JP2022072658A - Gold potassium cyanide crystal and gold potassium cyanide solution - Google Patents
Gold potassium cyanide crystal and gold potassium cyanide solution Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 35
- NRTDAKURTMLAFN-UHFFFAOYSA-N potassium;gold(3+);tetracyanide Chemical compound [K+].[Au+3].N#[C-].N#[C-].N#[C-].N#[C-] NRTDAKURTMLAFN-UHFFFAOYSA-N 0.000 title claims abstract description 29
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- 239000010703 silicon Substances 0.000 claims abstract description 13
- XTFKWYDMKGAZKK-UHFFFAOYSA-N potassium;gold(1+);dicyanide Chemical compound [K+].[Au+].N#[C-].N#[C-] XTFKWYDMKGAZKK-UHFFFAOYSA-N 0.000 claims description 46
- 239000000126 substance Substances 0.000 claims description 27
- 238000007747 plating Methods 0.000 abstract description 61
- 239000010931 gold Substances 0.000 abstract description 42
- 229910052737 gold Inorganic materials 0.000 abstract description 40
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 38
- 230000008961 swelling Effects 0.000 abstract description 24
- 229910001020 Au alloy Inorganic materials 0.000 abstract description 8
- 239000003353 gold alloy Substances 0.000 abstract description 8
- 239000000243 solution Substances 0.000 description 55
- 206010042674 Swelling Diseases 0.000 description 23
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 11
- 229910004298 SiO 2 Inorganic materials 0.000 description 10
- 230000007547 defect Effects 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 238000007772 electroless plating Methods 0.000 description 6
- 238000009713 electroplating Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229910021642 ultra pure water Inorganic materials 0.000 description 5
- 239000012498 ultrapure water Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 238000009616 inductively coupled plasma Methods 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- -1 Gold ion Chemical class 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- IZLAVFWQHMDDGK-UHFFFAOYSA-N gold(1+);cyanide Chemical compound [Au+].N#[C-] IZLAVFWQHMDDGK-UHFFFAOYSA-N 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- BIVUUOPIAYRCAP-UHFFFAOYSA-N aminoazanium;chloride Chemical compound Cl.NN BIVUUOPIAYRCAP-UHFFFAOYSA-N 0.000 description 1
- FRHBOQMZUOWXQL-UHFFFAOYSA-L ammonium ferric citrate Chemical compound [NH4+].[Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FRHBOQMZUOWXQL-UHFFFAOYSA-L 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004313 iron ammonium citrate Substances 0.000 description 1
- 235000000011 iron ammonium citrate Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000001579 optical reflectometry Methods 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- C23C18/42—Coating with noble metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/48—Electroplating: Baths therefor from solutions of gold
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Chemically Coating (AREA)
Abstract
Description
本発明は、シアン化金カリウム結晶に関し、特には、金めっき液や金合金めっき液として使用することができるシアン化金カリウム結晶及びシアン化金カリウム溶液に関する。 The present invention relates to a gold potassium cyanide crystal, and more particularly to a gold potassium cyanide crystal and a gold potassium cyanide solution that can be used as a gold plating solution or a gold alloy plating solution.
金（Ａｕ）は、電気伝導性や熱伝導性に優れていることから、電子部品材料として使用されている。軟質金めっきと呼ばれる純度の高い金めっきは、接触抵抗が低く、硬度が低いため、ＩＣ（集積回路）のボンディングワイヤなどに使用される。一方、硬質金めっきと呼ばれる純度の低い金めっきは、硬度が高く、光沢があるため、電子部品のコネクタや装飾用などに使用されている。金めっき液の金供給用の薬剤として、化学的な安定性や溶解容易性の観点から、シアン化金カリウムが使用されている。 Gold (Au) is used as an electronic component material because it has excellent electrical and thermal conductivity. High-purity gold plating called soft gold plating has low contact resistance and low hardness, and is therefore used for bonding wires of ICs (integrated circuits). On the other hand, low-purity gold plating called hard gold plating has high hardness and gloss, so it is used for connectors and decoration of electronic parts. Potassium gold cyanide is used as a chemical for supplying gold in a gold plating solution from the viewpoint of chemical stability and easiness of dissolution.
