JPH0214430B2 - - Google Patents
Info
- Publication number
- JPH0214430B2 JPH0214430B2 JP340985A JP340985A JPH0214430B2 JP H0214430 B2 JPH0214430 B2 JP H0214430B2 JP 340985 A JP340985 A JP 340985A JP 340985 A JP340985 A JP 340985A JP H0214430 B2 JPH0214430 B2 JP H0214430B2
- Authority
- JP
- Japan
- Prior art keywords
- copper
- borides
- grams
- bath
- plating
- 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.)
- Expired
Links
- 239000010949 copper Substances 0.000 claims description 43
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 41
- 229910052802 copper Inorganic materials 0.000 claims description 41
- 150000002500 ions Chemical class 0.000 claims description 14
- 229920006317 cationic polymer Polymers 0.000 claims description 10
- 239000008139 complexing agent Substances 0.000 claims description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 6
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 5
- 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
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- -1 sodium trimethoxyborohydride Chemical compound 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910000085 borane Inorganic materials 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- YIROYDNZEPTFOL-UHFFFAOYSA-N 5,5-Dimethylhydantoin Chemical compound CC1(C)NC(=O)NC1=O YIROYDNZEPTFOL-UHFFFAOYSA-N 0.000 claims description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical class OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 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
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical class O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 2
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- IENXJNLJEDMNTE-UHFFFAOYSA-N acetic acid;ethane-1,2-diamine Chemical class CC(O)=O.NCCN IENXJNLJEDMNTE-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 150000001447 alkali salts Chemical class 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- YJROYUJAFGZMJA-UHFFFAOYSA-N boron;morpholine Chemical compound [B].C1COCCN1 YJROYUJAFGZMJA-UHFFFAOYSA-N 0.000 claims description 2
- ZTQYEZDTWTZXPF-UHFFFAOYSA-N boron;propan-2-amine Chemical compound [B].CC(C)N ZTQYEZDTWTZXPF-UHFFFAOYSA-N 0.000 claims description 2
- OUDSFQBUEBFSPS-UHFFFAOYSA-N ethylenediaminetriacetic acid Chemical compound OC(=O)CNCCN(CC(O)=O)CC(O)=O OUDSFQBUEBFSPS-UHFFFAOYSA-N 0.000 claims description 2
- 239000000174 gluconic acid Substances 0.000 claims description 2
- 235000012208 gluconic acid Nutrition 0.000 claims description 2
- 229940015043 glyoxal Drugs 0.000 claims description 2
- 150000002596 lactones Chemical class 0.000 claims description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 2
- 229920002866 paraformaldehyde Polymers 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 claims description 2
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 claims 1
- 238000007747 plating Methods 0.000 description 40
- 229920000642 polymer Polymers 0.000 description 7
- NXLOLUFNDSBYTP-UHFFFAOYSA-N retene Chemical compound C1=CC=C2C3=CC=C(C(C)C)C=C3C=CC2=C1C NXLOLUFNDSBYTP-UHFFFAOYSA-N 0.000 description 6
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 239000003945 anionic surfactant Substances 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 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
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000024121 nodulation Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- USFMMZYROHDWPJ-UHFFFAOYSA-N trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium Chemical compound CC(=C)C(=O)OCC[N+](C)(C)C USFMMZYROHDWPJ-UHFFFAOYSA-N 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- FQERLIOIVXPZKH-UHFFFAOYSA-N 1,2,4-trioxane Chemical compound C1COOCO1 FQERLIOIVXPZKH-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- ICAIHGOJRDCMHE-UHFFFAOYSA-O ammonium cyanide Chemical compound [NH4+].N#[C-] ICAIHGOJRDCMHE-UHFFFAOYSA-O 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical group 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229940050410 gluconate Drugs 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- IHBKAGRPNRKYAO-UHFFFAOYSA-M methyl sulfate;trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium Chemical compound COS([O-])(=O)=O.CC(=C)C(=O)OCC[N+](C)(C)C IHBKAGRPNRKYAO-UHFFFAOYSA-M 0.000 description 1
- JVKAWJASTRPFQY-UHFFFAOYSA-N n-(2-aminoethyl)hydroxylamine Chemical group NCCNO JVKAWJASTRPFQY-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 125000005496 phosphonium group Chemical group 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- 238000009736 wetting Methods 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は無電解銅めつき浴に関する。更に詳細
に説明すれば本発明は、安定性があり、更にめつ
き速度が速く高品質の銅表面を形成し、外に付着
した銅の小瘤をかなり減少できる、すぐれた無電
解銅めつき浴に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an electroless copper plating bath. More specifically, the present invention provides an excellent electroless copper plating method that is stable, has a high plating speed, forms a high-quality copper surface, and can significantly reduce externally deposited copper nodules. Regarding bathing.
