an acidic property, and specifically includes carboxylic acid, sulfonic acid, sulfinic acid, and the like. In the present invention, in particular, carboxylic acid and sulfonic acid can be used. Here, the term “carboxylic acid” refers to a compound in which a hydrocarbon hydrogen atom is replaced by “—COOH”, and the term “sulfonic acid” refers to a hydrocarbon hydrogen atom that is a sulfone group (—SO 3 H ). The carboxylic acid that can be used is not particularly limited, but acetic acid, glycolic acid, citric acid, gluconic acid and the like are preferable. The sulfonic acid that can be used is not particularly limited, but methanesulfonic acid, ethanolsulfonic acid, phenolsulfonic acid, toluenesulfonic acid and the like are preferable. In addition, it is also possible to add sodium hydroxide, potassium hydroxide, aqueous ammonia, or a salt of these inorganic acids or organic acids as appropriate to adjust the pH.
当該水溶液に含まれる複素環式化合物は、次式：
本発明の別の具体例では、上記式においてＲ1〜Ｒ4のうちの少なくとも一つは炭素原子を表し、しかも当該炭素原子のうち少なくとも１個が保持する水素は、ある種の置換基によって置換されている。ここで、当該置換基の例としては、窒素、酸素及び硫黄から選択される少なくとも１個のヘテロ原子を含有する基、Ｃ1〜Ｃ6アルキル基及びアリール基などが挙げられる。１個以上のヘテロ原子を含有する基としては、ヒドロキシ基、アルコキシ基又はアミノ基が挙げられるが、この場合、アミノ基が最も好ましい。また、好ましいアルキル基としては、メチル、エチル、プロピル、ブチル、ペンチル、ヘキシルなど及びこれらの異性体が挙げられるが、これらに限定されない。より好ましいアルキル基は、メチル基、エチル基及びイソプロピル基である。好ましいアリール基はフェニル基である。これらの置換基を有する５員環複素環式化合物の例としては、５−アミノテトラゾール、３−アミノ−１，２，４−トリアゾール、３，５−ジメチルピラゾール、２−イソプロピルイミダゾール、５−フェニルテトラゾールなどが挙げられる。 In another embodiment of the present invention, at least one of R 1 to R 4 in the above formula represents a carbon atom, and the hydrogen held by at least one of the carbon atoms is a certain substituent. Has been replaced. Here, examples of the substituent include a group containing at least one hetero atom selected from nitrogen, oxygen and sulfur, a C 1 to C 6 alkyl group, an aryl group, and the like. Examples of the group containing one or more heteroatoms include a hydroxy group, an alkoxy group, and an amino group. In this case, an amino group is most preferable. Preferred alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl and the like and isomers thereof. More preferred alkyl groups are a methyl group, an ethyl group and an isopropyl group. A preferred aryl group is a phenyl group. Examples of 5-membered heterocyclic compounds having these substituents include 5-aminotetrazole, 3-amino-1,2,4-triazole, 3,5-dimethylpyrazole, 2-isopropylimidazole, and 5-phenyl. Examples include tetrazole.
また、別の具体例では、上記式において、Ｒ1とＲ2及び／又はＲ3とＲ4は、他の炭素環又は複素環と共に縮合環を形成することができる。ここで、他の炭素環の例としては、ベンゼン環が挙げられる。また、他の複素環の例としては、窒素、酸素及び硫黄よりなる群から選択される１個以上のヘテロ原子を含む５員環又は６員環が挙げられる。この縮合環化合物の具体例としては、当該５員環とベンゼン環との縮合環化合物であるインドール、インダゾール、ベンゾイミダゾール、ベンゾトリアゾール、カルバゾール及び当該５員環と他の複素環との縮合環であるプリン、カルボリンなどが挙げられる。好ましい縮合環化合物は、インドール、インダゾール、ベンゾイミダゾール及びベンゾトリアゾールである。また、これらの縮合環化合物は１個以上の置換基を有していてもよい。置換基の例としては、上記５員環化合物の置換誘導体について説明したもの又は低級アルキル基、例えばメチル基が挙げられる。当該置換基を有する縮合環化合物の例は、５−メチルベンゾトリアゾールである。 In another specific example, in the above formula, R 1 and R 2 and / or R 3 and R 4 can form a condensed ring together with other carbocycles or heterocycles. Here, a benzene ring is mentioned as an example of another carbocyclic ring. Examples of other heterocycles include 5-membered or 6-membered rings containing one or more heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur. Specific examples of the condensed ring compound include indole, indazole, benzimidazole, benzotriazole, carbazole and condensed rings of the 5-membered ring and other heterocyclic rings, which are condensed ring compounds of the 5-membered ring and a benzene ring. Some puddings, carbolines, etc. Preferred fused ring compounds are indole, indazole, benzimidazole and benzotriazole. Moreover, these condensed ring compounds may have one or more substituents. Examples of substituents include those described for the substituted derivatives of the 5-membered ring compounds or lower alkyl groups such as methyl groups. An example of the condensed ring compound having the substituent is 5-methylbenzotriazole.