シアン化金カリウムの製造方法として、シアン化カリウム溶液の電解槽中に金の陽極を配置し、陰極として金属板を配置して、電解することで、シアン化金カリウムを晶析させ、分離する方法が知られている（例えば特許文献１、２）。また、特許文献３には隔膜電解法によりシアン化金塩を晶析させ、結晶を分離した後、分離した溶液を活性炭処理することで、該溶液を隔膜電解法の陽極液として再使用する技術が知られている。 As a method for producing gold potassium cyanide, a gold anode is placed in an electrolytic bath of a potassium cyanide solution, a metal plate is placed as a cathode, and electrolysis is performed to crystallize and separate gold potassium cyanide. It is known (for example, Patent Documents 1 and 2). Further, Patent Document 3 describes a technique of crystallizing a gold cyanide by a diaphragm electrolysis method, separating the crystals, and then treating the separated solution with activated carbon to reuse the solution as an anode solution of the diaphragm electrolysis method. It has been known.
金（Ａｕ）は、電気伝導性や熱伝導性に優れ、触媒作用もなく、化学的腐食に対して耐性があり、酸化被膜を形成しないという優れた特性を示す。そして、金めっきや金合金めっきは、電気伝導性、熱伝導性、耐食性、低接触抵抗、ボンディング性、はんだ付け性、高周波特性、光反射性などの優れた特性を有することから、エレクトロニクス分野における各種電気接点、端子、コネクタピン、リードフレーム、ＩＣ、各種電気回路部品等、幅広く用いられている。 Gold (Au) exhibits excellent properties such as excellent electrical conductivity and thermal conductivity, no catalytic action, resistance to chemical corrosion, and no oxide film formation. Gold plating and gold alloy plating have excellent properties such as electrical conductivity, thermal conductivity, corrosion resistance, low contact resistance, bonding property, solderability, high frequency characteristics, and light reflectivity, and thus are used in the electronics field. It is widely used in various electric contacts, terminals, connector pins, lead frames, ICs, various electric circuit parts, and the like.
しかしながら、金めっきを厚く付着する場合、金めっき膜に膨れという欠陥が生じるという問題があった。このようなめっき膜の膨れの欠陥は、各種電子部品の不良の原因となり得る。このような問題に鑑み、本発明は、金めっき膜又は金合金めっき膜の形成に使用されるシアン化金カリウム結晶及びシアン化金カリウム溶液であって、めっき膜の膨れを低減することができるシアン化金カリウム結晶及びシアン金カリウム溶液を提供することを課題とする。 However, when the gold plating is thickly adhered, there is a problem that a defect called swelling occurs in the gold plating film. Such a defect in the swelling of the plating film can cause defects in various electronic components. In view of such problems, the present invention is a gold potassium cyanide crystal and a gold potassium cyanide solution used for forming a gold plating film or a gold alloy plating film, and can reduce swelling of the plating film. It is an object of the present invention to provide a gold potassium cyanide crystal and a potassium gold cyanide solution.
上記の課題を解決することができる本発明の第一の態様は、シリコン含有量が１０ｗｔｐｐｍ以下であるシアン化金カリウム結晶である。また、本発明の第二の態様はシアン化金カリウム溶液１０ｍＬに含まれる１．０μｍ以上の異物の数が１００個以下であることを特徴とするシアン化金カリウム溶液である。 The first aspect of the present invention capable of solving the above problems is a potassium gold cyanide crystal having a silicon content of 10 wtppm or less. The second aspect of the present invention is a potassium gold cyanide solution, characterized in that the number of foreign substances of 1.0 μm or more contained in 10 mL of the potassium gold cyanide solution is 100 or less.
本発明によれば、シアン化金カリウム溶液を用いて作製される金めっき膜又は金合金めっき膜において、めっき膜の膨れという欠陥が少ないという優れた効果を有する。 According to the present invention, in a gold plating film or a gold alloy plating film produced by using a gold potassium cyanide solution, there is an excellent effect that there are few defects such as swelling of the plating film.
