JP2018172265A - Copper sulfate, copper sulfate solution, plating solution, method for producing copper sulfate, method for producing semiconductor circuit board, and method for producing electronic apparatus - Google Patents
Copper sulfate, copper sulfate solution, plating solution, method for producing copper sulfate, method for producing semiconductor circuit board, and method for producing electronic apparatus Download PDFInfo
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Abstract
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本発明は、硫酸銅、硫酸銅溶液、めっき液、硫酸銅の製造方法、半導体回路基板の製造方法及び電子機器の製造方法に関する。 The present invention relates to a copper sulfate, a copper sulfate solution, a plating solution, a method for producing copper sulfate, a method for producing a semiconductor circuit board, and a method for producing an electronic device.
硫酸銅は、電解液、顔料、殺虫剤、防腐剤、媒染剤、電池用材料、医薬、半導体装置などの電子部品の電気めっき液の原料等に広く利用されている。 Copper sulfate is widely used as an electrolytic solution, pigment, insecticide, preservative, mordant, battery material, medicine, raw material for electroplating solution of electronic parts such as semiconductor devices, and the like.
例えば、電解液、顔料、殺虫剤、防腐剤、媒染剤、電池用材料、医薬、半導体装置などの電子部品の電気めっき液の原料等に使用可能な硫酸銅として、特許第３９８７０６９号公報（特許文献１）には、純度９９．９９ｗｔ％で、Ｆｅ、Ｃｒ、Ｎｉ等の遷移金属が３ｗｔｐｐｍ以下の高純度硫酸銅が記載されている。また、特許第３９４３５８３号（特許文献２）には、純度９９．９９９ｗｔ％以上の純度を備える高純度硫酸銅が記載されている。 For example, as a copper sulfate that can be used as a raw material for an electroplating solution of an electronic component such as an electrolytic solution, a pigment, an insecticide, an antiseptic, a mordant, a battery material, a medicine, and a semiconductor device, Japanese Patent No. 3987069 (Patent Document) 1) describes high-purity copper sulfate having a purity of 99.99 wt% and a transition metal such as Fe, Cr, or Ni of 3 wtppm or less. Japanese Patent No. 3943583 (Patent Document 2) describes high-purity copper sulfate having a purity of 99.999 wt% or more.
しかしながら、近年の様々な要求により、特許文献１及び特許文献２に記載される高純度硫酸銅よりも更に不純物を低減した硫酸銅への需要が高まってきている。 However, due to various recent demands, there is an increasing demand for copper sulfate in which impurities are further reduced as compared with the high-purity copper sulfate described in Patent Document 1 and Patent Document 2.
例えば、硫酸銅を銅めっき浴の原料として使用した場合、配線微細化に伴い、銅めっき浴の原料である硫酸銅中にアルミニウムが含有されることで、銅皮膜中にアルミニウムが析出して導電性を低下させる問題がある。 For example, when copper sulfate is used as a raw material for a copper plating bath, as the wiring becomes finer, aluminum is contained in the copper sulfate, which is the raw material for the copper plating bath, so that the aluminum is deposited in the copper film and becomes conductive. There is a problem of reducing the performance.
上記課題を鑑み、本発明は、アルミニウム濃度を低減した硫酸銅、硫酸銅溶液、めっき液、硫酸銅の製造方法、半導体回路基板の製造方法及び電子機器の製造方法を提供することを目的とする。 In view of the above problems, an object of the present invention is to provide a copper sulfate, a copper sulfate solution, a plating solution, a copper sulfate manufacturing method, a semiconductor circuit substrate manufacturing method, and an electronic device manufacturing method with reduced aluminum concentration. .
本発明の実施の形態に係る硫酸銅は一側面において、Ａｌ濃度が０．０８質量ｐｐｍ以下である。 In one aspect, the copper sulfate according to the embodiment of the present invention has an Al concentration of 0.08 mass ppm or less.
本発明の実施の形態に係る硫酸銅溶液は一側面において、上記硫酸銅を用いて液状化した硫酸銅溶液である。 In one aspect, the copper sulfate solution according to the embodiment of the present invention is a copper sulfate solution liquefied using the copper sulfate.
本発明の実施の形態に係る硫酸銅溶液は一側面において、Ａｌ濃度が０．０１９質量ｐｐｍ以下である。 In one aspect, the copper sulfate solution according to the embodiment of the present invention has an Al concentration of 0.019 ppm by mass or less.
本発明の実施の形態に係る硫酸銅溶液は別の一側面において、Ａｌ濃度が０．０１６質量ｐｐｍ以下である。 In another aspect of the copper sulfate solution according to the embodiment of the present invention, the Al concentration is 0.016 mass ppm or less.
本発明の実施の形態に係る硫酸銅溶液は更に別の一側面において、Ａｌ濃度が０．０１２質量ｐｐｍ以下である。 In yet another aspect of the copper sulfate solution according to the embodiment of the present invention, the Al concentration is 0.012 mass ppm or less.
本発明の実施の形態に係る硫酸銅の製造方法は一側面において、銅原料を濃硫酸に溶解させて得られる硫酸銅原料溶液を加熱して濃縮し、加熱濃縮後の硫酸銅原料溶液の温度が２５℃になるまで、冷却速度１５℃／ｈｒ以下で冷却し、硫酸銅五水和物の結晶を析出させることを含む。 In one aspect, a method for producing copper sulfate according to an embodiment of the present invention concentrates by heating a copper sulfate raw material solution obtained by dissolving a copper raw material in concentrated sulfuric acid, and the temperature of the copper sulfate raw material solution after heating and concentration. Until the temperature reaches 25 ° C., cooling at a cooling rate of 15 ° C./hr or less to precipitate copper sulfate pentahydrate crystals.
本発明の実施の形態に係るめっき液は一側面において、Ａｌ濃度が０．０１８質量ｐｐｍ以下である。 In one aspect, the plating solution according to the embodiment of the present invention has an Al concentration of 0.018 mass ppm or less.
本発明の実施の形態に係るめっき液は別の一側面において、Ａｌ濃度が０．０１２質量ｐｐｍ以下である。 In another aspect of the plating solution according to the embodiment of the present invention, the Al concentration is 0.012 ppm by mass or less.
本発明の実施の形態に係る半導体回路基板の製造方法は一側面において、上記めっき液を用いて、銅めっきを行うことを含む。 In one aspect, a method for manufacturing a semiconductor circuit substrate according to an embodiment of the present invention includes performing copper plating using the plating solution.
本発明の実施の形態に係る電子機器の製造方法は一側面において、上記半導体回路基板の製造方法で製造した半導体回路基板を用いて、電子機器を製造する。 In one aspect, a method for manufacturing an electronic device according to an embodiment of the present invention manufactures an electronic device using the semiconductor circuit substrate manufactured by the method for manufacturing a semiconductor circuit substrate.
本発明によれば、アルミニウム濃度を低減した硫酸銅、硫酸銅溶液、めっき液、硫酸銅の製造方法、半導体回路基板の製造方法及び電子機器の製造方法が提供できる。 According to the present invention, a copper sulfate, a copper sulfate solution, a plating solution, a copper sulfate manufacturing method, a semiconductor circuit substrate manufacturing method, and an electronic device manufacturing method with reduced aluminum concentration can be provided.
本発明の実施の形態に係る硫酸銅について以下に詳しく説明する。
本発明の実施の形態に係る硫酸銅は、Ａｌ濃度が０．０８質量ｐｐｍ以下であり、好ましくはＡｌ濃度が０．０５質量ｐｐｍ以下である硫酸銅である。硫酸銅中のＡｌ濃度を０．０８質量ｐｐｍ以下とすることにより、例えば、本発明の実施の形態に係る硫酸銅を銅めっき液の原料として利用した場合に、銅皮膜中のＡｌの析出や、Ａｌの析出によって生じる銅の結晶の欠陥の形成を抑制することができる。その結果、この銅皮膜が形成された半導体ウエハ、プリント基板、半導体回路基板或いはこれらを用いた半導体集積回路や電子機器などの電気的特性を向上させることができる。なお、本実施形態に係る硫酸銅は電解液、顔料、殺虫剤、防腐剤、媒染剤、電池用材料等にも利用でき、医薬等に利用した場合においてもアルツハイマー病の発症のリスクを低減できる効果が得られる可能性がある。
The copper sulfate according to the embodiment of the present invention will be described in detail below.
The copper sulfate according to the embodiment of the present invention is copper sulfate having an Al concentration of 0.08 mass ppm or less, and preferably an Al concentration of 0.05 mass ppm or less. By setting the Al concentration in the copper sulfate to 0.08 mass ppm or less, for example, when the copper sulfate according to the embodiment of the present invention is used as a raw material of the copper plating solution, the precipitation of Al in the copper film or , The formation of copper crystal defects caused by the precipitation of Al can be suppressed. As a result, it is possible to improve electrical characteristics of a semiconductor wafer, a printed board, a semiconductor circuit board, or a semiconductor integrated circuit or electronic device using the copper film on which the copper film is formed. In addition, the copper sulfate according to the present embodiment can be used for electrolytes, pigments, insecticides, preservatives, mordants, battery materials, and the like. May be obtained.
本発明の実施の形態に係る硫酸銅は更に、以下の（３−１）〜（３−４）のいずれか一つ、二つ、三つまたは四つを満たす硫酸銅である：
（３−１）Ｉｎ濃度が１．０質量ｐｐｍ以下である、
（３−２）Ｔｌ濃度が０．０５質量ｐｐｍ以下である、
（３−３）Ｓｎ濃度が１．０質量ｐｐｍ以下である、
（３−４）Ａｇ濃度が１．０質量ｐｐｍ以下である。
The copper sulfate according to the embodiment of the present invention is copper sulfate satisfying any one, two, three or four of the following (3-1) to (3-4):
(3-1) In concentration is 1.0 mass ppm or less,
(3-2) Tl concentration is 0.05 mass ppm or less,
(3-3) Sn concentration is 1.0 mass ppm or less,
(3-4) Ag concentration is 1.0 mass ppm or less.