本発明の銅又は銅合金用表面処理剤は、上に挙げた複素環式化合物を１種以上含有することができる。 The surface treating agent for copper or copper alloy of the present invention can contain one or more of the heterocyclic compounds listed above.
当該複素環式化合物の配合量は、総量として０．００５〜３重量％が好適範囲であり、より好ましくは総量として０．０１〜２重量％範囲であるが、これらに限定されない。なお、当該配合量が０．００１重量％未満では、銅又は銅合金への付着性が低下して十分な効果が得られず、３重量％を超えると効果が飽和し不経済である。 The compounding amount of the heterocyclic compound is preferably in the range of 0.005 to 3% by weight as the total amount, and more preferably in the range of 0.01 to 2% by weight as the total amount, but is not limited thereto. In addition, if the said compounding quantity is less than 0.001 weight%, the adhesiveness to copper or a copper alloy will fall, and sufficient effect will not be acquired, but if it exceeds 3 weight%, an effect will be saturated and it will be uneconomical.
銅又は銅合金表面の処理は、浸漬又はスプレー方式などにより、本発明の水溶液を銅又は銅合金の表面に均一に付着させる態様で実施される。処理される銅又は銅合金は、好ましくは無電解めっき層又は蒸着層からなる。当該処理は、具体的には、室温〜４０℃の範囲の処理温度で５〜１２０秒の処理時間にわたって実施される。この処理工程後に、水洗及び乾燥工程を実施する。なお、当該水洗及び乾燥は、一般的な水洗、乾燥工程で十分である。 The treatment of the copper or copper alloy surface is carried out in such a manner that the aqueous solution of the present invention is uniformly attached to the surface of the copper or copper alloy by dipping or spraying. The copper or copper alloy to be treated preferably consists of an electroless plating layer or a vapor deposition layer. Specifically, the treatment is performed at a treatment temperature in the range of room temperature to 40 ° C. for a treatment time of 5 to 120 seconds. After this treatment step, a water washing and drying step is performed. In addition, the said water washing and drying are enough for a general water washing and drying process.
この乾燥工程後に、表面処理剤で処理された銅又は銅合金の表面に感光性樹脂（フォトレジスト）をラミネートし、露光し、そしてアルカリ溶液で現像してレジスト面を形成させる。このときに、本発明の表面処理剤により処理された銅又は銅合金の表面と感光性樹脂との密着性が、従来技術と比較して有意に向上する。１種以上の複素環式化合物の付着により銅又は銅合金の表面と感光性樹脂（フォトレジスト）との密着性が向上する理論は明らかでないが、アクリル酸及び／又はメタクリル酸から成る感光性樹脂（フォトレジスト）が露光される過程で、当該複素環式化合物が銅及び銅合金の表面と感光性樹脂（フォトレジスト）との間でバインダー成分として作用し、それによって次工程での密着性が著しく向上するものと考えられる。 After this drying step, a photosensitive resin (photoresist) is laminated on the surface of copper or copper alloy treated with the surface treating agent, exposed, and developed with an alkaline solution to form a resist surface. At this time, the adhesion between the surface of the copper or copper alloy treated with the surface treating agent of the present invention and the photosensitive resin is significantly improved as compared with the prior art. Although the theory that the adhesion between the surface of copper or a copper alloy and a photosensitive resin (photoresist) is improved by the adhesion of one or more heterocyclic compounds is not clear, a photosensitive resin composed of acrylic acid and / or methacrylic acid In the process of exposing the (photoresist), the heterocyclic compound acts as a binder component between the surface of the copper and copper alloy and the photosensitive resin (photoresist), thereby improving the adhesion in the next step. It is thought that it will improve remarkably.