シアン化金カリウム溶液は、金めっき膜又は金合金めっき膜を形成するためのめっき液として使用さている。シアン化金カリウム溶液をめっき液として用いて、金めっき膜又は金合金めっき膜を形成した場合、めっき膜の膨れという欠陥が生じることがあった。そして、めっき膜の膨れは、製品歩留まりの低下を生じさせていた。シアン化金カリウム溶液に含まれる主な不純物としてＡｇ、Ｃｕ、Ｆｅなどの遷移金属が知られているが、これらの金属不純物を低減しても、めっき膜の膨れという欠陥を改善できなかった。 The gold potassium cyanide solution is used as a plating solution for forming a gold plating film or a gold alloy plating film. When a gold plating film or a gold alloy plating film is formed by using a gold potassium cyanide solution as a plating solution, a defect called swelling of the plating film may occur. The swelling of the plating film caused a decrease in product yield. Transition metals such as Ag, Cu, and Fe are known as the main impurities contained in the potassium gold cyanide solution, but even if these metal impurities are reduced, the defect of swelling of the plating film cannot be improved.
また、シアン化金カリウムを超純水に溶かし、ＩＣＰ分析を用いて不純物測定を行ったが、特に気になる不純物は確認できなかった。さらに調査を進めた結果、シアン化金カリウム溶液にＳｉＯ2を主とする酸化物が異物として浮遊し、それが、めっき液中に取り込まれ、めっき膜の膨れの原因となることが判明した。このＳｉＯ2を主とする酸化物はイオンでなく固形物として存在していたため、ＩＣＰで検出できなかったと考えられる。 In addition, potassium gold cyanide was dissolved in ultrapure water, and impurities were measured using ICP analysis, but no impurities of particular concern could be confirmed. As a result of further investigation, it was found that an oxide mainly composed of SiO 2 floats as a foreign substance in the potassium gold cyanide solution, and it is taken into the plating solution and causes swelling of the plating film. It is probable that this oxide mainly composed of SiO 2 was not detected by ICP because it existed as a solid substance rather than an ion.
上記の知見から、本発明の実施形態に係るシアン化金カリウム結晶は、シリコン含有量が１０ｗｔｐｐｍ以下であることを特徴とする。シリコン含有量を１０ｗｔｐｐｍ以下とすることで、上記異物の数を低減でき、これに起因するめっき膜の膨れを抑制することができる。好ましくは５ｗｔｐｐｍ以下であり、より好ましくは１ｗｔｐｐｍ以下である。めっき膜の膨れは、製品歩留まりを低下させることから、めっき膜の膨れの抑制は、製品歩留まりの改善に寄与することが期待できる。 From the above findings, the potassium gold cyanide crystal according to the embodiment of the present invention is characterized by having a silicon content of 10 wtppm or less. By setting the silicon content to 10 wtppm or less, the number of the foreign substances can be reduced, and the swelling of the plating film due to this can be suppressed. It is preferably 5 wtppm or less, and more preferably 1 wtppm or less. Since the swelling of the plating film reduces the product yield, it can be expected that the suppression of the swelling of the plating film contributes to the improvement of the product yield.
シアン化カリウムは、通常、シアン化水素と水酸化カリウムを反応させて製造され、反応容器として石英を用いて製造されている。そのため、ＳｉＯ2は、その石英が攪拌時の摩擦により混入しているものと考えられる。また、周囲の雰囲気からもＳｉＯ2が混入していることが判明した。これまで不純物としてＳｉＯ2が着目されることは皆無であり、シアン化金カリウムの製造時に混入するＳｉＯ2を低減することで、めっき膜の膨れを抑制できたことは極めて重要である。 Potassium cyanide is usually produced by reacting hydrogen cyanide with potassium hydroxide, and is produced using quartz as a reaction vessel. Therefore, it is considered that the quartz of SiO 2 is mixed due to friction during stirring. It was also found that SiO 2 was mixed in from the surrounding atmosphere. Until now, SiO 2 has never been the focus of attention as an impurity, and it is extremely important that the swelling of the plating film could be suppressed by reducing the amount of SiO 2 mixed in during the production of potassium gold cyanide.
