JPS6383282A - Method for supplying copper ion to chemical copper plating solution - Google Patents
Method for supplying copper ion to chemical copper plating solutionInfo
- Publication number
- JPS6383282A JPS6383282A JP22636586A JP22636586A JPS6383282A JP S6383282 A JPS6383282 A JP S6383282A JP 22636586 A JP22636586 A JP 22636586A JP 22636586 A JP22636586 A JP 22636586A JP S6383282 A JPS6383282 A JP S6383282A
- Authority
- JP
- Japan
- Prior art keywords
- plating
- tank
- soln
- copper
- solution
- 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.)
- Pending
Links
- 238000007747 plating Methods 0.000 title claims abstract description 64
- 239000010949 copper Substances 0.000 title claims abstract description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 16
- 239000000126 substance Substances 0.000 title claims abstract description 8
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 title claims description 32
- 229910001431 copper ion Inorganic materials 0.000 title claims description 31
- 238000000034 method Methods 0.000 title claims description 8
- 238000004090 dissolution Methods 0.000 claims abstract description 11
- 239000008139 complexing agent Substances 0.000 claims abstract description 9
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 8
- 239000003002 pH adjusting agent Substances 0.000 claims abstract description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 16
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 3
- 230000002159 abnormal effect Effects 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract 6
- 230000008021 deposition Effects 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 24
- 239000005751 Copper oxide Substances 0.000 description 14
- 229910000431 copper oxide Inorganic materials 0.000 description 14
- 239000007788 liquid Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000010979 pH adjustment Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003788 bath preparation Substances 0.000 description 2
- 238000007796 conventional method Methods 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
- 230000009467 reduction Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229940050410 gluconate Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000758 substrate Substances 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
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemically Coating (AREA)
Abstract
Description
【発明の詳細な説明】
本発明の対象とする化学銅めっき液は、２価銅イオン、
２価銅イオンの錯化剤、２価銅イオンの還元剤、ｐＨ調
整剤及び有機添加剤を組成とするものであり、その代表
例が前記したＥＤＴＡ浴である。この他にも、ロッシェ
ル塩浴、アミン類浴、グルコン酸塩浴、グルコペプトン
酸塩浴などが知られている。[Detailed Description of the Invention] The chemical copper plating solution targeted by the present invention includes divalent copper ions,
The composition includes a complexing agent for divalent copper ions, a reducing agent for divalent copper ions, a pH adjuster, and an organic additive, and a representative example thereof is the above-mentioned EDTA bath. In addition, Rochelle salt baths, amine baths, gluconate baths, glucopeptonate baths, and the like are known.
ＥＤＴＡ浴の場合、めっき皮膜の析出反応は次の通り生
ずる（（Ｌ）はＥＤＴＡとのキレート形成を示す）：
Ｃｕ” （Ｌ） ＋ ２ ＨＣＨＯ＋ ４０Ｈ−→Ｃｕ
’ ＋ ２ＨＣＯＯ″″＋Ｈ３↑＋２Ｈ２０＋（Ｌ）
こうして、例えばプリント回路基板のようなめつき液に
浸漬された被めっき材の所望の部位に銅皮膜が形成され
る。In the case of an EDTA bath, the precipitation reaction of the plated film occurs as follows ((L) indicates chelate formation with EDTA): Cu" (L) + 2 HCHO+ 40H-→Cu
'+2HCOO''''+H3↑+2H20+(L) In this way, a copper film is formed at a desired portion of the material to be plated, such as a printed circuit board, which is immersed in the plating solution.
消耗する銅イオンを補給する為に、本発明に従えば、第
１図に示すように、めつき槽１からめつき液が、好まし
くは一定量連続的に、抜出される０抜出されためつき液
は好ましくは一旦貯液槽２に貯められた後溶解槽３に移
される。溶解槽３には、エアー攪拌手段及び（或いは）
機械的攪拌手段を装備することが出来る。更に、溶解槽
３には、液温調節の為の冷却ジャケットが装備される０
２価銅イオン補給源として、本発明に従えば、酸化銅（
ＣｕＯ）が溶解槽に添加される。こうして生成する２価
銅イオン補給液は、補給槽４を経由してミキサ５に移行
される。In order to replenish the depleted copper ions, according to the present invention, as shown in FIG. The liquid is preferably once stored in the liquid storage tank 2 and then transferred to the dissolution tank 3. The dissolution tank 3 includes an air stirring means and/or
Mechanical stirring means may be provided. Furthermore, the melting tank 3 is equipped with a cooling jacket for adjusting the liquid temperature.
