JPS6345390A - Production of high purity copper by electrolytic refining - Google Patents
Production of high purity copper by electrolytic refiningInfo
- Publication number
- JPS6345390A JPS6345390A JP61188254A JP18825486A JPS6345390A JP S6345390 A JPS6345390 A JP S6345390A JP 61188254 A JP61188254 A JP 61188254A JP 18825486 A JP18825486 A JP 18825486A JP S6345390 A JPS6345390 A JP S6345390A
- Authority
- JP
- Japan
- Prior art keywords
- electrolytic
- copper
- anode
- soln
- electrolytic refining
- 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000010949 copper Substances 0.000 title claims abstract description 29
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 28
- 238000007670 refining Methods 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000011148 porous material Substances 0.000 claims abstract description 11
- 239000003792 electrolyte Substances 0.000 claims description 12
- 229920003002 synthetic resin Polymers 0.000 claims description 7
- 239000000057 synthetic resin Substances 0.000 claims description 7
- 239000010409 thin film Substances 0.000 claims description 7
- 239000012535 impurity Substances 0.000 abstract description 11
- 239000004033 plastic Substances 0.000 abstract 1
- 229920003023 plastic Polymers 0.000 abstract 1
- 239000002985 plastic film Substances 0.000 abstract 1
- 229920006255 plastic film Polymers 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 16
- 229910000365 copper sulfate Inorganic materials 0.000 description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 240000009029 Gluta renghas Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000012733 comparative method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000004992 fission Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Electrolytic Production Of Metals (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は、ＩＣやトランジスター等の半導体装置のボ
ンディングワイヤ等に使用される高純度銅素材の電解精
製による製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method of manufacturing a high-purity copper material used for bonding wires of semiconductor devices such as ICs and transistors by electrolytic refining.
一股に、高純度銅を得る方法としては、（ａ）硫酸、硫
酸銅混合水溶液中で、電気銅粗銅を陽極とし、種板とし
ての銅箔板を陰極として電解精製全行ない、このように
して得た電気銅をさらに１回〜数回電解精製を繰り返す
ことにより高純度電気銅を得る方法、
Φ）硫酸、硫酸銅混合水溶液中で電解精製して得た電気
銅を、さらにゾーンリファイニング法によシ精製を行な
う方法（特開昭６０−２４４０５４号公報参照）、
等が知られている。As a method for obtaining high-purity copper at once, (a) electrolytic refining is carried out in a mixed aqueous solution of sulfuric acid and copper sulfate, using electrolytic blister copper as an anode and a copper foil plate as a seed plate as a cathode. A method for obtaining high-purity electrolytic copper by repeating electrolytic refining one to several times. A method of purification by method (see Japanese Patent Application Laid-Open No. 60-244054) is known.
しかし、上記（ａ）の電解精製を繰シ返す方法では、陽
極と陰極とを隔離していないため、スライムが液中に分
散浮遊し、これが陰極に付着する定めに精製後の不純物
全体の濃度が十分に低下せず、しかも、電解液中の硫酸
濃度が、通常１５０〜２００ｙ／ｌ であるように電
解液中の８３度が高いので、電解精製を何度繰り返して
も陰啄析出銅中のＳ濃度は１ ｐｐｍ程度までしか低下
しない。このように不純物全体の＠度が十分に低下しな
いと電気伝導度および硬さに影響を及ぼすが、不純物の
中でも特てＳは銅の硬さに大きな影響？与え、硬さ全土
げる働きがある。この結果、従来の電解精製により製造
した高純度銅は、ピンカース硬さで３５以上となるため
、ボンディングワイヤとして用い次場合、結線時にゼン
デ・ｒングダメージを与えることが多く、ボンディング
ワイヤの素材として用いることは困難であった。However, in the method of repeating electrolytic refining in (a) above, since the anode and cathode are not isolated, the slime is dispersed and suspended in the liquid and adheres to the cathode, resulting in the overall concentration of impurities after purification. Moreover, the concentration of sulfuric acid in the electrolyte is usually 150 to 200 y/l, and the temperature in the electrolyte is high, so no matter how many times the electrolytic refining is repeated, The S concentration in this case decreases only to about 1 ppm. In this way, if the @ degree of all impurities is not sufficiently reduced, it will affect the electrical conductivity and hardness, but among impurities, does S in particular have a large effect on the hardness of copper? It has the function of giving and increasing the hardness of the entire body. As a result, high-purity copper produced by conventional electrolytic refining has a Pinkers hardness of 35 or higher, so when used as a bonding wire, it often causes bending damage during connection, so it is not suitable as a bonding wire material. It was difficult to use.