基板の無電解銅めつきは従来からよく知られて
いる。例えば、無電解すなわち自触媒作用銅めつ
き浴は、一般に銅（）イオン源、銅（）イオ
ン還元剤、キレート剤または錯化剤、およびPHア
ジヤスタを含む。更に、若し、めつきしようとす
る表面が所望の金属の析出により既に触媒の働き
をしないならば、めつき浴と接触させる前に、適
切な触媒を該表面に沈積させる。更に広く行なわ
れている基板を触媒作用化する手順の中には、金
属パラジウム粒子の層を形成するのに、塩化第一
錫の増感溶液および塩化パラジウムの活性剤を使
用するものがある。
Electroless copper plating of substrates is well known in the art. For example, an electroless or autocatalytic copper plating bath generally includes a source of copper() ions, a copper() ion reducing agent, a chelating agent or complexing agent, and a PH adjuster. Additionally, if the surface to be plated is already non-catalytic due to the deposition of the desired metal, a suitable catalyst is deposited on the surface prior to contact with the plating bath. Among the more widely practiced procedures for catalyzing substrates is the use of a stannous chloride sensitizing solution and a palladium chloride activator to form a layer of metallic palladium particles.
無電解銅めつきに関する技術は不断に改善され
つつあるけれども、更に改善の余地が残つてい
る。特定の問題が特に明白になるのは、印刷回路
（例えば高密度回路および、スルーホールやめく
ら穴のような多数の穴を含む印刷回路基板）に用
いられるような極めて高い品質の物品を作る場合
である。 Although the technology for electroless copper plating is constantly improving, there remains room for further improvement. Certain problems become particularly evident when producing very high quality articles such as those used in printed circuits (e.g., high-density circuits and printed circuit boards containing large numbers of holes, such as through-holes or blind holes). It is.
無電解銅めつきの歩どまりが低いのは、主に、
表面に銅が付着することにより小瘤が形成される
ことに起因する。基板上に不要な小瘤が作られる
と、基板上の回路間の接触により短絡が生じるこ
とがある。更に、保護被覆、はんだ付け、および
ピン挿入のようなプロセスも、表面に存在する小
瘤によつて悪影響を受ける。 The low yield of electroless copper plating is mainly due to
This is caused by the formation of nodules due to copper adhering to the surface. When unwanted nodules are created on the board, contact between circuits on the board can cause short circuits. Additionally, processes such as protective coatings, soldering, and pin insertion are also adversely affected by nodules present on the surface.
小瘤が形成される問題は、活性の度合の低い浴
を設け、浴およびめつきの状態を慎重に選択する
ことにより回避できるけれども、すぐれた安定性
を示し、同時にめつき速度を増大できる浴を設け
ることが有利であり望ましい。 Although the problem of nodule formation can be avoided by providing a less active bath and by carefully selecting the bath and plating conditions, it is important to have a bath that exhibits good stability and at the same time increases the plating rate. It is advantageous and desirable to provide one.
本発明の目的は、
第１に、すぐれた安定性を有する無電解めつき
浴を提供し、
第２に、めつき速度を増加できるめつき浴を提
供し、
第３に、すぐれた延性を有する高品質の沈積さ
れた銅を提供することである。
The objects of the present invention are, firstly, to provide an electroless plating bath with excellent stability; secondly, to provide a plating bath capable of increasing the plating rate; and thirdly, to provide a plating bath with excellent ductility. Our goal is to provide high quality deposited copper with
本発明の、すぐれた安定性を有する無電解銅め
つき浴は、
1PPB〜1000PPB（PPBは10億分の１部）の、
アクリルアミドまたはメタクリルアミドあるいは
両者からのカチオン重合体と、
硫酸銅（）として計算された約３〜約15グラ
ム（１リツトル当り）の量の、銅（）イオン源
と、
0.7〜７グラム（１リツトル当り）の量の、銅
（）イオン源の還元剤と、
20〜約50グラム（１リツトル当り）の量の銅
（）イオンの錯化剤と
によつて組成される。
The electroless copper plating bath of the present invention with excellent stability has a content of 1 PPB to 1000 PPB (PPB is parts per billion).
a cationic polymer from acrylamide or methacrylamide or both; a source of copper() ions in an amount of from about 3 to about 15 grams (per liter), calculated as copper() sulfate; 20 to about 50 grams (per liter) of a copper() ion complexing agent.