According to the present invention, copper oxide (
CuO) is added to the dissolution bath. The divalent copper ion replenishment liquid thus generated is transferred to the mixer 5 via the replenishment tank 4.
ミキサ５には、めつき槽１からの別途の循回系が存在し
、ここに２価銅イオン補給液と消費量に見合う ｐＨ調
節液及び２価銅イオンの還元剤が添加され、十分なる混
合後、これら液がめつき槽に戻して循回される。ＥＤＴ
Ａは建浴段階で加えれば後は基板と一緒に持ち出される
程度であシ、はとんど減らない。The mixer 5 has a separate circulation system from the plating tank 1, into which a divalent copper ion replenishment solution, a pH adjustment solution corresponding to the consumption amount, and a divalent copper ion reducing agent are added to ensure sufficient After mixing, these liquids are circulated back to the plating tank. E.D.T.
If A is added at the bath preparation stage, it will be taken out with the substrate afterwards, and the amount will hardly decrease.
補給される酸化銅は、銅粉末を空気中で加熱したシ、水
酸化銅、炭酸銅、硝酸銅等を加熱分解することにより、
また電気銅を硫酸ナトリウム浴で電解することにより工
業的に製造されうる。補給源酸化銅は、安価であること
、高純度であることそして易溶性であることが要求され
、これら要件を満たす新たな酸化銅製造方法として、オ
ートクレーブを用いてアンモニア水溶液或いはアンモニ
ア水溶液及び水酸化ナトリウムの水溶液と金属銅とを接
触反応させる方法が提唱されておシ、本発明目的にきわ
めて好適な酸化銅を入手することが出来る。The supplied copper oxide is produced by heating copper powder in the air, or by thermally decomposing copper hydroxide, copper carbonate, copper nitrate, etc.
It can also be produced industrially by electrolyzing electrolytic copper in a sodium sulfate bath. Replenishment source copper oxide is required to be inexpensive, highly pure, and easily soluble.As a new copper oxide production method that meets these requirements, an ammonia aqueous solution or an ammonia aqueous solution and hydroxide are produced using an autoclave. A method has been proposed in which an aqueous sodium solution and metallic copper undergo a contact reaction, and it is possible to obtain copper oxide which is extremely suitable for the purpose of the present invention.
溶解槽におけるめっき液温はめっき時温度より十分低温
とすることが好ましい０酸化銅を補給しようとするめつ
き液には、ＥＤＴＡ浴の場合を例にとると Ｃｕ２＋、
ＨＣＨＯ及びＮａＯＨが存在するため、めっき液温度が
めつき時温度と同等であると、銅イオン補給と同時にめ
っき皮膜析出反応が溶解槽内において生じやすい。めっ
き時温度は最適のめつき反応を生せしめる為に高温、例
えばＥＤＴＡ浴では７０℃前後に維持されている。めっ
き液の温度を下げる程、反応が起こシにくくなシ、こう
した不慮の銅析出を防止することが出来る。他方、温度
を下げる程酸化銅の溶解度が減少する。ＥＤＴＡ浴を代
表とする化学銅めっき浴において、めっき液の温度を４
０〜５０℃に管理することにより銅の析出反応を防止し
つつ充分なる酸化銅溶解速度が保証されることが判明し
た。It is preferable that the temperature of the plating solution in the dissolution tank is sufficiently lower than the temperature during plating.For example, in the case of an EDTA bath, Cu2+,
Due to the presence of HCHO and NaOH, if the plating solution temperature is equivalent to the temperature during plating, a plating film precipitation reaction is likely to occur in the dissolution tank at the same time as copper ion replenishment. The temperature during plating is maintained at a high temperature, for example, around 70° C. in an EDTA bath, in order to produce an optimal plating reaction. The lower the temperature of the plating solution, the less likely the reaction will occur, and such accidental copper precipitation can be prevented. On the other hand, the solubility of copper oxide decreases as the temperature decreases. In a chemical copper plating bath, typically an EDTA bath, the temperature of the plating solution is
It has been found that by controlling the temperature between 0 and 50°C, a sufficient copper oxide dissolution rate can be ensured while preventing the copper precipitation reaction.