本発明の実施の形態に係る硫酸銅は更にまた以下の（４−１）〜（４−４）のいずれか一つ、二つ、三つまたは四つを満たす硫酸銅である：
（４−１）Ｉｎ濃度が０．５質量ｐｐｍ以下である、
（４−２）Ｔｌ濃度が０．０５質量ｐｐｍ以下である、
（４−３）Ｓｎ濃度が０．５質量ｐｐｍ以下である、
（４−４）Ａｇ濃度が０．８質量ｐｐｍ以下である。
The copper sulfate according to the embodiment of the present invention is copper sulfate satisfying any one, two, three or four of the following (4-1) to (4-4):
(4-1) In concentration is 0.5 mass ppm or less,
(4-2) Tl concentration is 0.05 mass ppm or less,
(4-3) Sn concentration is 0.5 mass ppm or less,
(4-4) Ag concentration is 0.8 mass ppm or less.
本発明の実施の形態に係る硫酸銅は更にまた以下の（５−１）〜（５−４）のいずれか一つ、二つ、三つまたは四つを満たす硫酸銅である：
（５−１）Ｉｎ濃度が０．２質量ｐｐｍ以下である、
（５−２）Ｔｌ濃度が０．０５質量ｐｐｍ以下である、
（５−３）Ｓｎ濃度が０．２質量ｐｐｍ以下である、
（５−４）Ａｇ濃度が０．３質量ｐｐｍ以下である。
The copper sulfate according to the embodiment of the present invention is a copper sulfate satisfying any one, two, three or four of the following (5-1) to (5-4):
(5-1) In concentration is 0.2 mass ppm or less,
(5-2) The Tl concentration is 0.05 mass ppm or less.
(5-3) Sn concentration is 0.2 mass ppm or less,
(5-4) Ag concentration is 0.3 mass ppm or less.
本発明の実施の形態に係る硫酸銅の各元素濃度は以下の方法に従って測定した。 Each elemental concentration of copper sulfate according to the embodiment of the present invention was measured according to the following method.
（Ａｌ、Ｎａ、Ｋ、Ｃｏ、Ｃｒ、Ｎｉ、Ｚｎ、Ｃａ、Ｍｇ、Ｃｄ、Ｍｎ、Ｐｂの濃度分析）
硫酸銅中のＡｌ、Ｎａ、Ｋ、Ｃｏ、Ｃｒ、Ｎｉ、Ｚｎ、Ｃａ、Ｍｇ、Ｃｄ、Ｍｎ、Ｐｂの濃度分析を、電解法により銅を除去した後に、原子吸光法により測定を行った。測定装置にはフレームレス原子吸光装置Ｖａｒｉａｎ社製（Ａｇｉｌｅｎｔ社製）ＡＡ２８０Ｚ / ＧＴＡ１２０（ゼーマン原子吸光分光光度計）を使用した。
(Concentration analysis of Al, Na, K, Co, Cr, Ni, Zn, Ca, Mg, Cd, Mn, Pb)
Concentration analysis of Al, Na, K, Co, Cr, Ni, Zn, Ca, Mg, Cd, Mn, and Pb in copper sulfate was performed by atomic absorption after removing copper by an electrolytic method. A flameless atomic absorption apparatus Varian (Agilent) AA280Z / GTA120 (Zeeman atomic absorption spectrophotometer) was used as the measurement apparatus.
予め硫酸銅のサンプル１ｇと超純水とを１０ｍＬのメスフラスコに入れて、サンプルを超純水に溶解させた。その後、超純水で前述のメスフラスコをメスアップ（メスフラスコの標線とメスフラスコ中の液のメニスカス面の底部が一致するまで、メスフラスコに超純水を加える操作）して、１０ｍＬの硫酸銅水溶液を作製した。その後、得られた硫酸銅水溶液を、アノード及びカソード(２電極式)にＰｔ電極(Ｐｔ濃度が９９．９５質量％以上)を用い、４時間定電位分極して、前述の硫酸銅水溶液から銅を除いた。その後、Ａｌ、Ｎａ、Ｋ、Ｃｏ、Ｃｒ、Ｎｉ、Ｚｎ、Ｃａ、Ｍｇ、Ｃｄ、Ｍｎ、Ｐｂの各濃度を前述のシームレス原子吸光装置を用いて測定した。ここで、前述の超純水は電気伝導率が０．０５８８２μＳ／ｃｍ以下（電気抵抗率（比抵抗）が１７．０ＭΩ・ｃｍ以上）の水とした。硫酸銅のサンプルの質量測定に使用した精密天秤は、小数点以下４桁まで測定可能なものを用いた。測定値は４桁目まで使用した。なお、各元素のフレームレス原子吸光装置の標準液の濃度は１質量ｐｐｂとした。なお、前述の４時間定電位分極は、電流を０．１Ａと設定して３０分間行った後に、電流を０．１５Ａと設定して６０分間行い、その後、電流を０．２５Ａと設定して１５０分間行った。 In advance, 1 g of a copper sulfate sample and ultrapure water were placed in a 10 mL volumetric flask, and the sample was dissolved in ultrapure water. Thereafter, the volumetric flask described above is diluted with ultrapure water (an operation in which ultrapure water is added to the volumetric flask until the marked line of the volumetric flask and the bottom of the meniscus surface of the liquid in the volumetric flask coincide with each other). An aqueous copper sulfate solution was prepared. Thereafter, the obtained copper sulfate aqueous solution was subjected to constant potential polarization for 4 hours using a Pt electrode (Pt concentration of 99.95% by mass or more) for the anode and the cathode (two-electrode type), and the copper sulfate aqueous solution was subjected to copper oxidation. Was excluded. Thereafter, the concentrations of Al, Na, K, Co, Cr, Ni, Zn, Ca, Mg, Cd, Mn, and Pb were measured using the above-described seamless atomic absorption device. Here, the ultrapure water described above was water having an electric conductivity of 0.05882 μS / cm or less (electric resistivity (specific resistance) of 17.0 MΩ · cm or more). The precision balance used for the mass measurement of the copper sulfate sample was one capable of measuring up to 4 digits after the decimal point. Measurement values were used up to the fourth digit. In addition, the density | concentration of the standard solution of the flameless atomic absorption apparatus of each element was 1 mass ppb. The aforementioned 4-hour constant potential polarization was performed for 30 minutes with the current set to 0.1 A, then set for 60 minutes with the current set to 0.15 A, and then set to 0.25 A for the current. For 150 minutes.
各元素濃度は以下の計算式で算出した。
所定の元素の濃度（質量ｐｐｍ）＝硫酸銅水溶液中の所定の元素濃度（質量ｐｐｂ）×採取した硫酸銅水溶液サンプルを溶解させた水溶液の質量（ｇ）／採取した硫酸銅サンプルの質量（ｇ）×１０-3（質量ｐｐｍ／質量ｐｐｂ）＝硫酸銅水溶液中の元素濃度（質量ｐｐｂ）×１０（ｇ）／１（ｇ）×１０-3（質量ｐｐｍ／質量ｐｐｂ）
なお、上述の計算式の硫酸銅のサンプル質量には、精密天秤で測定した値を用いた。採取した硫酸銅サンプルを溶解させた水溶液の質量は１０ｇとした。
The concentration of each element was calculated by the following formula.
Predetermined element concentration (mass ppm) = predetermined element concentration in copper sulfate aqueous solution (mass ppb) × mass of aqueous solution in which collected copper sulfate aqueous sample was dissolved (g) / mass of collected copper sulfate sample (g ) × 10 −3 (mass ppm / mass ppb) = element concentration in copper sulfate aqueous solution (mass ppb) × 10 (g) / 1 (g) × 10 −3 (mass ppm / mass ppb)
In addition, the value measured with the precision balance was used for the sample mass of the copper sulfate of the above-mentioned calculation formula. The mass of the aqueous solution in which the collected copper sulfate sample was dissolved was 10 g.
（ＳｎおよびＡｓの濃度分析）
硫酸銅中のＳｎおよびＡｓの濃度分析は、以下の共沈法によりＳｎ及びＡｓを銅と分離した後に、原子吸光法により測定を行った。測定装置にはフレームレス原子吸光装置Ｖａｒｉａｎ社製（Ａｇｉｌｅｎｔ社製）ＡＡ２８０Ｚ / ＧＴＡ１２０（ゼーマン原子吸光分光光度計）を使用した。
(Sn and As concentration analysis)
The concentration analysis of Sn and As in copper sulfate was carried out by atomic absorption spectrometry after Sn and As were separated from copper by the following coprecipitation method. A flameless atomic absorption apparatus Varian (Agilent) AA280Z / GTA120 (Zeeman atomic absorption spectrophotometer) was used as the measurement apparatus.