このような問題点を解決すべく開発された方法が上記（
ト））に示した方法で、電解精製して得た電気銅を、さ
らにゾーンリファイニングする方法テするが、かかる方
法は、電解精製とゾーンリファイニングの２工程全含み
、製造工程も複雑で非常にコストがかかるので好ましく
ない。The method developed to solve these problems is described above (
There is a method of further zone refining the electrolytic copper obtained by electrolytic refining using the method shown in g)), but this method involves two steps, electrolytic refining and zone refining, and the manufacturing process is complicated. This is not preferred because it is very costly.
そこで、本発明者等は、コストのかからない電解精製工
程のみによシ、Ｓおよびその他の不純物が極めて少ない
高純度銅素材を製造すべく研究を行なった結果、
電気銅粗銅（純度： ９９．９９％以下）を陽極として
電解８ｆ裂するに当り、上記電気銅粗銅の１陽極を多孔
質合成樹脂で覆い、かつ電解液中の硫酸濃度を低く保持
すると、Ｓおよびその池の不純物の極めて少い高純度電
気銅（純度： ９９．９９９ ｓ％以上）を得ることが
できるという知見を得たのでちる。Therefore, the inventors of the present invention conducted research to produce a high-purity copper material with extremely low levels of S, S, and other impurities through an inexpensive electrolytic refining process, and as a result, produced electrolytic copper blister (purity: 99.99). % or less) as an anode, if one anode of the electrolytic copper blister is covered with a porous synthetic resin and the sulfuric acid concentration in the electrolyte is kept low, S and impurities in the pond can be extremely reduced. We have obtained the knowledge that high purity electrolytic copper (purity: 99.999 s% or more) can be obtained.
この発明は、上記知見にもとづいてなされたものであっ
て、
ポアサイズ：１．０μｍ以下の多孔質合成樹脂製薄膜で
覆った電気銅粗銅全陽極に用い、硫酸良度：５〜５０
？／ｌ の電解液中で電触精裂することによυ高純度
銅を得ることに特徴を有するものである。This invention was made based on the above knowledge, and is used in an electrolytic copper blister all-anode covered with a porous synthetic resin thin film with a pore size of 1.0 μm or less, and has a sulfuric acid quality of 5 to 50.
? It is characterized in that high-purity copper can be obtained by electrocatalytic fission in an electrolytic solution of /l.
つぎに、この発明の方法で多孔質合成樹脂製薄膜のポア
サイズおよび電解液中の硫酸）度を上記の通りに限定し
た理由について説明する。Next, the reason why the pore size of the porous synthetic resin thin film and the degree of sulfuric acid in the electrolytic solution are limited as described above in the method of the present invention will be explained.
（ａ） ポアサイズ
陽極付近に生じたスライム等の不純物が分散遊離して陰
極に達しないように隔離するための隔膜として多孔質合
成樹脂製薄膜を用いた場合、七つ薄膜のポアサイズが大
きい方が電解効率は向上するが、大きすぎると上記隔膜
としての作用全なさなくなり、陰極に生ずる高純度銅の
全不純物がボンディングワ・ｆヤとして許容されるｌｐ
ｐｍ１越える７ｈめに、上記ポアサイズ’ｉ−ｊ、ｏμ
ｍ以下とした。(a) Pore Size When a porous synthetic resin thin film is used as a diaphragm to prevent impurities such as slime generated near the anode from being dispersed and released and reaching the cathode, the larger pore size of the seven thin films is Although the electrolytic efficiency improves, if it is too large, it will not function as a diaphragm at all, and all impurities of high-purity copper generated at the cathode will be reduced to a level that is acceptable as a bonding wire.
At the 7th hour beyond pm1, the above pore size 'i-j, oμ
m or less.
ｆｂ） 硫酸濃度
電解精製により得られる高純度胴中のＳ成分の含有率？
少なくするためには、電解液中の硫酸濃度？できる限り
少なくする必要があるが、その濃度が５２／ｌ 未満で
は電解液としての作用が弱くなり電解効率も低下するの
で下限ｆ５？／ｌ とした。fb) Sulfuric acid concentration content of S component in high-purity shell obtained by electrolytic refining?
What should I do to reduce the sulfuric acid concentration in the electrolyte? It is necessary to reduce the amount as much as possible, but if the concentration is less than 52/l, the action as an electrolytic solution becomes weak and the electrolytic efficiency decreases, so the lower limit is f5? /l.