補給する銅イオンはフリーの錯化剤と等モルとすること
が最適条件であシ、これを超えると補給した酸化銅は溶
解せず、沈降するか或いは攪拌により液中に物理的に浮
遊した状態となる０この未溶解酸化銅は、槽、攪拌機の
摩耗等装置に悪影響を与え、ミキサーへの補給液とする
には固−液分離の必要性を生せしめる。例え分離機を設
けたとしても、分離機の目詰シを生せしめる。従って、
未溶解酸化銅をなるたけ低下させる為補給する銅イオン
の添加量はフリーの錯化剤と等モルまでとされる。反面
、補給銅イオン量が少ないと、めっき槽での本来のめつ
き反応に支障を生じるので、銅イオン添加量は錯化剤モ
ル量の８０チ以上は必要である。即ち、銅イオンの補給
効率と溶解性の観点から、フリーの錯化剤のモル量の８
０〜１００チに相当する銅イオンを酸化銅の形で補給す
ることが好ましい。こうして添加された酸化銅は全量が
、フリーの錯化剤とキレートをつくシ、めっき皮膜析出
の為の銅イオンと々シ、しかも消耗した銅イオンの補給
を保証する。The optimal condition is that the amount of copper ions to be replenished is equimolar to that of the free complexing agent; if this is exceeded, the replenished copper oxide will not dissolve and will either settle or become physically suspended in the liquid due to stirring. This undissolved copper oxide has an adverse effect on equipment such as wear of the tank and agitator, and requires solid-liquid separation in order to be used as a replenishment liquid for the mixer. Even if a separator is provided, the separator will become clogged. Therefore,
In order to reduce the amount of undissolved copper oxide as much as possible, the amount of copper ions added is set to be equal to the amount of the free complexing agent in moles. On the other hand, if the amount of supplementary copper ions is small, it will interfere with the original plating reaction in the plating bath, so the amount of copper ions added must be at least 80 times the mole amount of the complexing agent. That is, from the viewpoint of copper ion replenishment efficiency and solubility, the molar amount of free complexing agent is 8.
Preferably, copper ions corresponding to 0 to 100 Ti are supplied in the form of copper oxide. The entire amount of copper oxide added in this way chelates with the free complexing agent, thereby ensuring that the copper ions for depositing the plating film are replenished, and that the depleted copper ions are replenished.
めつき槽外の溶解槽において酸化銅をその溶解に最適の
条件の下でめっき液に溶解して２価銅イオン補給液とし
、その後消費された成分を添加混合した上でめっき槽に
戻すことが本発明の重要な点である。In a dissolution tank outside the plating tank, copper oxide is dissolved in the plating solution under optimal conditions for dissolving it to make a divalent copper ion replenishment solution, and then the consumed components are added and mixed before being returned to the plating tank. This is an important point of the present invention.
実施例１及び比較例１
第１図に示したフローに従い、Ｅ、ＤＴＡ浴を用いて一
定量のめつき液を抜出し、溶解槽において温度４５±１
℃で酸化銅をフリーの錯化剤と等モル補給した。その後
、この補給液をミキサーに送シ、ｐＨ調整液及び２価銅
イオン還元剤を加え、めっき槽に戻した（本発明）０
他方、めっき槽からめつき液をミキサーに抜出し、そこ
で硫酸銅、ｐＨ調整液及び２価銅イオンの還元剤を一緒
に添加混合し、めっき液に戻した（従来法）０
１回のサンプルめっき厚２５〜３０μｍとした場合、本
発明は従来法に比較して槽壁への銅の異常析出や液の分
解もなく、約２倍のめつき液の寿命延長が可能となった
。Example 1 and Comparative Example 1 According to the flow shown in FIG.