本実施形態に係るシアン化金カリウム溶液は、シアン化金カリウム溶液１０ｍＬに含まれる１．０μｍ以上の異物の数が１００個以下であることが好ましい。異物はＳｉＯ2を主とする酸化物から構成されるものであるが、他の成分からなるものであっても、めっき膜の膨れの原因となることから、異物の成分については特に問わない。このように１．０μｍ以上の異物の数を１００個以下とすることで、めっき膜の膨れを効果的に抑制することできる。 In the potassium gold cyanide solution according to the present embodiment, it is preferable that the number of foreign substances of 1.0 μm or more contained in 10 mL of the potassium gold cyanide solution is 100 or less. The foreign substance is composed of an oxide mainly composed of SiO 2 , but even if it is composed of other components, it causes swelling of the plating film, so the component of the foreign substance is not particularly limited. By setting the number of foreign substances of 1.0 μm or more to 100 or less in this way, swelling of the plating film can be effectively suppressed.
シアン化金カリウム溶液は、シアン化金カリウム結晶１ｇを純水／超純水１０ｍＬに溶かして作製されるものである。本実施形態に係るシアン化金カリウムは、シアン化金カリウム溶液に含まれる１．０μｍ以上の異物の数が５０個以下であることがより好ましい。さらに好ましくは異物の数が３０個以下、もっとも好ましくは異物の数が１０個以下である。このように異物の数を減らすことで、めっき膜の膨れを抑制することができ、製品歩留まりの低下を防ぐことができる。 The potassium gold cyanide solution is prepared by dissolving 1 g of potassium gold cyanide crystals in 10 mL of pure water / ultrapure water. It is more preferable that the number of foreign substances of 1.0 μm or more contained in the potassium gold cyanide solution according to the present embodiment is 50 or less. More preferably, the number of foreign substances is 30 or less, and most preferably the number of foreign substances is 10 or less. By reducing the number of foreign substances in this way, it is possible to suppress swelling of the plating film and prevent a decrease in product yield.
（シアン化金カリウムの製造方法）
シアン化金カリウムは、例えば、以下のようにして製造することができる。
市販されるシアン化カリウム結晶を純水に溶かし、シアン化カリウム溶液を作製する。次に、シアン化カリウム溶液を孔径０．１μｍ～１μｍの濾過フィルターで濾過する。この濾過工程により、不純物として混入するＳｉＯ2などの酸化物をある程度、除去することができる。
次に、濾過したシアン化カリウム溶液中で、金を陽極として電解して溶解する。陰極をイオン交換膜で仕切り、金が電着しないように不溶性電極を用いる。金濃度が一定の濃度になった時点で、陽極室からシアン化金カリウムの溶液を抜き出し、１００℃以上で加熱して、濃縮する（晶出させる）。
(Manufacturing method of potassium gold cyanide)
Potassium gold cyanide can be produced, for example, as follows.
A commercially available potassium cyanide crystal is dissolved in pure water to prepare a potassium cyanide solution. Next, the potassium cyanide solution is filtered through a filtration filter having a pore size of 0.1 μm to 1 μm. By this filtration step, oxides such as SiO 2 mixed as impurities can be removed to some extent.
Next, in the filtered potassium cyanide solution, gold is electrolyzed and dissolved as an anode. The cathode is partitioned by an ion exchange membrane, and an insoluble electrode is used to prevent gold electrodeposition. When the gold concentration reaches a certain concentration, the solution of potassium gold cyanide is withdrawn from the anode chamber and heated at 100 ° C. or higher to concentrate (crystallize).