予め硫酸銅のサンプル２ｇと超純水と５質量％の硝酸ランタン六水和物（Ｌａ（ＮＯ3）3・６Ｈ2Ｏ）水溶液１ｍＬとを混合して硫酸銅を溶解して、硫酸銅水溶液を作製した。そして、硫酸銅水溶液にアンモニア水を添加して当該硫酸銅水溶液のｐＨを１０〜１１とした。アンモニア水の添加により生じる銅の水酸化物を、アンモニア水を過剰に加えることにより銅とアンモニウムイオンの錯体として溶解した。前述のアンモニア水を添加することでランタンは水酸化物となり、ＳｎおよびＡｓと共に沈殿する。その後、ろ紙を用いて生じた沈殿物を液から分離した。得られた沈殿物に５０ｖｏｌ％の硝酸水溶液（濃硝酸体積：超純水体積＝１：１、温度５０〜８０℃）を加えて、沈殿物を溶解した後、乾固させた。その後、乾固して得られた物を超純水と塩酸から作成した希塩酸（濃塩酸体積：超純水体積＝１：９）で溶解し、得られた溶液を２０ｍＬのメスフラスコに入れた。なお、前述の濃塩酸として、塩化水素濃度が３６質量％の濃塩酸を用いた。そして、前述のメスフラスコをメスアップ（メスフラスコの標線とメスフラスコ中の液のメニスカス面の底部が一致するまで、メスフラスコに超純水を加える操作）して、２０ｍＬの測定用の溶液を作製した。その後、得られた測定用溶液を用いて、ＳｎおよびＡｓの各濃度を前述のフレームレス原子吸光装置を用いて測定した。ここで、前述の超純水は電気伝導率が０．０５８８２μＳ／ｃｍ以下（電気抵抗率（比抵抗）が１７．０ＭΩ・ｃｍ以上）の水とした。硫酸銅の質量測定に使用した精密天秤は、小数点以下４桁まで測定可能なものを用いた。測定値は４桁目まで使用した。各元素のフレームレス原子吸光装置の標準液の濃度は５０質量ｐｐｂとした。 In advance, 2 g of copper sulfate sample, ultrapure water, and 1 mL of 5% by weight lanthanum nitrate hexahydrate (La (NO 3 ) 3 .6H 2 O) aqueous solution were mixed to dissolve the copper sulfate. Was made. Then, aqueous ammonia was added to the copper sulfate aqueous solution to adjust the pH of the copper sulfate aqueous solution to 10-11. Copper hydroxide produced by the addition of aqueous ammonia was dissolved as a complex of copper and ammonium ions by adding an excess of aqueous ammonia. By adding the above ammonia water, lanthanum becomes hydroxide and precipitates together with Sn and As. Thereafter, a precipitate formed using a filter paper was separated from the liquid. A 50 vol% aqueous nitric acid solution (concentrated nitric acid volume: ultrapure water volume = 1: 1, temperature 50-80 ° C.) was added to the resulting precipitate to dissolve the precipitate, and then dried. Thereafter, the product obtained by drying was dissolved with dilute hydrochloric acid prepared from ultrapure water and hydrochloric acid (concentrated hydrochloric acid volume: ultrapure water volume = 1: 9), and the resulting solution was put into a 20 mL volumetric flask. . Note that concentrated hydrochloric acid having a hydrogen chloride concentration of 36% by mass was used as the concentrated hydrochloric acid. Then, the above measuring flask is measured up (operation for adding ultrapure water to the measuring flask until the marked line of the measuring flask and the bottom of the meniscus surface of the liquid in the measuring flask match), and 20 mL of the measuring solution. Was made. Thereafter, each concentration of Sn and As was measured using the obtained measurement solution using the above-mentioned flameless atomic absorption device. Here, the ultrapure water described above was water having an electric conductivity of 0.05882 μS / cm or less (electric resistivity (specific resistance) of 17.0 MΩ · cm or more). The precision balance used for the mass measurement of copper sulfate was one capable of measuring up to 4 digits after the decimal point. Measurement values were used up to the fourth digit. The concentration of the standard solution of the flameless atomic absorption device for each element was 50 mass ppb.
各元素濃度は以下の計算式で算出した。
所定の元素の濃度（質量ｐｐｍ）＝測定用溶液中の所定の元素の濃度（質量ｐｐｂ）×測定用溶液の質量（ｇ）／硫酸銅のサンプル質量（ｇ）×１０-3（質量ｐｐｍ／質量ｐｐｂ）＝測定用溶液中の所定の元素の濃度（質量ｐｐｂ）×２０（ｇ）／２（ｇ）×１０-3（質量ｐｐｍ／質量ｐｐｂ）
The concentration of each element was calculated by the following formula.
Concentration of predetermined element (mass ppm) = concentration of predetermined element in measurement solution (mass ppb) × mass of measurement solution (g) / sample weight of copper sulfate (g) × 10 −3 (mass ppm / Mass ppb) = concentration of a predetermined element in the measurement solution (mass ppb) × 20 (g) / 2 (g) × 10 −3 (mass ppm / mass ppb)
なお、上述の計算式の硫酸銅のサンプル質量には、精密天秤で測定した値を用いた。測定用溶液の質量は２０ｇとした。 In addition, the value measured with the precision balance was used for the sample mass of the copper sulfate of the above-mentioned calculation formula. The mass of the measurement solution was 20 g.
（Ｆｅ、Ｉｎ、Ｔｌ、Ａｇ、Ｔｉの濃度分析）
硫酸銅中のＦｅ、Ｉｎ、Ｔｌ、Ａｇ、Ｔｉの濃度分析は、ＩＣＰ−ＭＳ法によって行うことができる。具体的には、硫酸銅のサンプルを５００倍の超純水で希釈しＳＩＩナノテクノロジー社製、ＩＣＰ質量分析装置（ＳＰＷ９７００）で測定した結果を示す。
(Concentration analysis of Fe, In, Tl, Ag, Ti)
The concentration analysis of Fe, In, Tl, Ag, and Ti in copper sulfate can be performed by the ICP-MS method. Specifically, the result of diluting a copper sulfate sample with 500-fold ultrapure water and measuring with an ICP mass spectrometer (SPW9700) manufactured by SII NanoTechnology is shown.
前述のＩＣＰ−ＭＳ法による硫酸銅中のＦｅ、Ｉｎ、Ｔｌ、Ａｇ、Ｔｉの濃度分析は以下の方法により行うことができる。
（１）硫酸銅のサンプルを１（ｇ）採取する。なお、硫酸銅の質量測定に使用した精密天秤は、小数点以下４桁まで測定可能なものを用いた。測定値は４桁目まで使用した。
（２）前述の（１）の硫酸銅のサンプルと超純水とを５００ｍＬのメスフラスコに入れ、その後超純水（必要に応じて希硝酸を含む）で秤量線までメスアップして、硫酸銅水溶液を作製する。ここで、前述の超純水は電気伝導率が０．０５８８２μＳ／ｃｍ以下（電気抵抗率（比抵抗）が１７．０ＭΩ・ｃｍ以上）の水とした。なお、前述の水の電気伝導率は、ＪＩＳ Ｋ０５５２（１９９４）に基づいて測定可能である。また、前述の超純水は例えば、アドバンテック東洋株式会社製の超純水製造装置ＲＦＵ４００シリーズ等の市販の超純水製造装置を用いて製造することが可能である。
（３）（２）で作製した硫酸銅水溶液中のＦｅ、Ｉｎ、Ｔｌ、Ａｇ、Ｔｉの濃度を、ＳＩＩナノテクノロジー社製、ＩＣＰ質量分析装置（ＳＰＷ９７００）等のＩＣＰ質量分析装置で測定する。得られた硫酸銅水溶液中のＦｅ、Ｉｎ、Ｔｌ、Ａｇ、Ｔｉの濃度をそれぞれＣＦｅ（質量ｐｐｂ）、ＣＩｎ（質量ｐｐｂ）、ＣＴｌ（質量ｐｐｂ）、ＣＡｇ（質量ｐｐｂ）、ＣＴｉ（質量ｐｐｂ）とする。
The concentration analysis of Fe, In, Tl, Ag, and Ti in copper sulfate by the aforementioned ICP-MS method can be performed by the following method.
(1) Take 1 (g) of copper sulfate sample. In addition, the precision balance used for the mass measurement of copper sulfate used what can measure to four digits after a decimal point. Measurement values were used up to the fourth digit.
(2) Put the copper sulfate sample of the above (1) and ultrapure water into a 500 mL volumetric flask, then measure up to the weighing line with ultrapure water (containing dilute nitric acid if necessary), and add sulfuric acid. A copper aqueous solution is prepared. Here, the ultrapure water described above was water having an electric conductivity of 0.05882 μS / cm or less (electric resistivity (specific resistance) of 17.0 MΩ · cm or more). In addition, the above-mentioned electrical conductivity of water can be measured based on JIS K0552 (1994). Moreover, the above-described ultrapure water can be produced by using a commercially available ultrapure water production apparatus such as the ultrapure water production apparatus RFU400 series manufactured by Advantech Toyo Corporation.
(3) The concentration of Fe, In, Tl, Ag, and Ti in the aqueous copper sulfate solution prepared in (2) is measured with an ICP mass spectrometer such as an ICP mass spectrometer (SPW9700) manufactured by SII Nanotechnology. The concentrations of Fe, In, Tl, Ag, and Ti in the obtained aqueous copper sulfate solution were CFe (mass ppb), CIn (mass ppb), CTl (mass ppb), CAg (mass ppb), and CTi (mass ppb), respectively. And
以下の式により硫酸銅中のＦｅ、Ｉｎ、Ｔｌ、Ａｇ、Ｔｉの濃度を算出した。 The concentration of Fe, In, Tl, Ag, and Ti in copper sulfate was calculated from the following formula.