以下、実施例により本発明をより具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to these Examples.
（密着性試験）
実施例及び比較例の結果を表１に示す。評価はテープ引きはがし部のレジスト残留面積の観察によって行い、○はレジストはく離なし、△はレジストはく離面積５％未満、×はレジストのはく離面積５％以上を示す。
(Adhesion test)
The results of Examples and Comparative Examples are shown in Table 1. The evaluation is performed by observing the resist residual area at the tape peeling portion, where ◯ indicates no resist peeling, Δ indicates a resist peeling area of less than 5%, and x indicates a resist peeling area of 5% or more.
実施例１〜３
表１に示す実施例番号１〜３の組成の水溶液をイオン交換水で調整し、３５℃恒温とした。凡そ１μｍの膜厚の銅蒸着膜を有する基材をこれらの水溶液に２０秒間浸漬し、次いで、該基材を水洗し、そして乾燥させた。その後、乾燥した当該銅表面に、日立化成工業株式会社製の感光性樹脂（フォトレジスト）Ｐｈｏｔｅｃ ＲＹ−３２１５をラミネートし、６５ｍＪ／ｃｍ2にて露光し、そして１重量％の炭酸ナトリウムで最小現像時間の２倍時間で現像して、ライン／スペースが４０μｍ／４０μｍのレジスト面を形成させた。次いで、該基材を５０℃恒温にした２規定の塩酸に１分間浸漬し、更に３０℃恒温にした２規定の硫酸に１時間浸漬した。その後、レジスト面にテープを圧着し、これを垂直方向に引き剥がした。レジスト密着性をマイクロスコープにて確認した。
Examples 1-3
The aqueous solutions having the compositions of Example Nos. 1 to 3 shown in Table 1 were adjusted with ion-exchanged water to a constant temperature of 35 ° C. Substrates having a copper deposited film with a thickness of approximately 1 μm were immersed in these aqueous solutions for 20 seconds, and then the substrate was washed with water and dried. Thereafter, a photosensitive resin (photoresist) Phototec RY-3215 manufactured by Hitachi Chemical Co., Ltd. is laminated on the dried copper surface, exposed at 65 mJ / cm 2 , and minimally developed with 1 wt% sodium carbonate. Development was carried out in twice the time to form a resist surface with a line / space of 40 μm / 40 μm. Next, the substrate was immersed in 2N hydrochloric acid at a constant temperature of 50 ° C. for 1 minute, and further immersed in 2N sulfuric acid at a constant temperature of 30 ° C. for 1 hour. Thereafter, a tape was pressure-bonded to the resist surface and peeled off in the vertical direction. Resist adhesion was confirmed with a microscope.
実施例４〜６
表１に示す実施例番号４〜６の組成の水溶液をイオン交換水で調整し、２５℃恒温とした。凡そ０．５μｍの膜厚の無電解銅めっき膜を有する基材をこれらの水溶液に１５秒間浸漬し、次いで該基材を水洗し、そして乾燥させた。その後、乾燥した当該銅表面に、ニチゴー・モートン株式会社製の感光性樹脂（フォトレジスト）ＡＬＰＨＯ ＮＩＴ２２５をラミネートし、１００ｍＪ／ｃｍ2にて露光し、そして１重量％炭酸カリウムで最小現像時間の２倍時間で現像して、ライン／スペースが４０μｍ／４０μｍのレジスト面を形成させた。次いで、該基材を５０℃恒温にした２規定の塩酸に１分間浸漬し、更に３０℃恒温にした２規定の硫酸に１時間浸漬した。その後、このレジスト面にテープを圧着し、これを垂直方向に引き剥がした。レジスト密着性をマイクロスコープにて確認した。
Examples 4-6
The aqueous solutions having the compositions of Example Nos. 4 to 6 shown in Table 1 were adjusted with ion-exchanged water and kept at a constant temperature of 25 ° C. Substrates having an electroless copper plating film with a thickness of approximately 0.5 μm were immersed in these aqueous solutions for 15 seconds, and then the substrate was washed with water and dried. Thereafter, a photosensitive resin (photoresist) ALPHA NIT225 manufactured by Nichigo-Morton Co., Ltd. is laminated on the dried copper surface, exposed at 100 mJ / cm 2 , and a minimum development time of 2 with 1 wt% potassium carbonate. Development was performed in a double time to form a resist surface having a line / space of 40 μm / 40 μm. Next, the substrate was immersed in 2N hydrochloric acid at a constant temperature of 50 ° C. for 1 minute, and further immersed in 2N sulfuric acid at a constant temperature of 30 ° C. for 1 hour. Thereafter, a tape was pressure-bonded to the resist surface and peeled off in the vertical direction. Resist adhesion was confirmed with a microscope.