濃縮する際、初期に晶出した結晶の１％～１０％程度を除去した後、純水やアルコールで洗浄して、シアン化金カリウム結晶とする。初期に晶出した結晶中には、ＳｉＯ2を主とする酸化物などを核として成長した結晶が存在するため、これを除去する。その後、上記で得られたシアン化金カリウム結晶を温度５０～９０℃の純水／超純水に溶かし、活性炭フィルターなどで濾過した後、１０℃以下に冷却して、再結晶化することにより、不純物をさらに除去することができる（再結晶化処理）。 At the time of concentration, about 1% to 10% of the crystals initially crystallized are removed, and then washed with pure water or alcohol to obtain gold potassium cyanide crystals. Among the crystals crystallized in the early stage, there are crystals grown with oxides mainly composed of SiO 2 as nuclei, and these are removed. Then, the gold potassium cyanide crystals obtained above are dissolved in pure water / ultrapure water having a temperature of 50 to 90 ° C., filtered through an activated carbon filter or the like, cooled to 10 ° C. or lower, and recrystallized. , Impurities can be further removed (recrystallization treatment).
各種評価に使用した測定装置や測定条件等を以下に示す。
（シリコン含有量の測定）
シアン化金カリウム結晶をテフロン（登録商標）ビーカー内で酸を用いて分解し（ＳｉＯ2などが溶解）、酸で分解したシアン化金溶液に混合標準液を添加してマトリクスマッチング法で、ＩＣＰ（高周波誘導結合プラズマ）分析装置を用いて、シリコン含有量の測定を行う。
The measuring devices and measurement conditions used for various evaluations are shown below.
(Measurement of silicon content)
Potassium gold cyanide crystals are decomposed with an acid in a Teflon (registered trademark) beaker (SiO 2 etc. are dissolved), and a mixed standard solution is added to the gold cyanide solution decomposed with the acid, and ICP is performed by a matrix matching method. (High frequency inductively coupled plasma) The silicon content is measured using an analyzer.
（異物の測定）
シアン化金カリウム結晶１ｇを超純水１０ｍＬに溶かして、シアン化金カリウム溶液を作製し、該溶液をパーティクルカウンター（リオン製 ＫＳ－２８、光散乱法）を用いて、シアン化金カリウム溶液中の１．０μｍ以上の異物の数を分析する。
(Measurement of foreign matter)
1 g of potassium gold cyanide crystals is dissolved in 10 mL of ultrapure water to prepare a potassium gold cyanide solution, and the solution is mixed in the potassium gold cyanide solution using a particle counter (KS-28 manufactured by Rion, light scattering method). The number of foreign substances of 1.0 μm or more is analyzed.
（電解金めっきの条件）
金イオン供給源：シアン化金カリウム １２ｇ／Ｌ
遊離シアン化物イオン減：シアン化カリウム ２０ｇ／Ｌ
電導性向上：炭酸カリウム ２０Ｌ
ｐＨ緩衝剤：りん酸水素化ホウ酸塩 ２０／Ｌ
ｐＨ：１２
浴温：７０℃
電流密度：１Ａ／ｄｍ2
膜厚：５μｍ
(Conditions for electrolytic gold plating)
Gold ion source: Potassium gold cyanide 12 g / L
Free cyanide ion reduction: Potassium cyanide 20 g / L
Improved electrical conductivity: Potassium carbonate 20L
pH buffer: Borate hydride 20 / L
pH: 12
Bath temperature: 70 ° C
Current density: 1A / dm 2
Film thickness: 5 μm
（無電解金めっきの条件）
金イオン供給源：シアン化金カリウム ３ｇ／Ｌ
クエン酸アンモニウム ９０ｇ／Ｌ
塩酸ヒドラジン １９ｇ／Ｌ
ｐＨ：７．５
浴温：９５℃
(Conditions for electroless gold plating)
Gold ion source: Potassium gold cyanide 3 g / L
Ammonium ferric citrate 90g / L
Hydrazine hydrochloride 19g / L
pH: 7.5
Bath temperature: 95 ° C
（めっき膜の膨れの評価）
めっき膜をＳＥＭ（走査型電子顕微鏡：ＪＥＯＬ製ＪＳＭ－７０００Ｆ）で観察し、めっき膜に生じている凹凸のうち、凸部のサイズが５μｍ以上の拡がりを持つものを「ふくれ」と定義した。
(Evaluation of swelling of plating film)
The plating film was observed with an SEM (scanning electron microscope: JSM-7000F manufactured by JEOL), and among the irregularities generated in the plating film, those having a protrusion size of 5 μm or more were defined as “bulges”.