約1PPB〜約1000PPBの、アクリルアミドまた
はメタクリルアミドあるいは両者からのカチオン
重合体と、硫酸銅（）として計算された約３〜
約15グラム（１リツトル当り）の量の、銅（）
イオン源と、約0.7〜約７グラム（１リツトル当
り）の量の、銅（）イオン源の還元剤と、約20
〜約50グラム（１リツトル当り）の量の、銅
（）イオンの錯化剤とによつて組成された無電
解銅めつき浴は、安定性にすぐれ、めつき速度が
速く、外に付着する銅の小瘤をかなり減少して高
品質の銅を形成する。
from about 1 PPB to about 1000 PPB of a cationic polymer from acrylamide or methacrylamide or both, and from about 3 to about 300% calculated as copper sulfate ().
Copper () in an amount of approximately 15 grams (per liter)
an ion source, a copper() ion source reducing agent in an amount of about 0.7 to about 7 grams (per liter), and about 20
An electroless copper plating bath composed of ~50 grams (per liter) of copper() ion complexing agent has excellent stability, fast plating speed, and no adhesion to the outside. The copper nodules are significantly reduced to form high quality copper.
本発明による無電解銅めつき浴のすぐれた安定
性およびめつき速度の増加は、約1PPB〜約
1000PPB、できれば約1PPB〜約500PPBの、ア
クリルアミド及びメタクリルアミドの少なくとも
１方を含むカチオン重合体の使用により実現でき
ることが分つた。
The superior stability and increased plating rate of the electroless copper plating bath according to the present invention ranges from about 1 PPB to about
It has been found that this can be achieved by using a cationic polymer containing 1000 PPB, preferably from about 1 PPB to about 500 PPB, of at least one of acrylamide and methacrylamide.
濃縮されたカチオン重合体は、Cu+の酸化を促
進し、それによつてCu2Oの大量の沈澱を抑制し
浴の安定性を高めるとともに小瘤の形成を減少さ
せる。更に、本発明により、カチオン重合体は、
銅（）イオンに対する錯化剤またはキレート剤
として作用するものと考えられている。その上、
めつき浴中のカチオン重合体の存在は、金属イオ
ンとコーテイングされる表面との間をブリツジす
る配位子として作用し、それによつて電気化学反
応の速度を増加するので、めつき速度が増加す
る。 The concentrated cationic polymer promotes the oxidation of Cu + thereby inhibiting heavy precipitation of Cu 2 O, increasing bath stability and reducing nodule formation. Furthermore, according to the present invention, the cationic polymer is
It is thought to act as a complexing or chelating agent for copper() ions. On top of that,
The presence of cationic polymers in the plating bath increases the plating rate because it acts as a bridging ligand between the metal ions and the surface being coated, thereby increasing the rate of electrochemical reactions. do.
本発明で使用された良好なカチオン重合体は、
レテン（Reten）という商品名で入手できる。 Good cationic polymers used in the present invention are:
It is available under the trade name Reten.
アクリルアミド及びメタクリルアミドの少なく
とも１方を含む重合体は、少なくとも２つの活性
部分、すなわち有効なカチオン部分（moiety）
を含んでいるに違いないという点で、多機能カチ
オン物質である。該重合体は少なくとも水との混
和性があるが、できれば、水に溶解可能である
か、または少なくとも本発明で使用された水組成
物に溶解可能であることが望ましい。良好なカチ
オン部分は、第四級ホスホニウムおよび第四級ア
ンモニウム基である。少なくとも２つのカチオン
部分を含む重合体は市販されているので、本明細
書ではその詳細については説明を省略する。市販
の多機能カチオン重合体の例として、レテン210、
レテン220、およびレテン300がある。これらは、
ハーキユリーズ社（Hurcules Incorporated）−
デラウエア州ウイルミントン市−から市販されて
いる。これらの重合体についての説明は、同社の
広告VC−482Aの“水溶性重合体”（Water−
Soluble Polymers”）に記載されている。 The polymer containing at least one of acrylamide and methacrylamide has at least two active moieties, i.e., effective cationic moieties.