実施例７〜９
表１に示す実施例番号７〜９の組成の水溶液をイオン交換水で調整し、３０℃恒温とした。凡そ１μｍの膜厚の無電解銅めっき膜を有する基材をこれらの水溶液に１０秒間浸漬し、次いで、該基材を水洗し、そして乾燥させた。その後、乾燥した当該銅表面に、日立化成工業株式会社製の感光性樹脂（フォトレジスト）Ｐｈｏｔｅｃ ＲＹ−３２１５をラミネートし、６５ｍＪ／ｃｍ2にて露光し、そして１重量％の炭酸ナトリウムで最小現像時間の２倍時間で現像して、ライン／スペースが４０μｍ／４０μｍのレジスト面を形成させた。次いで、該基材を５０℃恒温にした２規定の塩酸に１分間浸漬し、更に３０℃恒温にした２規定の硫酸に１時間浸漬した。その後、レジスト面にテープを圧着し、これを垂直方向に引き剥がした。レジスト密着性をマイクロスコープにて確認した。
Examples 7-9
The aqueous solutions having the compositions of Example Nos. 7 to 9 shown in Table 1 were adjusted with ion-exchanged water and kept at a constant temperature of 30 ° C. A substrate having an electroless copper plating film having a thickness of about 1 μm was immersed in these aqueous solutions for 10 seconds, and then the substrate was washed with water and dried. Thereafter, a photosensitive resin (photoresist) Phototec RY-3215 manufactured by Hitachi Chemical Co., Ltd. is laminated on the dried copper surface, exposed at 65 mJ / cm 2 , and minimally developed with 1 wt% sodium carbonate. Development was carried out in twice the time to form a resist surface with a line / space of 40 μm / 40 μm. Next, the substrate was immersed in 2N hydrochloric acid at a constant temperature of 50 ° C. for 1 minute, and further immersed in 2N sulfuric acid at a constant temperature of 30 ° C. for 1 hour. Thereafter, a tape was pressure-bonded to the resist surface and peeled off in the vertical direction. Resist adhesion was confirmed with a microscope.
実施例１０〜１２
表１に示す実施例番号１０〜１２の組成の水溶液をイオン交換水で調整し、２５℃恒温とした。凡そ１．５μｍの膜厚の無電解銅めっき膜を有する基材をこれらの水溶液に２５秒間浸漬し、次いで、該基材を水洗し、そして乾燥させた。その後、乾燥した当該銅表面に、ニチゴー・モートン株式会社製の感光性樹脂（フォトレジスト）ＡＬＰＨＯ ＮＩＴ２２５をラミネートし、１００ｍＪ／ｃｍ2にて露光し、そして１重量％の炭酸カリウムで最小現像時間の２倍時間で現像して、ライン／スペースが４０μｍ／４０μｍのレジスト面を形成させた。次いで、該基材を５０℃恒温にした２規定の塩酸に１分間浸漬し、更に３０℃恒温にした２規定の硫酸に１時間浸漬した。レジスト面にテープを圧着し、これを垂直方向に引き剥がした。レジスト密着性をマイクロスコープにて確認した。
Examples 10-12
An aqueous solution having a composition of Example Nos. 10 to 12 shown in Table 1 was adjusted with ion-exchanged water and kept at a constant temperature of 25 ° C. A substrate having an electroless copper plating film with a thickness of about 1.5 μm was immersed in these aqueous solutions for 25 seconds, and then the substrate was washed with water and dried. Thereafter, a photosensitive resin (photoresist) ALPHA NIT225 manufactured by Nichigo-Morton Co., Ltd. is laminated on the dried copper surface, exposed at 100 mJ / cm 2 , and minimum development time with 1% by weight of potassium carbonate. Development was performed in twice the time to form a resist surface with a line / space of 40 μm / 40 μm. Next, the substrate was immersed in 2N hydrochloric acid at a constant temperature of 50 ° C. for 1 minute, and further immersed in 2N sulfuric acid at a constant temperature of 30 ° C. for 1 hour. The tape was pressure-bonded to the resist surface and peeled off in the vertical direction. Resist adhesion was confirmed with a microscope.