次に、本発明の実施例等について説明する。なお、以下の実施例は、あくまで代表的な例を示しているもので、本発明はこれらの実施例に制限される必要はなく、明細書に記載される技術思想の範囲で解釈されるべきものである。 Next, examples and the like of the present invention will be described. It should be noted that the following examples show only representative examples, and the present invention does not have to be limited to these examples and should be interpreted within the scope of the technical idea described in the specification. It is a thing.
（実施例１）
市販のシアン化カリウム結晶４００ｇを１Ｌの純水溶液に溶かした。次に、得られたシアン化カリウム液を０．１μのろ過フィルターでろ過した後、濾過液を陽極電解液用の溶液として、陽極に金を用いて電解を行った。金濃度が１０ｇ／Ｌになった時点で液を抜き出し、その後、１００℃以上で加熱して濃縮した。その際、初期に晶出した結晶１０％を除去した後、晶出したシアン化金カリウムをアルコール洗浄して、シアン化金カリウム結晶とした。さらに、その後、再結晶化処理を行い、シアン化金カリウム結晶を精製した。
(Example 1)
400 g of commercially available potassium cyanide crystals were dissolved in 1 L of a pure aqueous solution. Next, the obtained potassium cyanide solution was filtered through a 0.1 μ filter, and then electrolysis was performed using the filtered solution as a solution for the anode electrolytic solution and gold as the anode. The liquid was withdrawn when the gold concentration reached 10 g / L, and then heated at 100 ° C. or higher to concentrate. At that time, after removing 10% of the crystals initially crystallized, the crystallized potassium gold cyanide was washed with alcohol to obtain potassium gold cyanide crystals. Further, after that, a recrystallization treatment was carried out to purify the potassium gold cyanide crystals.
このようにして得られたシアン化金カリウム結晶について、シリコンの含有量を分析した結果、１ｗｔｐｐｍ未満であった。また、シアン化金カリウム結晶を超純水に溶かして、シアン化金カリウム溶液を作製し、該溶液をパーティクルカウンターを用いて１．０μｍ以上の異物の数を分析した。その結果、１．０μｍ以上の異物の個数は１～３個／１０ｍＬであった。また、実施例１のシアン化金カリウム溶液を用いて、電解めっき／無電解めっきを実施して、金めっき皮膜を形成し、得られた金めっき膜の表面を観察した結果、膨れの数は０個であった。以上の結果を表１に示す。 The silicon content of the potassium gold cyanide crystals thus obtained was analyzed and found to be less than 1 wtppm. Further, a potassium gold cyanide crystal was dissolved in ultrapure water to prepare a potassium gold cyanide solution, and the number of foreign substances having a size of 1.0 μm or more was analyzed using the solution using a particle counter. As a result, the number of foreign substances of 1.0 μm or more was 1 to 3/10 mL. Further, as a result of performing electrolytic plating / electroless plating using the gold potassium cyanide solution of Example 1 to form a gold plating film and observing the surface of the obtained gold plating film, the number of swellings was found. It was 0. The above results are shown in Table 1.
（実施例２）
実施例２では、０．１μのろ過フィルターでろ過しなかったこと、初期に晶出した結晶５％を除去したこと以外は、実施例１と同様の方法により、シアン化金カリウム結晶を製造した。シアン化金カリウム中のシリコンの含有量を分析した結果、１ｗｔｐｐｍであった。また、シアン化金カリウム溶液１０ｍＬに含まれる１．０μｍ以上の異物の数を分析した結果、異物の個数は８～１０個であった。また、実施例２のシアン化金カリウム溶液を用いて、電解めっき／無電解めっきを実施して、金めっき皮膜を形成し、得られた金めっき膜の表面を観察した結果、膨れの数は２個又は１個であった。
(Example 2)
In Example 2, potassium gold cyanide crystals were produced by the same method as in Example 1 except that the crystals were not filtered with a 0.1 μ filter and 5% of the crystals initially crystallized were removed. .. As a result of analyzing the content of silicon in potassium gold cyanide, it was 1 wtppm. Further, as a result of analyzing the number of foreign substances having a size of 1.0 μm or more contained in 10 mL of the potassium gold cyanide solution, the number of foreign substances was 8 to 10. Further, as a result of performing electrolytic plating / electroless plating using the gold potassium cyanide solution of Example 2 to form a gold plating film and observing the surface of the obtained gold plating film, the number of swellings was found. It was two or one.