It is a multifunctional cationic substance in that it must contain . The polymer is at least miscible with water, but preferably soluble in water, or at least soluble in the water composition used in the invention. Good cation moieties are quaternary phosphonium and quaternary ammonium groups. Since polymers containing at least two cationic moieties are commercially available, detailed description thereof will not be given herein. Examples of commercially available multifunctional cationic polymers include Rethene 210,
There are Reten 220 and Reten 300. these are,
Hurcules Incorporated −
Commercially available from Wilmington, Delaware. For an explanation of these polymers, see the company's advertisement VC-482A "Water-Soluble Polymers" (Water-Soluble Polymers)
Soluble Polymers”).
レテン210は散剤で、アクリルアミドとβ−メ
タクリルオキシエチルトリメチルアンモニウムの
硫酸メチルとの共重合体であり、600〜1200cpsの
１％溶液のブルツクフイールド粘度を有する。 Rethene 210 is a powder, a copolymer of acrylamide and β-methacryloxyethyltrimethylammonium with methyl sulfate, and has a Bruckfield viscosity of a 1% solution of 600 to 1200 cps.
レテン220も散剤で、アクリルアミドとβ−メ
タクリルオキシエチルトリメチルアンモニウムの
硫酸メチルとの共重合体であり、800〜1200cpsの
１％溶液のブルツクフイールド粘度を有する。 Rethene 220 is also a powder, a copolymer of acrylamide and β-methacryloxyethyltrimethylammonium with methyl sulfate, and has a Bruckfield viscosity of a 1% solution of 800-1200 cps.
レテン300は液体で、β−メタクリルオキシエ
チルトリメチルアンモニウムの硫酸メチルのホモ
ポリマであり、300〜700cpsの１％溶液のブルツ
クフイールド粘度を有する。 Rethene 300 is a liquid, a homopolymer of β-methacryloxyethyltrimethylammonium methyl sulfate, and has a Bruckfield viscosity of a 1% solution of 300-700 cps.
レテン重合体の分子量は一般に比較的高く、約
50000〜約1000000、またはそれ以上の範囲にわた
つて変化する。これらの高い分子量の重合体は固
体生成物で、それらの主要な基幹化学構造はポリ
アクリルアミドである。カチオンレテン（正電
荷）は、種々のテトラアルキルアンモニウム化合
物をポリアクリルアミドに付着させることにより
得られる。これらの４基のアンモニウム基は、重
合体の正電荷を供給する。アクリルアミドおよび
（または）メタクリルアミドからのカチオン重合
体が本発明に従つて付加される良好な無電解銅め
つき浴、ならびにその使用方法は米国特許第
3844799号、同第4152467号に開示されている。 The molecular weight of retene polymers is generally relatively high, approximately
Vary over a range of 50,000 to about 1,000,000, or more. These high molecular weight polymers are solid products and their main backbone chemical structure is polyacrylamide. Cationic rethenes (positively charged) are obtained by attaching various tetraalkylammonium compounds to polyacrylamide. These four ammonium groups provide the positive charge of the polymer. A good electroless copper plating bath to which a cationic polymer from acrylamide and/or methacrylamide is added according to the invention, and a method for its use, is described in U.S. Pat.
It is disclosed in No. 3844799 and No. 4152467.
このような無電解銅めつき浴は一般に、水溶性
の組成物で、銅（）イオン源、還元剤、銅
（）イオンの錯化剤、およびPHアジヤスタを含
む。また、メツキ浴にはシアン化物イオン源およ
びアニオン界面活性剤も含む。一般に使用される
銅（）イオン源は、使用される錯化剤の硫酸銅
（）または第２銅塩である。 Such electroless copper plating baths are generally water-soluble compositions that include a source of copper() ions, a reducing agent, a complexing agent for copper() ions, and a PH adjuster. The plating bath also includes a source of cyanide ions and an anionic surfactant. Commonly used sources of copper() ions are copper() sulfate or cupric salts of the complexing agent used.