Copper oxide was supplemented equimolarly with free complexing agent at °C. Thereafter, this replenishment solution was sent to a mixer, a pH adjustment solution and a divalent copper ion reducing agent were added thereto, and returned to the plating tank (this invention).On the other hand, the plating solution was extracted from the plating tank to a mixer, where copper sulfate, copper sulfate, A pH adjustment solution and a divalent copper ion reducing agent were added and mixed together and returned to the plating solution (conventional method).0 When the sample plating thickness was 25 to 30 μm at one time, the present invention There is no abnormal precipitation of copper on the tank walls or decomposition of the solution, making it possible to extend the life of the plating solution by about twice as much.
実施例２
めっき液の連続使用と生成めっき膜との関係を評価する
為と一カ試験を行った。ここでもＥＤＴＡ浴を使用した
。銅イオンを酸化銅で供給した場合、どの位のめつき寿
命があるかを判定するために、めっき浴中の８０４２−
濃度を一定（建浴時）に保持し、反応副生成物たるＨ
ＣＯＯＮａ 濃度のみを増加させて、めっき試験を行
った。Ｔ（ＣＯＯＮａ濃度の増加には、その都度試薬を
添加し、めっき浴の使用回数に見立てた。結果を第２及
び３図に示す。Example 2 A test was conducted to evaluate the relationship between the continuous use of a plating solution and the formed plating film. Again, an EDTA bath was used. In order to determine how long the plating life is when copper ions are supplied as copper oxide, 8042-
By keeping the concentration constant (at the time of bath preparation), the reaction by-product H
Plating tests were conducted by increasing only the COONa concentration. To increase the T(COONa concentration, a reagent was added each time, and the number of times the plating bath was used was measured. The results are shown in FIGS. 2 and 3.
第２及び３図には、生成皮膜の引張強度と伸びの評価結
果がそれぞれ示しである。試験ターンとは、同一のめつ
き浴について、１回のめつき操作（めっき厚２５ μｍ
）を行なうと１ターンとしてめっき回数を数えたもので
ある。銅めっきを印刷回路板に行なう場合、特にそのス
ルーホーにへの皮膜の性状が重要である０基板の変形に
追従しうる伸びとそのような変形を抑制する引張強度の
双方が高いことが好ましいが、実際的には伸びの方がめ
つき信頼性に大きく寄与する。従って、ここでは、引張
強度が３０ＫＱ／−以上で伸びが所定水準（５〜１０％
）に維持されるう限シ、めっき液の再使用が可能と判定
することにした。FIGS. 2 and 3 show the evaluation results of the tensile strength and elongation of the resulting film, respectively. A test turn is one plating operation (plating thickness 25 μm) using the same plating bath.
), the number of times of plating is counted as one turn. When copper plating is applied to a printed circuit board, the properties of the film especially on the through-holes are important.It is preferable that both the elongation that can follow the deformation of the board and the tensile strength that suppresses such deformation be high. In practice, elongation contributes more to plating reliability. Therefore, here, the tensile strength is 30KQ/- or more and the elongation is at a predetermined level (5 to 10%).
), it was decided that the plating solution could be reused as long as it was maintained.
従来法ではせいぜい６タ丁ンまでしか使用可能でなかっ
たが、本発明では１２〜１４ターンまでめっき液の寿命
が延長しうることか第２及び３図から確認しうる。It can be seen from Figures 2 and 3 that the life of the plating solution can be extended up to 12 to 14 turns with the present invention, whereas the conventional method can only be used for up to 6 turns.
発明の効果
本発明により、化学銅めっき液の寿命が従来の約２倍と
なシそして槽壁への銅析出や液分解が有効に防止され、
無電解めっき工程の大巾なコスト切下げと生産性の向上
が実現され、プリント回路板等エレクトロニクスデバイ
スのコストダウンに寄与する０Effects of the Invention According to the present invention, the life of the chemical copper plating solution is approximately twice that of the conventional one, and copper precipitation on the tank wall and solution decomposition are effectively prevented.
Significant cost reductions and productivity improvements in the electroless plating process have been achieved, contributing to cost reductions in electronic devices such as printed circuit boards.