Ｆｅ濃度（質量ｐｐｍ）＝採取した硫酸銅サンプルの水溶液中のＦｅ濃度（質量ｐｐｂ）×採取した硫酸銅サンプルの水溶液の質量（ｇ）／採取した硫酸銅サンプルの質量（ｇ）×１０-3（質量ｐｐｍ／質量ｐｐｂ）＝ＣＦｅ（質量ｐｐｂ）×（５００（ｇ））×１０-3（質量ｐｐｍ／質量ｐｐｂ）／１（ｇ）＝０．５００×ＣＦｅ（質量ｐｐｍ） Fe concentration (mass ppm) = Fe concentration (mass ppb) in the collected copper sulfate sample aqueous solution × mass of the collected copper sulfate sample aqueous solution (g) / mass of the collected copper sulfate sample (g) × 10 −3 (Mass ppm / mass ppb) = CFe (mass ppb) × (500 (g)) × 10 −3 (mass ppm / mass ppb) / 1 (g) = 0.500 × CFe (mass ppm)
Ｉｎ濃度（質量ｐｐｍ）＝採取した硫酸銅サンプルの水溶液中のＩｎ濃度（質量ｐｐｂ）×採取した硫酸銅サンプルの水溶液の質量（ｇ）／採取した硫酸銅サンプルの質量（ｇ）×１０-3（質量ｐｐｍ／質量ｐｐｂ）＝ＣＩｎ（質量ｐｐｂ）×（５００（ｇ））×１０-3（質量ｐｐｍ／質量ｐｐｂ）／１（ｇ）＝０．５００×ＣＩｎ（質量ｐｐｍ） In concentration (mass ppm) = In concentration (mass ppb) in the collected copper sulfate sample aqueous solution x Mass of the collected copper sulfate sample aqueous solution (g) / Mass of the collected copper sulfate sample (g) x 10-3 (Mass ppm / mass ppb) = CIn (mass ppb) × (500 (g)) × 10 −3 (mass ppm / mass ppb) / 1 (g) = 0.500 × CIn (mass ppm)
Ｔｌ濃度（質量ｐｐｍ）＝採取した硫酸銅サンプルの水溶液中のＴｌ濃度（質量ｐｐｂ）×採取した硫酸銅サンプルの水溶液の質量（ｇ）／採取した硫酸銅サンプルの質量（ｇ）×１０-3（質量ｐｐｍ／質量ｐｐｂ）＝ＣＴｌ（質量ｐｐｂ）×（５００（ｇ））×１０-3（質量ｐｐｍ／質量ｐｐｂ）／１（ｇ）＝０．５００×ＣＴｌ（質量ｐｐｍ） Tl concentration (mass ppm) = Tl concentration (mass ppb) in the collected copper sulfate sample aqueous solution × mass of the collected copper sulfate sample aqueous solution (g) / mass of the collected copper sulfate sample (g) × 10 −3 (Mass ppm / mass ppb) = CTl (mass ppb) × (500 (g)) × 10 −3 (mass ppm / mass ppb) / 1 (g) = 0.500 × CTl (mass ppm)
Ａｇ濃度（質量ｐｐｍ）＝採取した硫酸銅サンプルの水溶液中のＡｇ濃度（質量ｐｐｂ）×採取した硫酸銅サンプルの水溶液の質量（ｇ）／採取した硫酸銅サンプルの質量（ｇ）×１０-3（質量ｐｐｍ／質量ｐｐｂ）＝ＣＡｇ（質量ｐｐｂ）×（５００（ｇ））×１０-3（質量ｐｐｍ／質量ｐｐｂ）／１（ｇ）＝０．５００×ＣＡｇ（質量ｐｐｍ） Ag concentration (mass ppm) = Ag concentration (mass ppb) in the collected copper sulfate sample aqueous solution × mass of the collected copper sulfate sample aqueous solution (g) / mass of the collected copper sulfate sample (g) × 10 −3 (Mass ppm / mass ppb) = CAg (mass ppb) × (500 (g)) × 10 −3 (mass ppm / mass ppb) / 1 (g) = 0.500 × CAg (mass ppm)
Ｔｉ濃度（質量ｐｐｍ）＝採取した硫酸銅サンプルの水溶液中のＴｉ濃度（質量ｐｐｂ）×採取した硫酸銅サンプルの水溶液の質量（ｇ）／採取した硫酸銅サンプルの質量（ｇ）×１０-3（質量ｐｐｍ／質量ｐｐｂ）＝ＣＴｉ（質量ｐｐｂ）×（５００（ｇ））×１０-3（質量ｐｐｍ／質量ｐｐｂ）／１（ｇ）＝０．５００×ＣＴｉ（質量ｐｐｍ） Ti concentration (mass ppm) = Ti concentration (mass ppb) in the aqueous solution of the collected copper sulfate sample × mass (g) of the collected aqueous solution of the copper sulfate sample / mass (g) of the collected copper sulfate sample × 10 −3 (Mass ppm / mass ppb) = CTi (mass ppb) × (500 (g)) × 10 −3 (mass ppm / mass ppb) / 1 (g) = 0.500 × CTi (mass ppm)
なお、上述の計算式の硫酸銅のサンプル質量には、精密天秤で測定した値を用いた。測定用溶液の質量は５００ｇとした。 In addition, the value measured with the precision balance was used for the sample mass of the copper sulfate of the above-mentioned calculation formula. The mass of the measurement solution was 500 g.
（Ｃｌの濃度分析）
Ｃｌ濃度（塩化物イオン濃度）についてはイオンクロマトグラフを用いて測定した。具体的には、Ｄｉｏｎｅｘ社製イオンクロマトグラフ（ＩＣＳ-１５００型）を用いて測定を行った。
(Cl concentration analysis)
The Cl concentration (chloride ion concentration) was measured using an ion chromatograph. Specifically, the measurement was performed using an ion chromatograph (ICS-1500 type) manufactured by Dionex.
前述のイオンクロマトグラフによる硫酸銅中のＣｌの濃度分析は以下の方法により行うことができる。
（１）硫酸銅のサンプルを１（ｇ）採取する。なお、硫酸銅の質量測定に使用した精密天秤は、小数点以下４桁まで測定可能なものを用いた。測定値は４桁目まで使用した。
（２）前述の（１）の硫酸銅のサンプルと超純水とを１００ｍＬのメスフラスコに入れ、その後超純水で秤量線までメスアップして、硫酸銅水溶液を作製する。ここで、前述の超純水は電気伝導率が０．０５８８２μＳ／ｃｍ以下（電気抵抗率（比抵抗）が１７．０ＭΩ・ｃｍ以上）の水とした。なお、前述の水の電気伝導率は、ＪＩＳ Ｋ０５５２（１９９４）に基づいて測定可能である。また、前述の超純水は例えば、アドバンテック東洋株式会社製の超純水製造装置 ＲＦＵ４００シリーズ等の市販の超純水製造装置を用いて製造することが可能である。
（３）（２）で作製した硫酸銅水溶液中のＣｌの濃度を、Ｄｉｏｎｅｘ社製イオンクロマトグラフ（ＩＣＳ-１５００型）を用いて測定する。得られた硫酸銅水溶液中のＣｌ、の濃度をＣＣｌ（質量ｐｐｂ）とする。
The concentration analysis of Cl in copper sulfate by the aforementioned ion chromatograph can be performed by the following method.
(1) Take 1 (g) of copper sulfate sample. In addition, the precision balance used for the mass measurement of copper sulfate used what can measure to four digits after a decimal point. Measurement values were used up to the fourth digit.
(2) The copper sulfate sample of the above (1) and ultrapure water are placed in a 100 mL volumetric flask, and then measured up to a weighing line with ultrapure water to prepare an aqueous copper sulfate solution. Here, the ultrapure water described above was water having an electric conductivity of 0.05882 μS / cm or less (electric resistivity (specific resistance) of 17.0 MΩ · cm or more). In addition, the above-mentioned electrical conductivity of water can be measured based on JIS K0552 (1994). Moreover, the above-described ultrapure water can be produced using, for example, a commercially available ultrapure water production apparatus such as the ultrapure water production apparatus RFU400 series manufactured by Advantech Toyo Corporation.
(3) The concentration of Cl in the aqueous copper sulfate solution prepared in (2) is measured using an ion chromatograph (ICS-1500 type) manufactured by Dionex. The concentration of Cl in the obtained aqueous copper sulfate solution is CCl (mass ppb).
以下の式により硫酸銅中のＣｌの濃度を算出した。
Ｃｌ濃度（質量ｐｐｍ）＝採取した硫酸銅サンプルの水溶液中のＣｌ濃度（質量ｐｐｂ）×採取した硫酸銅サンプルの水溶液の質量（ｇ）／採取した硫酸銅サンプルの質量（ｇ）×１０-3（質量ｐｐｍ／質量ｐｐｂ）＝ＣＣｌ（質量ｐｐｂ）×（１００（ｇ））×１０-3（質量ｐｐｍ／質量ｐｐｂ）／１（ｇ）＝０．１００×ＣＣｌ（質量ｐｐｍ）
なお、上述の計算式の硫酸銅のサンプル質量には、精密天秤で測定した値を用いた。測定用溶液の質量は１００ｇとした。
The concentration of Cl in copper sulfate was calculated from the following equation.
Cl concentration (mass ppm) = Cl concentration (mass ppb) in an aqueous solution of the collected copper sulfate sample × mass (g) of the aqueous solution of the collected copper sulfate sample / mass (g) of the collected copper sulfate sample × 10 −3 (Mass ppm / mass ppb) = CCl (mass ppb) × (100 (g)) × 10 −3 (mass ppm / mass ppb) / 1 (g) = 0.100 × CCl (mass ppm)
In addition, the value measured with the precision balance was used for the sample mass of the copper sulfate of the above-mentioned calculation formula. The mass of the measurement solution was 100 g.
本実施形態に係る硫酸銅は、Ｃｕ以外の金属不純物の濃度の合計が３０質量ｐｐｍ以下であり、一実施態様においては合計が２５質量ｐｐｍ以下であり、別の一実施態様においては合計が２０質量ｐｐｍ以下であり、更に別の一実施態様においては合計が１５質量ｐｐｍ以下である。 In the copper sulfate according to this embodiment, the total concentration of metal impurities other than Cu is 30 ppm by mass or less, and in one embodiment, the total is 25 ppm by mass or less, and in another embodiment, the total is 20 ppm. In another embodiment, the total is 15 ppm by mass or less.
本実施形態において「Ｃｕ以外の金属不純物の濃度の合計」は、Ｎａ、Ｋ、Ｃｏ、Ｃｒ、Ｎｉ、Ｚｎ、Ａｌ、Ｃａ、Ｍｇ、Ｃｄ、Ｍｎ、Ｐｂ、Ｓｎ、Ａｓ、Ｃｌ、Ｆｅ、Ａｇ、Ｔｌ、Ｔｉ、Ｉｎを分析対象とし、分析した結果得られた各元素の濃度の合計をＣｕ以外の金属不純物の濃度の合計とした。 In this embodiment, “the total concentration of metal impurities other than Cu” is Na, K, Co, Cr, Ni, Zn, Al, Ca, Mg, Cd, Mn, Pb, Sn, As, Cl, Fe, and Ag. Tl, Ti, and In were analyzed, and the total concentration of each element obtained as a result of the analysis was defined as the total concentration of metal impurities other than Cu.
硫酸銅中のＡｌ、Ｉｎ、Ｔｌ、Ａｇ、Ｓｎ濃度（質量ｐｐｍ）については、前述と同様の方法により測定した。また、前述のその他の元素も前述と同様に測定した。 About Al, In, Tl, Ag, and Sn density | concentration (mass ppm) in copper sulfate, it measured by the method similar to the above-mentioned. The other elements described above were measured in the same manner as described above.