銅（）イオン源は一般に、１リツトル当り約
３グラム〜約15グラムの量で使用されるが、でき
れば硫酸銅（）として計算された、１リツトル
当り約８グラム〜約12グラムの量で使用されるの
が望ましい。 Copper() ion sources are generally used in amounts of about 3 grams to about 15 grams per liter, preferably in amounts of about 8 grams to about 12 grams per liter, calculated as copper() sulfate. It is desirable that
最も一般に使用される還元剤はホルムアルデヒ
ドで、本発明の良好な実施例では、１リツトル当
り約0.7グラム〜約７グラムの量で使用されるが
できれば１リツトル当り約0.7グラム〜約2.2グラ
ムの量を使用するのが最も望ましい。 The most commonly used reducing agent is formaldehyde, which in preferred embodiments of the invention is used in amounts of from about 0.7 grams to about 7 grams per liter, preferably from about 0.7 grams to about 2.2 grams per liter. It is most preferable to use
他の還元剤の例には、パラホルムアルデヒド、
トリオキサン、ジメチルヒダントイン、およびグ
リオキサールのようなホルムアルデヒド誘導体ま
たは前駆物質；アルカリ金属およびアルカリ硼化
水素（ナトリウムおよびカリウム硼化水素）のよ
うな硼化水素ならびにナトリウムトリメトキシ硼
化水素のような置換硼化水素；アミンボラン（イ
ソプロピルアミンボランおよびモルホリンボラ
ン）のようなボランがある。 Examples of other reducing agents include paraformaldehyde,
Formaldehyde derivatives or precursors such as trioxane, dimethylhydantoin, and glyoxal; alkali metal and hydrogen borides such as alkali hydrogen borides (sodium and potassium borohydride) and substituted borides such as sodium trimethoxyborohydride Hydrogen; Boranes such as amine borane (isopropylamine borane and morpholine borane).
適切な還元剤の例としては、ロツシエル塩、エ
チレンジアミン四酢酸と、エチレンジアミン四酢
酸のナトリウム（単ナトリウム、２ナトリウム、
３ナトリウムおよび４ナトリウム）と、ニトリロ
３酢酸およびそのアルカリ塩と、グルコン酸と、
グルコン酸塩と、トリエタノールアミンと、グル
コノ（γ）ラクトンと、Ｎ−ヒドロキシエチルま
たはエチレンジアミントリアセテートのような変
性エチレンジアミンアセテートとがある。更に、
いくつかの他の適切な銅（）錯化剤が、米国特
許第2996408号、同第3075856号、同第3075855号、
同第2938805号に示唆されている。 Examples of suitable reducing agents include Rothsiel's salt, ethylenediaminetetraacetic acid, and sodium (monosodium, disodium,
trisodium and tetrasodium), nitrilotriacetic acid and its alkali salts, gluconic acid,
These include gluconate, triethanolamine, glucono(gamma) lactone, and modified ethylenediamine acetate, such as N-hydroxyethyl or ethylenediamine triacetate. Furthermore,
Some other suitable copper complexing agents are described in U.S. Pat. No. 2,996,408;
It is suggested in the same No. 2938805.
錯化剤の量は、一般に１リツトル当り約20グラ
ム〜約50グラム、すなわち３〜４倍のモル過剰の
溶液に存在する銅（）イオンの量に応じて決ま
る。 The amount of complexing agent will generally depend on the amount of copper() ions present in the solution from about 20 grams to about 50 grams per liter, or a 3- to 4-fold molar excess.
また、めつき浴は、被覆される表面の湿潤を補
助するアニオン界面活性剤を含むことが望まし
い。条件に合つたアニオン界面活性剤の例として
“ガフアク（Gafac）RE−610”の商品名で市販
されている有機燐酸エステルがある。一般に、ア
ニオン界面活性剤は、１リツトル当り約0.02グラ
ム〜0.3グラムの範囲の量が存在する。 It is also desirable that the plating bath contain an anionic surfactant to assist in wetting the surface being coated. An example of an anionic surfactant that meets the requirements is an organic phosphate ester commercially available under the trade name "Gafac RE-610." Generally, the anionic surfactant is present in an amount ranging from about 0.02 grams to 0.3 grams per liter.