第１図は本発明の好ましい具体例のフローシート、第２
図は実施例における引張強度と試験ターン数との関係を
示すグラフ、そして第３図は同じく伸びと試験ターン数
の関係を示すグラフである。
１：めつき槽 ２：抜出し液貯液槽
３：溶解槽 ４；補給槽 ５：ミキサ第１図
第２図
試、！ｉ灸ターン数−
第３図
手続補正書
昭和６２年９月８日
特許庁長官 小 川 邦 夫 殿
事件の表示 昭和６１年 特願第２２６３６５ 号発
明の名称 化学銅めっき液への銅イオン補給方法補正
をする者
事件との関係 特許出願人名称
日本鉱業株式会社FIG. 1 is a flow sheet of a preferred embodiment of the present invention;
The figure is a graph showing the relationship between tensile strength and the number of test turns in Examples, and FIG. 3 is a graph showing the relationship between elongation and the number of test turns. 1: Plating tank 2: Extracted liquid storage tank 3: Dissolution tank 4: Replenishment tank 5: Mixer Figure 1 Figure 2 Test,! Number of moxibustion turns - Figure 3 Procedural amendment September 8, 1985 Kunio Ogawa, Commissioner of the Patent Office Display of the case 1985 Patent application No. 226365 Title of the invention Method for replenishing copper ions to chemical copper plating solution Relationship with the case of the person making the amendment Name of the patent applicant
Japan Mining Co., Ltd.
Claims (1)
つき槽から前記めつき液の一部を抜出し、溶解槽におい
て酸化銅（ＣｕＯ）を該めつき液に溶解して２価銅イオ
ン補給液を生成し、該２価銅イオン補給液をｐＨ調整剤
及び２価銅イオン還元剤を加えた後めつき槽に戻して循
回することを特徴とする化学銅めつき液への銅イオン補
給方法。 ２）溶解槽における溶解温度をめつき時温度より低くす
る特許請求の範囲第１項記載の方法。 ３）溶解槽における銅イオン添加量をフリーの錯化剤と
等モルまでとする特許請求の範囲第１項又は第２項記載
の方法。 ４）２価銅イオン補給液をミキサーに導入し、該ミキサ
ーにてめつき槽から別途抜出されためつき液の一部並び
にｐＨ調整剤及び２価銅イオン還元剤と混合した後めつ
き槽に戻す特許請求の範囲第１〜３項のうちのいずれか
一項記載の方法。[Claims] 1) A method for replenishing copper ions to a chemical copper plating solution, wherein a part of the plating solution is extracted from a plating tank, and copper oxide (CuO) is added to the plating solution in a dissolving tank. A divalent copper ion replenishing solution is produced by dissolving the divalent copper ion replenishing solution, and after adding a pH adjuster and a divalent copper ion reducing agent, the divalent copper ion replenishing solution is returned to the plating tank and circulated. How to replenish copper ions to chemical copper plating solution. 2) The method according to claim 1, wherein the melting temperature in the melting tank is lower than the plating temperature. 3) The method according to claim 1 or 2, wherein the amount of copper ions added in the dissolution tank is up to equimolar with the free complexing agent. 4) The divalent copper ion replenishing solution is introduced into the mixer, and mixed with a part of the plating solution separately extracted from the plating tank, a pH adjuster, and a divalent copper ion reducing agent in the mixer, and then mixed with the plating tank. A method according to any one of claims 1 to 3 reverting to.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22636586A JPS6383282A (en) | 1986-09-26 | 1986-09-26 | Method for supplying copper ion to chemical copper plating solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22636586A JPS6383282A (en) | 1986-09-26 | 1986-09-26 | Method for supplying copper ion to chemical copper plating solution |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6383282A true JPS6383282A (en) | 1988-04-13 |
Family
ID=16844000
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22636586A Pending JPS6383282A (en) | 1986-09-26 | 1986-09-26 | Method for supplying copper ion to chemical copper plating solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6383282A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003033765A1 (en) * | 2001-10-17 | 2003-04-24 | Ebara Corporation | Plating apparatus |
-
1986
- 1986-09-26 JP JP22636586A patent/JPS6383282A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003033765A1 (en) * | 2001-10-17 | 2003-04-24 | Ebara Corporation | Plating apparatus |
| US7297210B2 (en) | 2001-10-17 | 2007-11-20 | Ebara Corporation | Plating apparatus |
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