硫酸銅中の全有機炭素（ＴＯＣ）濃度は１０質量ｐｐｍ以下であることが好ましく、５質量ｐｐｍ以下が好ましく、１質量ｐｐｍ以下が好ましく、０．１質量ｐｐｍ以下が更に好ましい。硫酸銅中のＴＯＣ濃度は、島津製作所製、全有機炭素計（ＴＯＣ−Ｖ）を用いて測定した。なお、全有機炭素の測定は硫酸銅水溶液中の銅濃度が２５〜５０ｇ／Ｌとなるように、硫酸銅のサンプルを超純水（電気抵抗率（比抵抗）が１７．０ＭΩ・ｃｍ以上の水）に溶解させて得られた硫酸銅水溶液を用いて行った。なお、硫酸銅中の全有機炭素（ＴＯＣ）濃度は以下の式で算出した。 The total organic carbon (TOC) concentration in the copper sulfate is preferably 10 mass ppm or less, preferably 5 mass ppm or less, preferably 1 mass ppm or less, and more preferably 0.1 mass ppm or less. The TOC concentration in copper sulfate was measured using a total organic carbon meter (TOC-V) manufactured by Shimadzu Corporation. In addition, the measurement of the total organic carbon is carried out so that the copper concentration in the copper sulfate aqueous solution is 25 to 50 g / L, and the copper sulfate sample is ultrapure water (electric resistivity (specific resistance) is 17.0 MΩ · cm or more). It was carried out using an aqueous copper sulfate solution obtained by dissolving in water. In addition, the total organic carbon (TOC) density | concentration in copper sulfate was computed with the following formula | equation.
全有機炭素濃度（質量ｐｐｍ）＝採取した硫酸銅サンプルの水溶液中の全有機炭素濃度（質量ｐｐｂ）×採取した硫酸銅サンプルの水溶液の質量（ｇ）／採取した硫酸銅サンプルの質量（ｇ）×１０-3（質量ｐｐｍ／質量ｐｐｂ） Total organic carbon concentration (mass ppm) = total organic carbon concentration (mass ppb) in collected copper sulfate sample aqueous solution × mass of collected copper sulfate sample aqueous solution (g) / mass of collected copper sulfate sample (g) × 10 −3 (mass ppm / mass ppb)
本発明の実施の形態に係る硫酸銅は、硫酸銅の無水物および／または硫酸銅の水和物を含むことができる。硫酸銅の水和物としては、硫酸銅一水和物、硫酸銅三水和物、硫酸銅五水和物等があげられる。また、本発明の実施の形態に係る硫酸銅は、公知の硫酸銅の水和物を含んでも良い。また、本願明細書、特許請求の範囲、要約において「硫酸銅」の文言を使用した場合には、当該「硫酸銅」は、硫酸銅の無水物および硫酸銅の水和物を含む概念であるとする。 The copper sulfate according to the embodiment of the present invention may include an anhydrous copper sulfate and / or a hydrated copper sulfate. Examples of copper sulfate hydrates include copper sulfate monohydrate, copper sulfate trihydrate, copper sulfate pentahydrate and the like. Further, the copper sulfate according to the embodiment of the present invention may include a known copper sulfate hydrate. In addition, when the term “copper sulfate” is used in the present specification, claims, and abstract, the “copper sulfate” is a concept including an anhydride of copper sulfate and a hydrate of copper sulfate. And
また、本実施形態に係る硫酸銅は、硫酸銅の濃度（硫酸銅が全て五水和物になっていると仮定した場合の硫酸銅五水和物の濃度）が９９．９質量％以上９９．９９９質量％以下であり、一実施態様においては９９．９質量％以上９９．９９５質量％以下であり、別の一実施態様においては、９９．９質量％以上９９．９９２質量％以下であり、更に別の一実施態様においては、９９．９質量％以上９９．９９質量％以下であり、更に別の一実施態様においては、９９．９質量％以上９９．９９質量％未満である。 Further, the copper sulfate according to the present embodiment has a copper sulfate concentration (concentration of copper sulfate pentahydrate when it is assumed that the copper sulfate is all pentahydrate) of 99.9% by mass or more. 999 mass% or less, and in one embodiment, 99.9 mass% or more and 99.995 mass% or less, and in another embodiment, 99.9 mass% or more and 99.992 mass% or less. In still another embodiment, it is 99.9% by mass or more and 99.99% by mass or less, and in yet another embodiment, it is 99.9% by mass or more and less than 99.99% by mass.
硫酸銅の濃度は、以下の式によって評価した結果を示す。
硫酸銅サンプル中の銅濃度の測定チオ硫酸ナトリウム滴定法により測定した。
銅濃度の測定方法(チオ硫酸ナトリウム滴定法)については下記の通りとした。
所定量の硫酸銅サンプルを採取し、超純水に溶解をして、硫酸銅の濃度が２５５ｇ／Ｌである硫酸銅水溶液を作製する。硫酸銅サンプルの質量測定に使用した精密天秤は、小数点以下４桁まで測定可能なものを用いた。ここで、前述の超純水は電気伝導率が０．０５８８２μＳ／ｃｍ以下（電気抵抗率（比抵抗）が１７．０ＭΩ・ｃｍ以上）の水とした。測定値は４桁目まで使用した。その後、以下の（１）（２）の操作を行った。
（１）前述の硫酸銅水溶液を２ｍＬ採取し、過剰のヨウ化カリウムを添加する。
硫酸銅水溶液にヨウ化カリウムを添加することで以下の反応が進行する。
２Ｃｕ2+ ＋ ４ＫＩ → ２ＣｕＩ ＋ Ｉ2 ＋ ４Ｋ+
（２）チオ硫酸ナトリウムで（１）の反応で発生したＩ2量を滴定することにより測定した。具体的にはヨウ素の紫色が消え、白濁液になるまで滴定した。そして、滴定に使用したチオ硫酸ナトリウムの物質量（モル）を算出した。
Ｉ2 ＋ ２Ｎａ2Ｓ2Ｏ3 → Ｎａ2Ｓ4Ｏ6 ＋ ２ＮａＩ
滴下したチオ硫酸ナトリウムと同じ量の物質量（モル）を硫酸銅サンプル中に含まれる銅の物質量とした。
The density | concentration of copper sulfate shows the result evaluated by the following formula | equation.
Measurement of copper concentration in copper sulfate sample It was measured by sodium thiosulfate titration method.
The copper concentration measurement method (sodium thiosulfate titration method) was as follows.
A predetermined amount of copper sulfate sample is collected and dissolved in ultrapure water to prepare a copper sulfate aqueous solution having a copper sulfate concentration of 255 g / L. The precision balance used for the mass measurement of the copper sulfate sample was one that can measure up to four decimal places. Here, the ultrapure water described above was water having an electric conductivity of 0.05882 μS / cm or less (electric resistivity (specific resistance) of 17.0 MΩ · cm or more). Measurement values were used up to the fourth digit. Thereafter, the following operations (1) and (2) were performed.
(1) Collect 2 mL of the aqueous copper sulfate solution and add excess potassium iodide.
The following reaction proceeds by adding potassium iodide to an aqueous copper sulfate solution.
2Cu 2+ + 4KI → 2CuI + I 2 + 4K +
(2) The amount of I 2 generated in the reaction of (1) was measured by titration with sodium thiosulfate. Specifically, titration was performed until the purple color of iodine disappeared and a cloudy liquid was formed. And the substance amount (mol) of the sodium thiosulfate used for the titration was computed.
I 2 + 2Na 2 S 2 O 3 → Na 2 S 4 O 6 + 2NaI
The same amount of substance (mole) as the dropped sodium thiosulfate was used as the amount of copper contained in the copper sulfate sample.
銅濃度は以下の式に従って測定した。
硫酸銅サンプル中に含まれる銅の質量（ｇ）＝硫酸銅サンプル中に含まれる銅の物質量（ｍｏｌ）×銅の原子量（ｇ／ｍｏｌ）＝ヨウ素（Ｉ2）の滴定に必要であったチオ硫酸ナトリウムの物質量（ｍｏｌ）×銅の原子量（ｇ／ｍｏｌ）
The copper concentration was measured according to the following formula.
The mass of copper contained in the copper sulfate sample (g) = the amount of copper contained in the copper sulfate sample (mol) × the atomic weight of copper (g / mol) = necessary for titration of iodine (I 2 ) Substance amount of sodium thiosulfate (mol) x atomic weight of copper (g / mol)
硫酸銅サンプル中に含まれる硫酸銅５水和物の質量（ｇ）＝硫酸銅サンプル中に含まれる銅の質量（ｇ）×３．９２９２００９
（硫酸銅が全て硫酸銅５水和物になっていると仮定した。）
Mass of copper sulfate pentahydrate contained in copper sulfate sample (g) = Mass of copper contained in copper sulfate sample (g) × 3.9292009
(Assumed that all copper sulfate is copper sulfate pentahydrate.)
硫酸銅の濃度（質量％）＝硫酸銅サンプル中に含まれる硫酸銅５水和物の質量（ｇ）／硫酸銅サンプルの質量（ｇ）×１００（％）＝硫酸銅サンプル中の銅の質量（ｇ）×３．９２９２００９／硫酸銅サンプルの質量（ｇ）×１００（％） Concentration (mass%) of copper sulfate = mass of copper sulfate pentahydrate contained in the copper sulfate sample (g) / mass of copper sulfate sample (g) × 100 (%) = mass of copper in the copper sulfate sample (G) × 3.9292009 / mass of copper sulfate sample (g) × 100 (%)
本発明の実施形態に係る硫酸銅の製造方法について説明する。
まず、銅を含む原料と濃硫酸水溶液とを反応槽内において撹拌しながら加熱することで濃硫酸水溶液中に銅を含む原料を溶解させて硫酸銅原料溶液を得る。撹拌手段は特に制限されないが、例えば空気を吹き込んで撹拌することができる。
The manufacturing method of the copper sulfate which concerns on embodiment of this invention is demonstrated.
First, the raw material containing copper and the concentrated sulfuric acid aqueous solution are heated while stirring in the reaction tank to dissolve the raw material containing copper in the concentrated sulfuric acid aqueous solution, thereby obtaining a copper sulfate raw material solution. The stirring means is not particularly limited, but for example, air can be blown to stir.