更に、浴のPHは一般に、例えば、所望のPHを得
るのに必要な量の、水酸化ナトリウムまたは水酸
化カリウムのような塩基性化合物の付加により調
整される。本発明に従つて使用される無電解銅め
つき浴の良好なPHは、11.6と11.8の間である。 Additionally, the PH of the bath is generally adjusted by the addition of a basic compound such as, for example, sodium hydroxide or potassium hydroxide in the amount necessary to obtain the desired PH. A good PH for the electroless copper plating bath used according to the invention is between 11.6 and 11.8.
また、できれば、めつき浴は、シアン化物イオ
ン、等に１リツトル当り約10〜約25ミリグラムの
シアン化物イオンを含み、0.0002〜0.0004モルの
範囲内の浴中シアン化物イオン濃度にすることが
望ましい。本発明によつて使用できるシアン化物
の例として、アルカリ金属、アルカリ土類金属お
よびシアン化アンモニウムがある。更に、めつき
浴には、従来からよく知られているような他の小
量の添加剤を含むことがある。 Preferably, the plating bath also contains about 10 to about 25 milligrams of cyanide ion per liter, such as cyanide ions, and preferably the cyanide ion concentration in the bath is within the range of 0.0002 to 0.0004 moles. . Examples of cyanides that can be used according to the invention include alkali metals, alkaline earth metals and ammonium cyanide. Additionally, the plating bath may contain other minor additives as are well known in the art.
本発明の良好なめつき浴は、1.060〜1.080の範
囲内の特定の比重を有する。更に、浴の温度は、
70℃と80℃の間に維持するのが望ましく、最も望
ましいのは70℃と75℃の間である。良好なシアン
化物イオン濃度に関連した良好なめつき温度に関
する説明は米国特許第3844799号に記載されてい
る。 A good plating bath of the present invention has a specific specific gravity within the range of 1.060 to 1.080. Furthermore, the temperature of the bath is
Preferably it is maintained between 70°C and 80°C, most preferably between 70°C and 75°C. A discussion of good plating temperatures associated with good cyanide ion concentrations is provided in US Pat. No. 3,844,799.
更に、米国特許第4152467号で説明しているよ
うに、浴のO2は2PPMと4PPMの間に、できれば
約2.5PPM〜約3.5PPMの間に維持することが望
ましい。O2の含有量は、酸素および不活性気体
を浴に注入することにより調整される。 Further, as explained in US Pat. No. 4,152,467, it is desirable to maintain the bath O2 between 2 and 4 PPM, preferably between about 2.5 PPM and about 3.5 PPM. The content of O 2 is adjusted by injecting oxygen and inert gas into the bath.
浴に対する気体注入速度は一般に、1000ガロン
当り毎分約１〜約20標準立方フイートであるが、
約５〜10標準立方フイートが望ましい。 Gas injection rates into the bath generally range from about 1 to about 20 standard cubic feet per minute per 1000 gallons, but
Approximately 5 to 10 standard cubic feet is preferred.
本発明に従つて行なわれる良好なめつき速度は
１時間当り約0.2〜約0.3ミルの銅めつきの厚さで
ある。 A good plating rate performed in accordance with the present invention is a copper plating thickness of about 0.2 to about 0.3 mil per hour.
本発明の無電解銅めつき浴を、制約されない下
記の例によつて示す。 The electroless copper plating bath of the present invention is illustrated by the following non-limiting example.
例 １
めつき浴は、約９グラム／リツトルの硫酸銅
（）、約２ミリリツトル／リツトルのホルムアル
デヒド、約36グラム／リツトルのエチレンジアミ
ン四酢酸、約９ミリグラム／リツトルのシアン化
ナトリウム、約1.2PPBのレテン210、および約
0.05グラム／リツトルの“ガフアク”を含むのが
望ましい。浴は約1.2のPHを有する。浴は、約73
℃の温度のめつき槽を介して供給される。めつき
槽は、表面に薄い層の銅を有する基板を含む。め
つき中の浴の酸素含有量は、約3PPMである。め
つき速度は約0.2ミル／時間である。基板の小瘤
等級は１である（小瘤等級は2.54cm平方当りの小
瘤数で、１が最上級、５が最下級である）。同様
な結果が、被覆銅の無電解めつきを触媒する誘電
性の基板によつて得られる。Example 1 A plating bath consists of approximately 9 grams/liter of copper sulfate, approximately 2 milliliters/liter of formaldehyde, approximately 36 grams/liter of ethylenediaminetetraacetic acid, approximately 9 milligrams/liter of sodium cyanide, and approximately 1.2 PPB. Reten 210, and approx.