一方、電解液の硫酸濃度が５０り／ｌ を越えると上記
稍製銅中のＳ濃度が０．５ ｐｐｍを越え、デンディン
グワイヤとして実用に供せるビッカース硬さ°３５全越
えるのでその上成金５ Ｑ ？／ｌ としブと。On the other hand, if the sulfuric acid concentration in the electrolyte exceeds 50 l/l, the S concentration in the fine copper will exceed 0.5 ppm, and the Vickers hardness for practical use as a bending wire will exceed 35 degrees. 5 Q? /l Toshibu.
〔実箔夕１１〕
つぎに、この発明の電解精製による高純度銅の製造方法
を実殉し１１ ′Ｌｒこより具体的）て説明する。[Actual Foil Example 11] Next, the method for producing high-purity copper by electrolytic refining of the present invention will be explained in more detail using an actual example.
この発明の実施例で用いる電解精製装置が、第１図に示
されておシ、恒＠槽１内に電解槽２全設置し、恒温槽１
内に設けられた温度センサー８およびヒーター９を液温
制御装置Ｃに接続し、恒温槽の温度全制御すると同時に
電解槽２内の電解液６の温度全恒温に制御する。上記電
解液６ば、電解液循環装置Ｂによってたえず循環され、
電解液は孔７から供給される。陽極３および陰極４は、
電流制御装置Ａに接続されており、上記陽極３は多孔質
合成樹脂製薄膜からなるアノードパック５で包囲されて
いる。The electrolytic refining apparatus used in the embodiment of the present invention is shown in FIG.
A temperature sensor 8 and a heater 9 provided inside the electrolytic cell 2 are connected to a liquid temperature control device C to control the entire temperature of the constant temperature bath and, at the same time, control the temperature of the electrolytic solution 6 in the electrolytic cell 2 to a constant temperature. The electrolyte 6B is constantly circulated by an electrolyte circulation device B,
Electrolyte is supplied from hole 7. The anode 3 and the cathode 4 are
It is connected to a current control device A, and the anode 3 is surrounded by an anode pack 5 made of a porous synthetic resin thin film.
上記電解精製装置を用い、 陽極：電気銅粗銅板（純度： ９９．９９％）。Using the above electrolytic refining device, Anode: Electrolytic copper blister plate (purity: 99.99%).
陰画：チタン板。Negative: titanium plate.
７／−Ｆノ々ッグ：フロロボア（商品名、住友電工製の
炉布、ポアサイズ：第１表に表示）。7/-F Nogu: Fluorobor (trade name, furnace cloth manufactured by Sumitomo Electric Industries, pore size: shown in Table 1).
電流密度： １−５ Ａ／ ｄｍ” 。Current density: 1-5 A/dm".
連歌時間：２４時間。Renga time: 24 hours.
からなる条件で本発明法１〜１０および比軟法１〜４を
実施した。Methods 1 to 10 of the present invention and specific soft methods 1 to 4 were carried out under the following conditions.
電解ｇは、硫酸銅結晶を純水に溶解し、Ｃｕ：６０９／
１． Ｈ２ＳＯ４： ５ ？／ｌの割合で含有させ、Ｂ
ｅ（ボーメ比重計による比重値）埃２０の硫酸銅水溶液
全つくり、この硫酸銅水溶液に硫酸を添加して第１表に
示されるように電解液の硫酸濃度をいろいろと変化せし
めた。また、アノートノ々ッグも０．１〜２．０μｍの
種々のポアサイズのものを使用した。In electrolysis, copper sulfate crystals are dissolved in pure water, and Cu:609/
1. H2SO4: 5? B
e (Specific gravity value determined by Baume hydrometer) A complete aqueous solution of copper sulfate of dust 20 was prepared, and sulfuric acid was added to the aqueous solution of copper sulfate to vary the sulfuric acid concentration of the electrolyte as shown in Table 1. Moreover, various pore sizes of 0.1 to 2.0 μm were used for Anot Nog.
かかる条件で電解精製して得た精裂銅の不純物Ｎ度を測
定し、さらに、これらの精裂銅を真空溶解し、鋳造して
インゴットとし、これらのインゴットのビッカース硬さ
についても測定し、その結果を第１表に示し念。The impurity N degree of the finely divided copper obtained by electrolytic refining under these conditions was measured, and the finely divided copper was vacuum melted and cast into ingots, and the Vickers hardness of these ingots was also measured, The results are shown in Table 1.