実施例１３〜１４
表１に示す実施例番号１３〜１４の組成の水溶液をイオン交換水で調整し、２５℃恒温とした。凡そ１．０μｍの膜厚の無電解銅めっき膜を有する基材をこれらの水溶液に２５秒間浸漬し、次いで、該基材を水洗し、そして乾燥させた。その後、乾燥した当該銅表面に、ニチゴー・モートン株式会社製の感光性樹脂（フォトレジスト）ＡＬＰＨＯ ＮＩＴ２２５をラミネートし、１００ｍＪ／ｃｍ2にて露光し、そして１重量％の炭酸カリウムで最小現像時間の２倍時間で現像して、ライン／スペースが４０μｍ／４０μｍのレジスト面を形成させた。次いで、該基材を５０℃恒温にした２規定の塩酸に１分間浸漬し、更に３０℃恒温にした２規定の硫酸に１時間浸漬した。レジスト面にテープを圧着し、これを垂直方向に引き剥がした。レジスト密着性をマイクロスコープにて確認した。
Examples 13-14
The aqueous solutions having the compositions of Example Nos. 13 to 14 shown in Table 1 were adjusted with ion-exchanged water and kept at a constant temperature of 25 ° C. A substrate having an electroless copper plating film with a thickness of about 1.0 μm was immersed in these aqueous solutions for 25 seconds, and then the substrate was washed with water and dried. Thereafter, a photosensitive resin (photoresist) ALPHA NIT225 manufactured by Nichigo-Morton Co., Ltd. is laminated on the dried copper surface, exposed at 100 mJ / cm 2 , and minimum development time with 1% by weight of potassium carbonate. Development was performed in twice the time to form a resist surface with a line / space of 40 μm / 40 μm. Next, the substrate was immersed in 2N hydrochloric acid at a constant temperature of 50 ° C. for 1 minute, and further immersed in 2N sulfuric acid at a constant temperature of 30 ° C. for 1 hour. The tape was pressure-bonded to the resist surface and peeled off in the vertical direction. Resist adhesion was confirmed with a microscope.
比較例１
凡そ１μｍの膜厚の銅蒸着膜を有する基材をイオン交換水で調整した５％硫酸に２０秒間浸漬し、次いで水洗し、そして乾燥させた。乾燥した当該銅表面に日立化成工業株式会社製の感光性樹脂（フォトレジスト）Ｐｈｏｔｅｃ ＲＹ−３２１５をラミネートし、６５ｍＪ／ｃｍ2にて露光し、１重量％の炭酸ナトリウムで最小現像時間の２倍時間で現像して、ライン／スペースが４０μｍ／４０μｍのレジスト面を形成させた。次いで、該基材を５０℃恒温にした２規定の塩酸に１分間浸漬し、更に３０℃恒温にした２規定の硫酸に１時間浸漬した。その後、レジスト面にテープを圧着し、これを垂直方向に引き剥がした。レジスト密着性をマイクロスコープにて確認した。
Comparative Example 1
A substrate having a copper vapor deposition film with a thickness of about 1 μm was immersed in 5% sulfuric acid prepared with ion exchange water for 20 seconds, then washed with water and dried. Dry the copper surface by Hitachi Chemical Co., Ltd. of the photosensitive resin (photoresist) Photec RY-3215 was laminated, exposed at 65 mJ / cm 2, 2 times the minimum developing time 1 wt% of sodium carbonate Development was performed over time to form a resist surface with a line / space of 40 μm / 40 μm. Next, the substrate was immersed in 2N hydrochloric acid at a constant temperature of 50 ° C. for 1 minute, and further immersed in 2N sulfuric acid at a constant temperature of 30 ° C. for 1 hour. Thereafter, a tape was pressure-bonded to the resist surface and peeled off in the vertical direction. Resist adhesion was confirmed with a microscope.