（実施例３）
実施例３では、初期に晶出した結晶１％を除去したこと、再結晶化を実施しなかったこと以外は、実施例１と同様の方法により、シアン化金カリウム結晶を製造した。シアン化金カリウム中のシリコンの含有量を分析した結果、３～５ｗｔｐｐｍであった。また、シアン化金カリウム溶液１０ｍＬに含まれる１．０μｍ以上の異物の数を分析した結果、異物の個数は２６～２８個であった。また、実施例３のシアン化金カリウム溶液を用いて、電解めっき／無電解めっきを実施して、金めっき皮膜を形成し、得られた金めっき膜の表面を観察した結果、膨れの数は４個又は３個であった。
(Example 3)
In Example 3, gold potassium cyanide crystals were produced by the same method as in Example 1 except that 1% of the crystals initially crystallized were removed and recrystallization was not performed. As a result of analyzing the content of silicon in potassium gold cyanide, it was 3 to 5 wtppm. Further, as a result of analyzing the number of foreign substances having a size of 1.0 μm or more contained in 10 mL of the potassium gold cyanide solution, the number of foreign substances was 26 to 28. Further, as a result of performing electrolytic plating / electroless plating using the gold potassium cyanide solution of Example 3 to form a gold plating film and observing the surface of the obtained gold plating film, the number of swellings was found. It was 4 or 3.
（実施例４）
実施例４では、０．１μのろ過フィルターでろ過しなかったこと、再結晶化を実施しなかったこと以外は、実施例１と同様の方法により、シアン化金カリウム結晶を製造した。シアン化金カリウム中のシリコンの含有量を分析した結果、９～１０ｗｔｐｐｍであった。また、シアン化金カリウム溶液１０ｍＬに含まれる１．０μｍ以上の異物の数を分析した結果、異物の個数は９６～１００個であった。また、実施例４のシアン化金カリウム溶液を用いて、電解めっき／無電解めっきを実施して、金めっき皮膜を形成し、得られた金めっき膜の表面を観察した結果、膨れの数は１０個又は９個であった。
(Example 4)
In Example 4, gold potassium cyanide crystals were produced by the same method as in Example 1 except that the crystals were not filtered with a 0.1 μ filter and recrystallization was not performed. As a result of analyzing the content of silicon in potassium gold cyanide, it was 9 to 10 wtppm. Further, as a result of analyzing the number of foreign substances having a size of 1.0 μm or more contained in 10 mL of the potassium gold cyanide solution, the number of foreign substances was 96 to 100. Further, as a result of performing electrolytic plating / electroless plating using the gold potassium cyanide solution of Example 4 to form a gold plating film and observing the surface of the obtained gold plating film, the number of swellings was found. It was 10 or 9.
（比較例１）
市販のシアン化カリウム結晶４００ｇを１Ｌの純水溶液に溶かした。得られた溶液を１μのろ過フィルターでろ過し、シアン化金カリウム溶液を製造した。得られたシアン化金カリウム溶液において、１．０μｍ以上の異物の個数は４５８～４９８個／１０ｍＬであった。また、シアン化金カリウム結晶中のシリコン含有量は１８～２１ｗｔｐｐｍであった。次に、比較例１のシアン化金カリウム溶液を用いて、電解めっき／無電解めっきを実施して、金めっき皮膜を形成した。得られた金めっき膜の表面を観察した結果、膨れの数は２６個又は２４個であった。
(Comparative Example 1)
400 g of commercially available potassium cyanide crystals were dissolved in 1 L of a pure aqueous solution. The obtained solution was filtered through a 1 μ filter to produce a potassium gold cyanide solution. In the obtained potassium gold cyanide solution, the number of foreign substances having a size of 1.0 μm or more was 458 to 498/10 mL. The silicon content in the potassium gold cyanide crystals was 18 to 21 wtppm. Next, electroplating / electroless plating was performed using the gold potassium cyanide solution of Comparative Example 1 to form a gold plating film. As a result of observing the surface of the obtained gold plating film, the number of swellings was 26 or 24.