Preferably, it contains 0.05 grams/liter of "Gafuaku". The bath has a PH of approximately 1.2. The bath is about 73
It is fed through a plating bath at a temperature of ℃. The plating bath includes a substrate with a thin layer of copper on its surface. The oxygen content of the bath during plating is approximately 3 PPM. The plating rate is about 0.2 mil/hour. The nodule grade of the substrate is 1 (the nodule grade is the number of nodules per 2.54 cm square, where 1 is the highest grade and 5 is the lowest grade). Similar results are obtained with dielectric substrates that catalyze electroless plating of coated copper.
本発明の無電解銅めつき浴は安定性にすぐれ、
めつき速度が早く、めつき中に小瘤の形成を、完
全にではないが、かなり排除し、更に、浴の耐用
期間が比較的長い（例えば、約１週間使用できる
浴もある）。
The electroless copper plating bath of the present invention has excellent stability,
The plating speed is fast, the formation of nodules during plating is largely, but not entirely, eliminated, and the bath life is relatively long (eg, some baths can be used for about a week).
Claims (1)
トルの量の銅（）イオン源と、 ホルムアルデヒド、パラホルムアルデヒド、ト
リオキサン、ジメチルヒダントイン、およびグリ
オキサールのようなホルムアルデヒド誘導体また
は前駆物質；アルカリ金属およびアルカリ硼化水
素（ナトリウムおよびカリウム硼化水素）のよう
な硼化水素ならびにナトリウムトリメトキシ硼化
水素のような置換硼化水素；アミンボラン（イソ
プロピルアミンボランおよびモルホリンボラン）
のようなボランより成る群から選ばれた0.7〜７
グラム／リツトルの量の還元剤と、 ロツシエル塩、エチレンジアミン四酢酸、エチ
レンジアミン四酢酸のナトリウム（単ナトリウ
ム、２ナトリウム、３ナトリウムおよび４ナトリ
ウム）、ニトリロ３酢酸およびそのアルカリ塩、
グルコン酸、グルコン酸塩、トリエタノールアミ
ン、グルコノ（γ）ラクトン、Ｎ−ヒドロキシエ
チルまたはエチレンジアミントリアセテートのよ
うな変性エチレンジアミンアセテートより成る群
から選ばれた20〜50グラム／リツトルの量の錯化
剤と、 1PPB〜1000PPBの、アクリルアミド及びメタ
クリルアミドの少なくとも１方を含むカチオン重
合体と、 を含む安定性を有する無電解銅めつき浴。Claims: 1. A source of copper () ions in an amount of 3 to 15 grams per liter, calculated as copper sulfate, and formaldehyde derivatives or precursors such as formaldehyde, paraformaldehyde, trioxane, dimethylhydantoin, and glyoxal; Hydrogen borides such as alkali metal and alkali borides (sodium and potassium borides) and substituted borides such as sodium trimethoxyborohydride; amine borane (isopropylamine borane and morpholine borane)
0.7 to 7 selected from the group consisting of borans such as
a reducing agent in an amount of grams per liter and Rothsiel salt, ethylenediaminetetraacetic acid, sodium (monosodium, disodium, trisodium and tetrasodium) of ethylenediaminetetraacetic acid, nitrilotriacetic acid and its alkali salts,
a complexing agent selected from the group consisting of gluconic acid, gluconate salts, triethanolamine, glucono(γ)lactone, N-hydroxyethyl or modified ethylenediamine acetate such as ethylenediamine triacetate in an amount of 20 to 50 grams/liter; , 1 PPB to 1000 PPB of a cationic polymer containing at least one of acrylamide and methacrylamide;
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US61127884A | 1984-05-17 | 1984-05-17 | |
| US611278 | 1984-05-17 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60245783A JPS60245783A (en) | 1985-12-05 |
| JPH0214430B2 true JPH0214430B2 (en) | 1990-04-09 |
Family
ID=24448389
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP340985A Granted JPS60245783A (en) | 1984-05-17 | 1985-01-14 | Electroless copper plating bath |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0164580B1 (en) |
| JP (1) | JPS60245783A (en) |
| DE (1) | DE3573139D1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02161130A (en) * | 1988-12-15 | 1990-06-21 | Hino Motors Ltd | Control device for turbo-charger |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4654126A (en) * | 1985-10-07 | 1987-03-31 | International Business Machines Corporation | Process for determining the plating activity of an electroless plating bath |