比較例２
凡そ０．５μｍの膜厚の無電解銅めっき膜を有する基材をイオン交換水で調整した５％硫酸に２０秒間浸漬し、次いで水洗し、乾燥させた。乾燥した当該銅表面にニチゴー・モートン株式会社製の感光性樹脂（フォトレジスト）ＡＬＰＨＯ ＮＩＴ２２５をラミネートし、１００ｍＪ／ｃｍ2にて露光し、そして１重量％の炭酸カリウムで最小現像時間の２倍時間で現像して、ライン／スペースが４０μｍ／４０μｍのレジスト面を形成させた。次いで、該基材を５０℃恒温にした２規定の塩酸に１分間浸漬し、更に３０℃恒温にした２規定の硫酸に１時間浸漬した。その後、レジスト面にテープを圧着し、これを垂直方向に引き剥がした。レジスト密着性をマイクロスコープにて確認した。
Comparative Example 2
A substrate having an electroless copper plating film having a thickness of about 0.5 μm was immersed in 5% sulfuric acid prepared with ion exchange water for 20 seconds, then washed with water and dried. The dried copper surface is laminated with a photosensitive resin (photoresist) ALPHA NIT225 manufactured by Nichigo-Morton, exposed at 100 mJ / cm 2 , and twice the minimum development time with 1% by weight of potassium carbonate. And a resist surface having a line / space of 40 μm / 40 μm was formed. Next, the substrate was immersed in 2N hydrochloric acid at a constant temperature of 50 ° C. for 1 minute, and further immersed in 2N sulfuric acid at a constant temperature of 30 ° C. for 1 hour. Thereafter, a tape was pressure-bonded to the resist surface and peeled off in the vertical direction. Resist adhesion was confirmed with a microscope.
比較例３〜６
表１に示す比較例番号３〜６の組成の水溶液をイオン交換水で調整し、３０℃恒温とした。凡そ１μｍの膜厚の無電解銅めっき膜を有する基材をこれらの水溶液に２０秒間浸漬し、次いで水洗し、そして乾燥させた。乾燥した当該銅表面にニチゴー・モートン株式会社製の感光性樹脂（フォトレジスト）ＡＬＰＨＯ ＮＩＴ２２５をラミネートし、１００ｍＪ／ｃｍ2にて露光し、そして１重量％の炭酸ナトリウムで最小現像時間の２倍時間で現像して、ライン／スペースが４０μｍ／４０μｍのレジスト面を形成させた。次いで、当該基材を５０℃恒温にした２規定の塩酸に１分間浸漬し、更に３０℃恒温にした２規定の硫酸に１時間浸漬した。その後、レジスト面にテープを圧着し、これを垂直方向に引き剥がした。レジスト密着性をマイクロスコープにて確認した。
Comparative Examples 3-6
An aqueous solution having a composition of Comparative Example Nos. 3 to 6 shown in Table 1 was adjusted with ion-exchanged water to a constant temperature of 30 ° C. A substrate having an electroless copper plating film with a thickness of about 1 μm was immersed in these aqueous solutions for 20 seconds, then washed with water and dried. The dried copper surface is laminated with a photosensitive resin (photoresist) ALPHA NIT225 manufactured by Nichigo-Morton, exposed at 100 mJ / cm 2 , and twice the minimum development time with 1 wt% sodium carbonate. And a resist surface having a line / space of 40 μm / 40 μm was formed. Subsequently, the substrate was immersed in 2N hydrochloric acid at a constant temperature of 50 ° C. for 1 minute, and further immersed in 2N sulfuric acid at a constant temperature of 30 ° C. for 1 hour. Thereafter, a tape was pressure-bonded to the resist surface and peeled off in the vertical direction. Resist adhesion was confirmed with a microscope.