（比較例２）
市販のシアン化カリウム結晶４００ｇを１Ｌの純水溶液に溶かして、シアン化金カリウム溶液を製造した。このようにして製造したシアン化金カリウム溶液において、１．０μｍ以上の異物の個数は７１８～７４６個／１０ｍＬであった。また、シアン化金カリウム溶液中のシリコン含有量は４７～５２ｗｔｐｐｍであった。次に、比較例２のシアン化金カリウム溶液を用いて、電解めっき／無電解めっきを実施して、金めっき皮膜を形成した。得られた金めっき膜の表面を観察した結果、膨れの数は５２個又は４８個であった。
(Comparative Example 2)
400 g of commercially available potassium cyanide crystals were dissolved in 1 L of a pure aqueous solution to produce a gold potassium cyanide solution. In the potassium gold cyanide solution thus produced, the number of foreign substances having a size of 1.0 μm or more was 718 to 746/10 mL. The silicon content in the potassium gold cyanide solution was 47 to 52 wtppm. Next, electroplating / electroless plating was performed using the gold potassium cyanide solution of Comparative Example 2 to form a gold plating film. As a result of observing the surface of the obtained gold plating film, the number of swellings was 52 or 48.
本発明は、シアン化金カリウム溶液を用いて作製される金めっき膜または金合金めっき膜において、めっき膜の膨れという欠陥が少ないという優れた効果を有する。本発明に係るシアン化金カリウムを含むめっき液は、エレクトロニクス分野における各種電気接点、端子、コネクタピン、リードフレーム、ＩＣ、各種電気回路部品等、における、めっき液として有用である。
The present invention has an excellent effect that the gold plating film or the gold alloy plating film produced by using the potassium gold cyanide solution has few defects such as swelling of the plating film. The plating solution containing potassium gold cyanide according to the present invention is useful as a plating solution in various electric contacts, terminals, connector pins, lead frames, ICs, various electric circuit parts, etc. in the field of electronics.
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| CN202080102530.0A CN115867694A (en) | 2020-10-30 | 2020-11-18 | Gold potassium cyanide crystal and gold potassium cyanide solution |
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| JPH04219314A (en) * | 1990-12-19 | 1992-08-10 | Tanaka Kikinzoku Kogyo Kk | Production of gold cyanide |
| JPH04221086A (en) * | 1990-12-19 | 1992-08-11 | Tanaka Kikinzoku Kogyo Kk | Production of gold cyanide |
| JPH0874061A (en) * | 1994-08-30 | 1996-03-19 | Internatl Business Mach Corp <Ibm> | Feeding solution and method for feeding for electroless goldplating bath |
| CN106637314A (en) * | 2016-12-15 | 2017-05-10 | 广东光华科技股份有限公司 | Preparation method of sodium gold sulfide solution for cyanide-free gold plating |
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| CN102978592B (en) * | 2012-12-24 | 2014-11-05 | 厦门大学 | Method for depositing gold nanoparticles on silicon surface by wet process |
| CN103757675B (en) * | 2014-01-20 | 2016-05-11 | 厦门大学 | A kind of fine and close gold thin film method of AFM silicon needle point pulse plating nano thickness |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH04219314A (en) * | 1990-12-19 | 1992-08-10 | Tanaka Kikinzoku Kogyo Kk | Production of gold cyanide |
| JPH04221086A (en) * | 1990-12-19 | 1992-08-11 | Tanaka Kikinzoku Kogyo Kk | Production of gold cyanide |
| JPH0874061A (en) * | 1994-08-30 | 1996-03-19 | Internatl Business Mach Corp <Ibm> | Feeding solution and method for feeding for electroless goldplating bath |
| CN106637314A (en) * | 2016-12-15 | 2017-05-10 | 广东光华科技股份有限公司 | Preparation method of sodium gold sulfide solution for cyanide-free gold plating |
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