銅を含む原料としては、市販の硫酸銅結晶（濃度９５〜９９．９質量％）を用いることができる。この硫酸銅結晶には、Ｎａ、Ｍｇ、Ａｌ、Ｃａ、Ｉｎ、Ｓｎ、Ａｇ等の不純物が含まれている。或いは、純度９９．９９％以上の電気銅を濃硫酸の水溶液により溶解させた溶液を、銅を含む原料として使用することができる。濃硫酸としては、市販の濃硫酸（硫酸濃度９５〜９９．９質量％）を用いることができる。濃硫酸の水溶液に用いる水は超純水であることが好ましい。前述の超純水の電気抵抗率は１５ＭΩ・ｃｍ以上であることが好ましい。電気抵抗率が１５ＭΩ・ｃｍ以上の超純水を用いることにより、濃硫酸の水溶液中の前述のＮａ、Ｍｇ、Ａｌ、Ｃａ、Ｉｎ、Ｓｎ、Ａｇ等の不純物を低減することが出来る場合があり、得られる硫酸銅中のＡｌ等の元素の濃度をより低減することができる場合があるからである。前述の超純水の電気抵抗率は１５．５ＭΩ・ｃｍ以上であることがより好ましく、１６．０ＭΩ・ｃｍ以上であることがより好ましく、１６．５ＭΩ・ｃｍ以上であることがより好ましく、１７．０ＭΩ・ｃｍ以上であることがより好ましい。 As a raw material containing copper, commercially available copper sulfate crystals (concentration 95 to 99.9% by mass) can be used. The copper sulfate crystal contains impurities such as Na, Mg, Al, Ca, In, Sn, and Ag. Alternatively, a solution in which electrolytic copper having a purity of 99.99% or more is dissolved with an aqueous solution of concentrated sulfuric acid can be used as a raw material containing copper. As concentrated sulfuric acid, commercially available concentrated sulfuric acid (sulfuric acid concentration 95-99.9 mass%) can be used. The water used for the concentrated sulfuric acid aqueous solution is preferably ultrapure water. The electrical resistivity of the above-described ultrapure water is preferably 15 MΩ · cm or more. Impurities such as Na, Mg, Al, Ca, In, Sn, and Ag in the aqueous solution of concentrated sulfuric acid may be reduced by using ultrapure water having an electrical resistivity of 15 MΩ · cm or more. This is because the concentration of elements such as Al in the obtained copper sulfate may be further reduced. The electrical resistivity of the above-described ultrapure water is more preferably 15.5 MΩ · cm or more, more preferably 16.0 MΩ · cm or more, and more preferably 16.5 MΩ · cm or more, 17 More preferably, it is 0.0 MΩ · cm or more.
次に、硫酸銅原料溶液を、例えば４０〜１００℃、好ましくは約１００℃に加熱しながら、硫酸銅原料溶液中の水分を蒸発させ、硫酸銅原料溶液の銅濃度が例えば１００〜２５０ｇ／Ｌとなるまで濃縮する。濃縮された硫酸銅原料溶液を反応槽内で徐々に冷却することにより、硫酸銅（例えば硫酸銅五水和物）の結晶を析出させることができる。 Next, while heating the copper sulfate raw material solution to, for example, 40 to 100 ° C., preferably about 100 ° C., water in the copper sulfate raw material solution is evaporated, and the copper concentration of the copper sulfate raw material solution is, for example, 100 to 250 g / L. Concentrate until Crystals of copper sulfate (eg, copper sulfate pentahydrate) can be precipitated by gradually cooling the concentrated copper sulfate raw material solution in the reaction vessel.
冷却工程では、加熱濃縮後の硫酸銅原料溶液の温度が２５℃になるまでの冷却温度を適正な速度に制御することが重要である。即ち、冷却速度が遅いほど平衡に近い条件となり、不純物は析出する硫酸銅中には含まれにくくなり、不純物は硫酸銅原料溶液中に残存する傾向を示す。このため、冷却速度を遅くするほど析出する硫酸銅中のアルミニウム等の硫酸銅五水和物を構成する元素（Ｃｕ、Ｓ、Ｏ、Ｈ）以外の元素の濃度を低くすることができる。 In the cooling step, it is important to control the cooling temperature at an appropriate rate until the temperature of the copper sulfate raw material solution after heat concentration reaches 25 ° C. That is, the slower the cooling rate, the closer to the equilibrium condition, the impurities are less likely to be contained in the precipitated copper sulfate, and the impurities tend to remain in the copper sulfate raw material solution. For this reason, the concentration of elements other than the elements (Cu, S, O, H) constituting the copper sulfate pentahydrate such as aluminum in the precipitated copper sulfate can be reduced as the cooling rate is lowered.
具体的には、硫酸銅原料溶液の温度が加熱濃縮している際の温度（例えば１００℃）から２５℃になるまでの硫酸銅原料溶液の冷却速度（硫酸銅原料溶液の温度が低下する速度）を１５℃／ｈｒ以下とし、より好ましくは１０℃／ｈｒ以下とし、更に好ましくは７℃／ｈｒ以下とし、より更に好ましくは、５℃／ｈｒ以下とする。冷却手段は特に限定されないが、例えば、水冷、徐冷、空冷、熱交換器を用いた冷却等の冷却方法が利用可能である。 Specifically, the cooling rate of the copper sulfate raw material solution from the temperature at which the temperature of the copper sulfate raw material solution is heated and concentrated (for example, 100 ° C.) to 25 ° C. (the rate at which the temperature of the copper sulfate raw material solution decreases) ) Is set to 15 ° C./hr or less, more preferably 10 ° C./hr or less, further preferably 7 ° C./hr or less, and still more preferably 5 ° C./hr or less. Although the cooling means is not particularly limited, for example, a cooling method such as water cooling, gradual cooling, air cooling, or cooling using a heat exchanger can be used.
冷却工程によって、硫酸銅原料溶液から硫酸銅の析出物が得られる。得られた硫酸銅はその主成分が硫酸銅五水和物である場合が多い。得られた硫酸銅の析出物を固液分離し、乾燥後、気流搬送して個別に包装することにより、本実施形態に係る硫酸銅（結晶製品）が得られる。 By the cooling step, a copper sulfate precipitate is obtained from the copper sulfate raw material solution. In many cases, the obtained copper sulfate is mainly composed of copper sulfate pentahydrate. The obtained copper sulfate precipitate is subjected to solid-liquid separation, dried, air-carryed and individually packaged to obtain the copper sulfate (crystal product) according to the present embodiment.
本実施形態に係る硫酸銅（結晶製品）に、超純水等の溶媒を加えて、溶媒に前述の硫酸銅を溶解させることにより、本実施形態に係る硫酸銅溶液が得られる。硫酸銅を溶解するための溶媒としては、水、一つ若しくは複数の有機溶媒、一つ若しくは複数の無機溶媒、または、水、一つ若しくは複数の有機溶媒および一つ若しくは複数の無機溶媒からなる群から選択される一種以上を含む溶媒があげられる。有機溶媒としては、アルコール、芳香族炭化水素、脂肪酸、鎖式炭化水素、環式炭化水素、有機酸を用いることが出来る。また、無機溶媒として硫酸、塩酸、硝酸、フッ酸等の無機酸等を用いることが出来る。なお、溶媒として水を用いた場合には硫酸銅水溶液を得ることが出来る。 A copper sulfate solution according to the present embodiment is obtained by adding a solvent such as ultrapure water to the copper sulfate (crystal product) according to the present embodiment and dissolving the copper sulfate in the solvent. The solvent for dissolving copper sulfate consists of water, one or more organic solvents, one or more inorganic solvents, or water, one or more organic solvents and one or more inorganic solvents. Examples thereof include a solvent containing one or more selected from the group. As the organic solvent, alcohol, aromatic hydrocarbon, fatty acid, chain hydrocarbon, cyclic hydrocarbon, or organic acid can be used. In addition, inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, and hydrofluoric acid can be used as the inorganic solvent. When water is used as the solvent, an aqueous copper sulfate solution can be obtained.
前述の硫酸銅水溶液を用いる際に使用する超純水の電気抵抗率は１５．０ＭΩ・ｃｍ以上であること好ましく、１５．５ＭΩ・ｃｍ以上であることがより好ましく、１６．０ＭΩ・ｃｍ以上であることがより好ましく、１６．５ＭΩ・ｃｍ以上であることがより好ましく、１７．０ＭΩ・ｃｍ以上であることが更により好ましい。電気抵抗率が１５ＭΩ・ｃｍ以上の超純水を用いることにより、硫酸銅水溶液中のＮａ、Ｍｇ、Ａｌ、Ｃａ、Ｉｎ、Ｓｎ、Ａｇ等の不純物の濃度を低減することが出来る場合があるからである。 The electrical resistivity of the ultrapure water used when using the aqueous copper sulfate solution is preferably 15.0 MΩ · cm or more, more preferably 15.5 MΩ · cm or more, and 16.0 MΩ · cm or more. More preferably, it is more preferably 16.5 MΩ · cm or more, and even more preferably 17.0 MΩ · cm or more. By using ultrapure water having an electrical resistivity of 15 MΩ · cm or more, the concentration of impurities such as Na, Mg, Al, Ca, In, Sn, and Ag in the aqueous copper sulfate solution may be reduced. It is.
前述の硫酸銅溶液は、銅濃度が５０〜１００ｇ／Ｌ程度である。また、前述の硫酸銅溶液中のＡｌ濃度は０．０１９質量ｐｐｍ以下であることが好ましく、０．０１６質量ｐｐｍ以下であることがより好ましく、０．０１２質量ｐｐｍ以下であることが更により好ましい。また、前述の硫酸銅溶液中のＴＯＣ濃度は１．１０質量ｐｐｍ以下であることが好ましい。前述の硫酸銅溶液中のＴＯＣ濃度は、０．９質量ｐｐｍ以下が更に好ましく、０．７質量ｐｐｍ以下がより更に好ましく、０．１５質量ｐｐｍ以下がより更に好ましい。 The copper sulfate solution has a copper concentration of about 50 to 100 g / L. Further, the Al concentration in the above-described copper sulfate solution is preferably 0.019 mass ppm or less, more preferably 0.016 mass ppm or less, and still more preferably 0.012 mass ppm or less. . Moreover, it is preferable that the TOC density | concentration in the above-mentioned copper sulfate solution is 1.10 mass ppm or less. The TOC concentration in the aforementioned copper sulfate solution is more preferably 0.9 mass ppm or less, still more preferably 0.7 mass ppm or less, and still more preferably 0.15 mass ppm or less.
上述の硫酸銅又は硫酸銅溶液を用いてめっき液を作成することができる。本実施形態に係るめっき液は、Ａｌ濃度が０．０１８質量ｐｐｍ以下であり、好ましくは０．０１２質量ｐｐｍ以下である。 A plating solution can be prepared using the above-described copper sulfate or copper sulfate solution. The plating solution according to this embodiment has an Al concentration of 0.018 mass ppm or less, preferably 0.012 mass ppm or less.