比較例７
表１に示す比較例番号７の組成の水溶液をイオン交換水で調整し、２５℃恒温とした。凡そ１．０μｍの膜厚の無電解銅めっき膜を有する基材をこの水溶液に２５秒間浸漬し、次いで、該基材を水洗し、そして乾燥させた。その後、乾燥した当該銅表面に、ニチゴー・モートン株式会社製の感光性樹脂（フォトレジスト）ＡＬＰＨＯ ＮＩＴ２２５をラミネートし、１００ｍＪ／ｃｍ2にて露光し、そして１重量％の炭酸カリウムで最小現像時間の２倍時間で現像して、ライン／スペースが４０μｍ／４０μｍのレジスト面を形成させた。次いで、該基材を５０℃恒温にした２規定の塩酸に１分間浸漬し、更に３０℃恒温にした２規定の硫酸に１時間浸漬した。レジスト面にテープを圧着し、これを垂直方向に引き剥がした。レジスト密着性をマイクロスコープにて確認した。
Comparative Example 7
An aqueous solution having the composition of Comparative Example No. 7 shown in Table 1 was adjusted with ion-exchanged water and kept at a constant temperature of 25 ° C. A substrate having an electroless copper plating film with a thickness of approximately 1.0 μm was immersed in this aqueous solution for 25 seconds, and then the substrate was washed with water and dried. Thereafter, a photosensitive resin (photoresist) ALPHA NIT225 manufactured by Nichigo-Morton Co., Ltd. is laminated on the dried copper surface, exposed at 100 mJ / cm 2 , and minimum development time with 1% by weight of potassium carbonate. Development was performed in twice the time to form a resist surface with a line / space of 40 μm / 40 μm. Next, the substrate was immersed in 2N hydrochloric acid at a constant temperature of 50 ° C. for 1 minute, and further immersed in 2N sulfuric acid at a constant temperature of 30 ° C. for 1 hour. The tape was pressure-bonded to the resist surface and peeled off in the vertical direction. Resist adhesion was confirmed with a microscope.
比較例８
表１に示す比較例番号８の水溶液をイオン交換水で調整し、３０℃恒温とした。凡そ０．５μｍの膜厚の無電解銅めっき膜を有する基材を硫酸５重量％水溶液に１分間浸漬し、ついで充分に水洗を行なった後、先に調整した比較例番号７の水溶液に２０秒間浸漬し、次いで水洗し、そして乾燥させた。乾燥した当該銅表面にニチゴー・モートン株式会社製の感光性樹脂（フォトレジスト）ＡＬＰＨＯ ＮＩＴ２２５をラミネートし、１００ｍＪ／ｃｍ2にて露光し、そして１重量％の炭酸ナトリウムで最小現像時間の２倍時間で現像して、ライン／スペースが４０μｍ／４０μｍのレジスト面を形成させた。次いで、当該基材を５０℃恒温にした２規定の塩酸に１分間浸漬し、更に３０℃恒温にした２規定の硫酸に１時間浸漬した。その後、レジスト面にテープを圧着し、これを垂直方向に引き剥がした。レジスト密着性をマイクロスコープにて確認した。
Comparative Example 8
The aqueous solution of Comparative Example No. 8 shown in Table 1 was adjusted with ion-exchanged water to a constant temperature of 30 ° C. A base material having an electroless copper plating film having a thickness of about 0.5 μm is immersed in a 5 wt% sulfuric acid aqueous solution for 1 minute, and then sufficiently washed with water. Soaked for 2 seconds, then washed with water and dried. The dried copper surface is laminated with a photosensitive resin (photoresist) ALPHA NIT225 manufactured by Nichigo-Morton, exposed at 100 mJ / cm 2 , and twice the minimum development time with 1 wt% sodium carbonate. And a resist surface having a line / space of 40 μm / 40 μm was formed. Subsequently, the substrate was immersed in 2N hydrochloric acid at a constant temperature of 50 ° C. for 1 minute, and further immersed in 2N sulfuric acid at a constant temperature of 30 ° C. for 1 hour. Thereafter, a tape was pressure-bonded to the resist surface and peeled off in the vertical direction. Resist adhesion was confirmed with a microscope.
表１に示すように、本発明によって銅又は銅合金の表面と感光性樹脂（フォトレジスト）との密着性が改善されることが確認された。 As shown in Table 1, it was confirmed that the adhesion between the surface of copper or copper alloy and the photosensitive resin (photoresist) was improved by the present invention.
Claims (6)
によって表される１種以上の複素環式化合物と、無機酸及び有機酸よりなる群から選択される１種以上の酸とを含有し、しかもｐＨが４以下で、ハロゲン化合物、過硫酸塩及び過酸化水素を含有しない水溶液からなる銅又は銅合金用表面処理剤。 The following formula:
And at least one acid selected from the group consisting of inorganic acids and organic acids , and having a pH of 4 or less, a halogen compound, a persulfate, and A surface treating agent for copper or a copper alloy comprising an aqueous solution containing no hydrogen peroxide .
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