| JPH0723539B2 (en) * | 1986-11-06 | 1995-03-15 | 日本電装株式会社 | Chemical copper plating solution and method for forming copper plating film using the same |
| AU579776B2 (en) * | 1986-11-06 | 1988-12-08 | Nippondenso Co. Ltd. | Electroless copper plating solution and process for electrolessly plating copper |
| US4814009A (en) * | 1986-11-14 | 1989-03-21 | Nippondenso Co., Ltd. | Electroless copper plating solution |
| JP2595319B2 (en) * | 1988-07-20 | 1997-04-02 | 日本電装株式会社 | Chemical copper plating solution and method for forming copper plating film using the same |
| US5965211A (en) * | 1989-12-29 | 1999-10-12 | Nippondenso Co., Ltd. | Electroless copper plating solution and process for formation of copper film |
| JP4293622B2 (en) | 2003-10-17 | 2009-07-08 | 日鉱金属株式会社 | Electroless copper plating solution |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1530167A (en) * | 1967-07-03 | 1968-06-21 | Shipley Co | Composition and process for the electroless chemical deposition of copper on objects with a catalytic surface |
| JPS5230131B2 (en) * | 1973-07-11 | 1977-08-05 | ||
| JPS5220339A (en) * | 1975-08-08 | 1977-02-16 | Hitachi Ltd | Chemical copper plating solution |
-
1985
- 1985-01-14 JP JP340985A patent/JPS60245783A/en active Granted
- 1985-05-10 DE DE8585105723T patent/DE3573139D1/en not_active Expired
- 1985-05-10 EP EP19850105723 patent/EP0164580B1/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02161130A (en) * | 1988-12-15 | 1990-06-21 | Hino Motors Ltd | Control device for turbo-charger |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0164580A3 (en) | 1986-12-30 |
| JPS60245783A (en) | 1985-12-05 |
| EP0164580A2 (en) | 1985-12-18 |
| DE3573139D1 (en) | 1989-10-26 |
| EP0164580B1 (en) | 1989-09-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4269625A (en) | Bath for electroless depositing tin on substrates | |
| JPS5818430B2 (en) | Electroless plating bath and plating method | |
| EP0156212B1 (en) | Process for plating copper from electroless plating compositions | |
| US3032436A (en) | Method and composition for plating by chemical reduction | |
| JPH0247551B2 (en) | ||
| KR100930879B1 (en) | Stabilizers for electroless plating solutions and methods of using the same | |
| US5935306A (en) | Electroless gold plating bath | |
| JP2927142B2 (en) | Electroless gold plating bath and electroless gold plating method | |
| JPH0214430B2 (en) | ||
| CA1188458A (en) | Electroless gold plating | |
| US6911230B2 (en) | Plating method | |
| US4171225A (en) | Electroless copper plating solutions | |
| WO2017050662A1 (en) | Plating bath composition for electroless plating of gold and a method for depositing a gold layer | |
| JP2002180259A (en) | Metal deposition acceleration compound in plating liquid and plating liquid containing the same | |
| US4985076A (en) | Autocatalytic electroless gold plating composition | |
| KR850001554B1 (en) | Electroless bath for plating copper | |
| US3915718A (en) | Chemical silver bath | |
| US4450191A (en) | Ammonium ions used as electroless copper plating rate controller | |
| US4655833A (en) | Electroless copper plating bath and improved stability | |
| US4978559A (en) | Autocatalytic electroless gold plating composition | |
| JPH08176837A (en) | Electroless nickel-phosphorus plating solution | |
| JPH02294487A (en) | Tetraaza-ligand system as complex formation agent for nonelectrolytic deposition of cop- per | |
| JP3227505B2 (en) | Substitution type electroless gold plating solution | |
| US20070175358A1 (en) | Electroless gold plating solution | |
| EP3517651B1 (en) | Electroless gold plating bath |