本実施形態に係るめっき液は、さらに以下の（２０−１）〜（２０−４）のいずれか一つ、二つ、三つ又は四つを満たす。
（２０−１）Ｉｎ濃度が、０．２３質量ｐｐｍ以下である、
（２０−２）Ｔｌ濃度が、０．０１質量ｐｐｍ以下である、
（２０−３）Ｓｎ濃度が、０．２３質量ｐｐｍ以下である、
（２０−４）Ａｇ濃度が、０．２３質量ｐｐｍ以下である。
The plating solution according to the present embodiment further satisfies any one of the following (20-1) to (20-4), two, three, or four.
(20-1) In concentration is 0.23 mass ppm or less.
(20-2) The Tl concentration is 0.01 mass ppm or less.
(20-3) Sn concentration is 0.23 mass ppm or less,
(20-4) Ag concentration is 0.23 mass ppm or less.
本実施形態に係るめっき液は、さらに以下の（２１−１）〜（２１−４）のいずれか一つ、二つ、三つ又は四つを満たす。
（２１−１）Ｉｎ濃度が、０．０１質量ｐｐｍ以下である、
（２１−２）Ｔｌ濃度が、０．０１質量ｐｐｍ以下である、
（２１−３）Ｓｎ濃度が、０．０１質量ｐｐｍ以下である、
（２１−４）Ａｇ濃度が、０．０１質量ｐｐｍ以下である。
The plating solution according to the present embodiment further satisfies any one of the following (21-1) to (21-4), two, three, or four.
(21-1) In concentration is 0.01 mass ppm or less,
(21-2) The Tl concentration is 0.01 mass ppm or less.
(21-3) Sn concentration is 0.01 mass ppm or less.
(21-4) Ag concentration is 0.01 mass ppm or less.
さらに銅濃度が５０〜１００ｇ／Ｌであることが好ましい。さらに好ましくは、銅濃度が５０〜９０ｇ／Ｌである。 Further, the copper concentration is preferably 50 to 100 g / L. More preferably, the copper concentration is 50 to 90 g / L.
本実施形態に係るめっき液は、上述の濃度が９９．９質量％以上９９．９９９質量％以下である硫酸銅を用いて調製することができ、上記めっき液を用いて銅めっきを行うことにより半導体回路基板を製造することができる。本実施形態の一実施態様においては、上記めっき液を用いて銅めっきを行った半導体回路基板を用いて電子機器を製造することができる。 The plating solution which concerns on this embodiment can be prepared using the copper sulfate whose above-mentioned density | concentration is 99.9 mass% or more and 99.999 mass% or less, and by performing copper plating using the said plating solution. A semiconductor circuit board can be manufactured. In one embodiment of the present embodiment, an electronic device can be manufactured using a semiconductor circuit substrate on which copper plating is performed using the plating solution.
以下に本発明の実施例を比較例と共に示すが、これらの実施例は本発明及びその利点をよりよく理解するために提供するものであり、発明が限定されることを意図するものではない。 Examples of the present invention will be described below together with comparative examples, but these examples are provided for better understanding of the present invention and its advantages, and are not intended to limit the invention.
銅原料として市販の硫酸銅（Ｃｕ：９９％以上、Ｎａ：１０ｐｐｍ、Ｍｇ：１．５ｐｐｍ、Ａｌ：４．５ｐｐｍ、Ｃａ：３．９ｐｐｍ、Ｉｎ：５．６ｐｐｍ、Ｓｎ：１０ｐｐｍ、Ａｇ：３．５ｐｐｍ）を電気抵抗率が１５ＭΩ・ｃｍ以上である超純水と混合し、１００℃で加熱撹拌して硫酸銅原料溶液を作製した。その後、前述した硫酸銅原料溶液を濃縮槽に移して温度１００℃で２〜１０時間保持することにより、硫酸銅原料溶液中の水分を蒸発させて、銅濃度が１５０〜２５０ｇ／Ｌになるまで濃縮した。加熱濃縮後の硫酸銅原料溶液を晶出槽に移し、晶出槽において、硫酸銅原料溶液が２５℃になるまで、表１に示す冷却速度で冷却した。冷却後の処理物を固液分離装置へ供給して固液分離することにより、硫酸銅（硫酸銅五水和物）の析出物を得た。硫酸銅の析出物を乾燥させることにより、実施例１〜３及び比較例１に係る硫酸銅の結晶製品を得た。 Commercially available copper sulfate as a copper raw material (Cu: 99% or more, Na: 10 ppm, Mg: 1.5 ppm, Al: 4.5 ppm, Ca: 3.9 ppm, In: 5.6 ppm, Sn: 10 ppm, Ag: 3. 5 ppm) was mixed with ultrapure water having an electric resistivity of 15 MΩ · cm or more, and heated and stirred at 100 ° C. to prepare a copper sulfate raw material solution. Thereafter, the above-described copper sulfate raw material solution is transferred to a concentration tank and kept at a temperature of 100 ° C. for 2 to 10 hours to evaporate the water in the copper sulfate raw material solution until the copper concentration reaches 150 to 250 g / L. Concentrated. The copper sulfate raw material solution after heat concentration was transferred to a crystallization tank, and cooled in the crystallization tank at a cooling rate shown in Table 1 until the copper sulfate raw material solution reached 25 ° C. The treated product after cooling was supplied to a solid-liquid separator and subjected to solid-liquid separation to obtain a precipitate of copper sulfate (copper sulfate pentahydrate). The copper sulfate crystal product according to Examples 1 to 3 and Comparative Example 1 was obtained by drying the precipitate of copper sulfate.
実施例１〜３及び比較例１〜３に係る硫酸銅に対し、前述の測定方法により、硫酸銅中のＮａ、Ｋ、Ｃｏ、Ｃｒ、Ｎｉ、Ｚｎ、Ａｌ、Ｃａ、Ｍｇ、Ｃｄ、Ｍｎ、Ｐｂ、Ｓｎ、Ａｓ、Ｃｌ、Ｆｅ、Ａｇ、Ｔｌ、ＴｉおよびＩｎの濃度と硫酸銅の濃度を測定した。硫酸銅中の不純物元素をＮａ、Ｋ、Ｃｏ、Ｃｒ、Ｎｉ、Ｚｎ、Ａｌ、Ｃａ、Ｍｇ、Ｃｄ、Ｍｎ、Ｐｂ、Ｓｎ、Ａｓ、Ｃｌ、Ｆｅ、Ａｇ、Ｔｌ、ＴｉおよびＩｎとし、これらの濃度の分析結果の合計をＣｕ以外の不純物の合計濃度とした。実施例１〜３及び比較例１〜３に係る硫酸銅中のＡｌ、Ｉｎ、Ｔｌ、Ｓｎ、Ａｇの濃度、不純物の合計濃度、全有機炭素（ＴＯＣ）濃度の測定結果を表１に示す。 For the copper sulfates according to Examples 1 to 3 and Comparative Examples 1 to 3, Na, K, Co, Cr, Ni, Zn, Al, Ca, Mg, Cd, Mn, The concentration of Pb, Sn, As, Cl, Fe, Ag, Tl, Ti and In and the concentration of copper sulfate were measured. Impurity elements in copper sulfate are Na, K, Co, Cr, Ni, Zn, Al, Ca, Mg, Cd, Mn, Pb, Sn, As, Cl, Fe, Ag, Tl, Ti, and In. The sum of the concentration analysis results was taken as the total concentration of impurities other than Cu. Table 1 shows the measurement results of the concentrations of Al, In, Tl, Sn, and Ag, the total concentration of impurities, and the total organic carbon (TOC) concentration in copper sulfate according to Examples 1 to 3 and Comparative Examples 1 to 3.
実施例１〜３及び比較例１〜３に係る硫酸銅を用いて硫酸銅水溶液を作製し、下記に示す所定の添加剤を加えて電気めっき液を作製した。シリコンウエハ上に化学蒸着（ＣＶＤ）法を用いてＳｉＯ2膜を堆積させた。このＳｉＯ2膜の表面にバリア層であるＴａ層をスパッタリングにより設けた。そして、更にＴａ層の上に厚み８０ｎｍのＣｕシード層をスパッタリングにより形成した後、電気銅めっきにより厚さ３０μｍの銅皮膜を形成した。また、実施例１〜３及び比較例１〜３に係る硫酸銅についてそれぞれ、４５ｇのサンプルを採取し、超純水（電気抵抗率は１５ＭΩ・ｃｍ以上）に当該サンプルを溶解して２００ｍＬの硫酸銅水溶液とした。（下記の電気めっき浴と硫酸銅と、その他の液の比率が同じとしている。）そして、前述の測定方法において硫酸銅サンプルを当該硫酸銅水溶液と読み替えて前述の方法により硫酸銅水溶液中のＡｌ濃度と全有機炭素濃度を測定した。その結果を表に示す。 Copper sulfate aqueous solution was produced using the copper sulfate which concerns on Examples 1-3 and Comparative Examples 1-3, the predetermined additive shown below was added, and the electroplating liquid was produced. A SiO 2 film was deposited on the silicon wafer by chemical vapor deposition (CVD). A Ta layer as a barrier layer was provided on the surface of the SiO 2 film by sputtering. Further, after a Cu seed layer having a thickness of 80 nm was formed on the Ta layer by sputtering, a copper film having a thickness of 30 μm was formed by electrolytic copper plating. In addition, for each of the copper sulfates according to Examples 1 to 3 and Comparative Examples 1 to 3, a 45 g sample was taken, and the sample was dissolved in ultrapure water (electrical resistivity of 15 MΩ · cm or more) to obtain 200 mL of sulfuric acid. A copper aqueous solution was used. (The ratio of the following electroplating bath, copper sulfate, and other liquids is the same.) Then, in the measurement method described above, the copper sulfate sample is read as the copper sulfate aqueous solution, and Al in the copper sulfate aqueous solution is obtained by the method described above. Concentration and total organic carbon concentration were measured. The results are shown in the table.