上記第１表の本発明法１〜１０にみられるように、電解
液中の硫酸濃度が５〜５０ ？／ｌ の範囲内で、かつ
多孔質合成樹脂製薄膜からなるアノードバッグのポアサ
イズが１．０μｍ以下である条件下で電解精製して得た
精裂銅のＳ含有率は０．５ｐｐｍ以下となり、全不純物
の含有率も１．０ ｐｐｍ以下となっており、かつビッ
カース硬さもボンディングワイヤとして許容される３５
以下となるが、上記硫酸濃度およびポアサイズの一方ま
たは双方ともがこの発明の範囲外にある比較法１〜４で
得られた電解精製鋼は、Ｓ含有率が０．５ ｐｐｍを越
えるかまたはＳ含有率が０．５ ｐｐｍ以下であっても
全不純物含有率が非常に多くなり、ボンディングワイヤ
として許容されるピンカース硬さ：３５を越えている。As seen in methods 1 to 10 of the present invention in Table 1 above, the sulfuric acid concentration in the electrolyte is 5 to 50? /l and the pore size of the anode bag made of a porous synthetic resin thin film is 1.0 μm or less. The S content of finely divided copper obtained by electrolytic refining is 0.5 ppm or less, The total impurity content is 1.0 ppm or less, and the Vickers hardness is 35, which is acceptable as a bonding wire.
However, the electrolytically refined steels obtained by Comparative Methods 1 to 4 in which one or both of the sulfuric acid concentration and pore size are outside the scope of the present invention have an S content of more than 0.5 ppm or an S content of more than 0.5 ppm. Even if the content is 0.5 ppm or less, the total impurity content is extremely high and exceeds the Pinkers hardness of 35, which is acceptable as a bonding wire.
したがって、この発明の方法によれば、ＩＣ。Therefore, according to the method of this invention, an IC.
トランジスター等の半導体装置結線用の軟質のゼンデイ
ングワイヤーとして使用することができる高純度銅を、
電解精製工程のみによって製造することができ、この結
果従来よシも安価な製造が可能となう、しかもゼンディ
ングワイ゛ヤ以外の高純度銅利用分野にも適用が可能で
ある等工業上有用な効果をもたらすものである。High-purity copper that can be used as soft bending wire for connecting semiconductor devices such as transistors.
It can be manufactured using only the electrolytic refining process, and as a result, it can be manufactured at a lower cost than conventional methods.It is also industrially useful, as it can be applied to other fields of high-purity copper use other than shending wire. It brings about a great effect.
第１図は、この発明の実施例で使用された電解精製装置
の断面概略図である。
ｌ・・・恒温槽、 ２・・・電解槽、３・・
・陽極、 ４・・・陰極、５・・・アノー
トノ々ッグ、 ６・・・電解液、７・・・孔、 、
８・・・温度センサー、９・・・ヒーターFIG. 1 is a schematic cross-sectional view of an electrolytic refining apparatus used in an embodiment of the present invention. l... Constant temperature bath, 2... Electrolytic bath, 3...
・Anode, 4...Cathode, 5...Annotnog, 6...Electrolyte, 7...Hole, ,
8...Temperature sensor, 9...Heater
Claims (1)
液中の硫酸濃度を５〜５０ｇ／ｌとし、上記陽極をポア
サイズ：１．０μｍ以下の合成樹脂製薄膜で包囲して電
解精製することを特徴とする電解精製による高純度銅の
製造方法。When performing electrolytic refining using electrolytic copper blister as an anode, the sulfuric acid concentration in the electrolyte should be 5 to 50 g/l, and the anode should be surrounded by a synthetic resin thin film with a pore size of 1.0 μm or less for electrolytic refining. A method for producing high-purity copper using electrolytic refining.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61188254A JPS6345390A (en) | 1986-08-11 | 1986-08-11 | Production of high purity copper by electrolytic refining |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61188254A JPS6345390A (en) | 1986-08-11 | 1986-08-11 | Production of high purity copper by electrolytic refining |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6345390A true JPS6345390A (en) | 1988-02-26 |
Family
ID=16220469
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61188254A Pending JPS6345390A (en) | 1986-08-11 | 1986-08-11 | Production of high purity copper by electrolytic refining |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6345390A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10214066B2 (en) | 2013-03-15 | 2019-02-26 | Indian Motorcycle International, LLC | Two-wheeled vehicle |
-
1986
- 1986-08-11 JP JP61188254A patent/JPS6345390A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10214066B2 (en) | 2013-03-15 | 2019-02-26 | Indian Motorcycle International, LLC | Two-wheeled vehicle |
| US11260712B2 (en) | 2013-03-15 | 2022-03-01 | Indian Motorcycle International, LLC | Two-wheeled vehicle |
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