電気めっき浴及び電気めっき条件は以下の通りである。
（電気めっき浴及び電気めっき条件）
・電気めっき浴
電気めっき浴として以下の組成のめっき浴を用いた。
硫酸銅（硫酸銅五水和物として添加、銅：５７．３ｇ／Ｌ）濃度：２２５ｇ／Ｌ
硫酸濃度 ：５５ｇ／Ｌ
塩化物イオン ：６０ｐｐｍ
ポリエチレングリコール（平均分子量 １００００）濃度 ：５００ｍｇ／Ｌ
ビス（３−スルホプロピル）ジスルフィド（ＳＰＳ）濃度：２０ｍｇ／Ｌ
ヤヌスグリーン濃度 ：１ｍｇ／Ｌ
溶媒には超純水（電気抵抗率は１５ＭΩ・ｃｍ以上）を用いた。
・電気めっき条件
めっき条件は、めっき浴温度４０℃、陰極電流密度２．０Ａ／ｄｍ2、陽極電流密度２．０Ａ／ｄｍ2、めっき時間：７０〜９０分間とした。
The electroplating bath and electroplating conditions are as follows.
(Electroplating bath and electroplating conditions)
Electroplating bath A plating bath having the following composition was used as the electroplating bath.
Copper sulfate (added as copper sulfate pentahydrate, copper: 57.3 g / L) Concentration: 225 g / L
Sulfuric acid concentration: 55 g / L
Chloride ion: 60ppm
Polyethylene glycol (average molecular weight 10,000) concentration: 500 mg / L
Bis (3-sulfopropyl) disulfide (SPS) concentration: 20 mg / L
Janus Green concentration: 1mg / L
As the solvent, ultrapure water (electric resistivity is 15 MΩ · cm or more) was used.
Electroplating conditions The plating conditions were a plating bath temperature of 40 ° C., a cathode current density of 2.0 A / dm 2 , an anode current density of 2.0 A / dm 2 , and a plating time of 70 to 90 minutes.
この銅皮膜に対し、四探針法により電気抵抗値を測定することにより、めっき性を評価した。めっき性の評価は、電気抵抗値が０．０２０×１０-4Ω／ｃｍ未満の場合を◎、０．０２０×１０-4Ω／ｃｍ以上、０．０４０×１０-4Ω／ｃｍ未満の場合を○、０．０４０×１０-4Ω／ｃｍ以上の場合を×として評価した。結果を表１に示す。 With respect to this copper film, the plating resistance was evaluated by measuring the electric resistance value by a four-point probe method. For the evaluation of the plating property, when the electric resistance value is less than 0.020 × 10 −4 Ω / cm, ◎, 0.020 × 10 −4 Ω / cm or more, and less than 0.040 × 10 −4 Ω / cm The case was evaluated as ○, and the case of 0.040 × 10 −4 Ω / cm or more was evaluated as ×. The results are shown in Table 1.
硫酸銅原料溶液から硫酸銅五水和物を析出させる際の冷却速度を適正な速度に調整した実施例１〜３では、Ａｌ濃度を０．０８質量ｐｐｍ以下に低減することができ、めっき性も良好であった。また、硫酸銅溶液のＡｌ濃度を０．０１９質量ｐｐｍ以下とすることで、めっき性も良好であった。一方、冷却速度が速すぎる比較例１では、Ａｌを低減させることができず、めっき性も良好ではなかった。比較例２は特許第３９８７０６９号、比較例３は特許第３９４３５８３号に記載された高純度硫酸銅の製造方法に準じて製造した硫酸銅を用いて、実施例１と同様の条件で銅皮膜を形成したものである。比較例２及び３ともに硫酸銅濃度は高いが、実施例１〜３に比べてアルミニウム濃度が高いため、銅皮膜の電気抵抗値が高くなり、実施例１〜３に比べてめっき性に劣る結果となった。 In Examples 1 to 3 in which the cooling rate when the copper sulfate pentahydrate was precipitated from the copper sulfate raw material solution was adjusted to an appropriate rate, the Al concentration could be reduced to 0.08 mass ppm or less, and the plating property Was also good. Moreover, plating property was also favorable by Al concentration of a copper sulfate solution being 0.019 mass ppm or less. On the other hand, in Comparative Example 1 where the cooling rate was too fast, Al could not be reduced and the plating property was not good. In Comparative Example 2, a copper film was formed under the same conditions as in Example 1 using copper sulfate produced according to the method for producing high purity copper sulfate described in Japanese Patent No. 3987069 and Comparative Example 3 in Japanese Patent No. 3943583. Formed. Although the copper sulfate concentration is high in both Comparative Examples 2 and 3, since the aluminum concentration is higher than in Examples 1 to 3, the electrical resistance value of the copper film is high, and the plating performance is inferior to that in Examples 1 to 3. It became.
なお、上述の組成のめっき液を用い、半導体ウエハ、中でも貫通シリコンビアを有する半導体ウエハの配線形成を行うことができる。また、上述の組成以外、たとえば、特許第５３８８１９１号に記載の組成等、既知の組成のめっき液を用いて半導体ウエハの配線形成や半導体回路基板上の回路形成を行うことができる。すなわち、上述の組成のめっき液により、集積回路や、当該集積回路を搭載したパッケージ基板等の半導体回路基板の形成をすることができる。 In addition, wiring of a semiconductor wafer, especially a semiconductor wafer having a through silicon via can be formed by using the plating solution having the above-described composition. In addition to the above-described composition, for example, wiring of a semiconductor wafer or circuit formation on a semiconductor circuit substrate can be performed using a plating solution having a known composition such as the composition described in Japanese Patent No. 5388191. That is, an integrated circuit or a semiconductor circuit substrate such as a package substrate on which the integrated circuit is mounted can be formed using the plating solution having the above composition.
Claims (25)
（３−１）Ｉｎ濃度が１．０質量ｐｐｍ以下である、
（３−２）Ｔｌ濃度が０．０５質量ｐｐｍ以下である、
（３−３）Ｓｎ濃度が１．０質量ｐｐｍ以下である、
（３−４）Ａｇ濃度が１．０質量ｐｐｍ以下である。 The copper sulfate according to claim 1 or 2, satisfying any one, two, three or four of the following (3-1) to (3-4):
(3-1) In concentration is 1.0 mass ppm or less,
(3-2) Tl concentration is 0.05 mass ppm or less,
(3-3) Sn concentration is 1.0 mass ppm or less,
(3-4) Ag concentration is 1.0 mass ppm or less.
（４−１）Ｉｎ濃度が０．５質量ｐｐｍ以下である、
（４−２）Ｔｌ濃度が０．０５質量ｐｐｍ以下である、
（４−３）Ｓｎ濃度が０．５質量ｐｐｍ以下である、
（４−４）Ａｇ濃度が０．８質量ｐｐｍ以下である。 The copper sulfate according to claim 1 or 2, satisfying any one, two, three or four of the following (4-1) to (4-4):
(4-1) In concentration is 0.5 mass ppm or less,
(4-2) Tl concentration is 0.05 mass ppm or less,
(4-3) Sn concentration is 0.5 mass ppm or less,
(4-4) Ag concentration is 0.8 mass ppm or less.
（５−１）Ｉｎ濃度が０．２質量ｐｐｍ以下である、
（５−２）Ｔｌ濃度が０．０５質量ｐｐｍ以下である、
（５−３）Ｓｎ濃度が０．２質量ｐｐｍ以下である、
（５−４）Ａｇ濃度が０．３質量ｐｐｍ以下である。 The copper sulfate according to claim 1 or 2, satisfying any one, two, three or four of the following (5-1) to (5-4):
(5-1) In concentration is 0.2 mass ppm or less,
(5-2) The Tl concentration is 0.05 mass ppm or less.
(5-3) Sn concentration is 0.2 mass ppm or less,
(5-4) Ag concentration is 0.3 mass ppm or less.
（２０−１）Ｉｎ濃度が、０．２３質量ｐｐｍ以下である、
（２０−２）Ｔｌ濃度が、０．０１質量ｐｐｍ以下である、
（２０−３）Ｓｎ濃度が、０．２３質量ｐｐｍ以下である、
（２０−４）Ａｇ濃度が、０．２３質量ｐｐｍ以下である。 The plating solution according to claim 18 or 19, satisfying any one, two, three, or four of the following (20-1) to (20-4).
(20-1) In concentration is 0.23 mass ppm or less.
(20-2) The Tl concentration is 0.01 mass ppm or less.
(20-3) Sn concentration is 0.23 mass ppm or less,
(20-4) Ag concentration is 0.23 mass ppm or less.
（２１−１）Ｉｎ濃度が、０．０１質量ｐｐｍ以下である、
（２１−２）Ｔｌ濃度が、０．０１質量ｐｐｍ以下である、
（２１−３）Ｓｎ濃度が、０．０１質量ｐｐｍ以下である、
（２１−４）Ａｇ濃度が、０．０１質量ｐｐｍ以下である。 The plating solution according to claim 18 or 19, satisfying any one, two, three or four of the following (21-1) to (21-4).
(21-1) In concentration is 0.01 mass ppm or less,
(21-2) The Tl concentration is 0.01 mass ppm or less.
(21-3) Sn concentration is 0.01 mass ppm or less.
(21-4) Ag concentration is 0.01 mass ppm or less.
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| TW107105888A TW201837239A (en) | 2017-03-31 | 2018-02-22 | Copper sulfate, copper sulfate solution, plating solution, method for producing copper sulfate, method for producing semiconductor circuit board, and method for producing electronic apparatus |
| KR1020180036817A KR102056980B1 (en) | 2017-03-31 | 2018-03-29 | Copper sulfate, copper sulfate solution, plating solution, method of manufacturing copper sulfate, method of manufacturing semiconductor circuit board, and method of manufacturing electronic device |
| CN201810269274.9A CN108821325A (en) | 2017-03-31 | 2018-03-29 | The manufacturing method of copper sulphate, its manufacturing method and its solution, plating solution, the manufacturing method of semiconductor circuit base plate and e-machine |
| CN201810269118.2A CN108689426A (en) | 2017-03-31 | 2018-03-29 | The manufacturing method of copper sulphate, its manufacturing method and its solution, plating solution, the manufacturing method of semiconductor circuit base plate and e-machine |
| US15/941,316 US20180282891A1 (en) | 2017-03-31 | 2018-03-30 | Copper sulfate, copper sulfate solution, plating solution, method for producing copper sulfate, method for producing semiconductor circuit board, and method for producing electronic apparatus |
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