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WO2019187250A1 - Co anode, and co electroplating method using co anode - Google Patents

Co anode, and co electroplating method using co anode Download PDF

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Publication number
WO2019187250A1
WO2019187250A1 PCT/JP2018/037118 JP2018037118W WO2019187250A1 WO 2019187250 A1 WO2019187250 A1 WO 2019187250A1 JP 2018037118 W JP2018037118 W JP 2018037118W WO 2019187250 A1 WO2019187250 A1 WO 2019187250A1
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WIPO (PCT)
Prior art keywords
anode
particles
purity
plating
wiring
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PCT/JP2018/037118
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French (fr)
Japanese (ja)
Inventor
周平 村田
由将 小井土
孝幸 浅野
賢吾 神永
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Ｊｘ金属株式会社
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Application filed by Ｊｘ金属株式会社 filed Critical Ｊｘ金属株式会社
Priority to CN201880091917.3A priority Critical patent/CN111971423A/en
Priority to US17/041,229 priority patent/US20210010149A1/en
Priority to SG11202009378RA priority patent/SG11202009378RA/en
Priority to KR1020207027944A priority patent/KR102435667B1/en
Publication of WO2019187250A1 publication Critical patent/WO2019187250A1/en

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/10—Electrodes, e.g. composition, counter electrode
    • C25D17/12—Shape or form
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/10—Electrodes, e.g. composition, counter electrode
    • 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
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt

Definitions

  • the present invention relates to a Co anode and an electric Co plating method using the Co anode.
  • electric Cu plating is used for forming Cu wiring in PWB (printed wiring board) or the like, but recently, it is also used for forming Cu wiring for semiconductors.
  • a pure Cu anode or a phosphorus-containing Cu anode is used as an anode of electric Cu plating for forming a Cu wiring.
  • a pure Cu anode or a phosphorus-containing Cu anode used for electric Cu plating is described in, for example, Patent Document 1, and the purity is controlled within a predetermined range and the impurity content is controlled below a predetermined value. It is described that adhesion of particles to a semiconductor wafer manufactured using the pure Cu anode or phosphorus-containing Cu anode can be suppressed.
  • Patent Document 2 discloses that the surface of the phosphorus-containing Cu anode is preliminarily applied when performing electro Cu plating on the semiconductor wafer. A technique for forming a fine crystal layer in which the crystal grain size is controlled within a predetermined range is described.
  • Patent Document 1 and Patent Document 2 improve the plating defects by suppressing particles generated when Cu wiring or the like is formed by electric Cu plating, and are useful for fine wiring. Although it is going to obtain wiring etc., in the electroplating using such a conventional Cu anode, there exists room for improvement in the point of EM tolerance or the reduction of wiring resistance. Therefore, the development of a new electroplating anode to replace the Cu anode and capable of suppressing plating defects, which is a conventional problem, is awaited.
  • anode for electroplating that replaces a Cu anode and that can suppress plating defects.
  • the present inventors have found that, in the technical field of fine wiring formation, Cu to Co wiring is used in the cutting-edge local wiring having a narrow wiring and a relatively short wiring distance. Focused on the fact that the replacement is going to be done. It is known that the Co wiring has good EM resistance with respect to the Cu wiring, and the wiring resistance can be suppressed lower than that of the Cu wiring when the wiring distance is short because the barrier metal layer can be thinned.
  • the embodiment of the present invention completed on the basis of the above knowledge is dissolved in dilute nitric acid having a nitric acid concentration of 20% by mass, and then measured with a particle counter in liquid based on JIS B9925.
  • the embodiment of the present invention is an electric Co plating method using the Co anode according to the embodiment of the present invention.
  • an anode for electroplating that is a new electroplating substitute for the Cu anode and that can suppress plating defects.
  • Example 5 (purity: 3N, magnification: 300 times), (b) Example 3 (purity: 4N, magnification: 300 times), (c) Example 1 (purity: 5N, magnification: 300 times) It is a SEM image of.
  • 10 is a graph of an EDX spectrum of Example 3.
  • 2 is a graph of an EDX spectrum of Example 1.
  • Co anode configuration In the Co anode according to the embodiment of the present invention, the number of particles having a particle diameter of 0.5 ⁇ m or more was measured based on JIS B 9925 using a liquid particle counter after being dissolved in dilute nitric acid having a nitric acid concentration of 20 mass%. 6000 pieces / g or less.
  • the Co anode has good EM resistance with respect to the Cu anode, and the wiring resistance can be suppressed lower than that of the Cu wiring when the wiring distance is short because the barrier metal layer can be thinned.
  • the number of particles having a particle size of 0.5 ⁇ m or more is controlled to 6000 particles / g or less, the occurrence of abnormal deposition of plating is suppressed when electroplating is performed using a Co anode. Defects can be suppressed satisfactorily.
  • Particles are solid inclusions present in the structure of the Co anode, and mean particles that do not dissolve in dilute nitric acid in the implementation of the liquid particle counter described later.
  • the impurities of the Co anode also include substances that dissolve in dilute nitric acid (for example, metals that have a strong ionization tendency). However, even if such a substance exists as a coarse structure in the Co anode, it is ionized in the process of electroplating, so that it is taken into the plating film in a very fine form at the ion level.
  • inclusions (particles) that do not dissolve in dilute nitric acid are electrochemically stable, they are taken into the plating film while maintaining a form close to that in the Co anode. For this reason, even if the Co anodes have the same purity, the larger the proportion of particles in the impurities, the larger the size of the impurities taken into the plating film, and the more likely the plating failure occurs.
  • the present invention pays attention to this point and provides a Co anode in which the number of particles that are solid inclusions that are not dissolved in dilute nitric acid is controlled to a predetermined number or more.
  • Particles are mainly caused by impurities contained in the Co raw material, impurities or products mixed in the manufacturing process.
  • the particles are, for example, one or more selected from the group consisting of metals, metal oxides, carbon, carbon compounds, and chlorine compounds.
  • the particles may be one or more metals selected from the group consisting of Fe, Mg, Cr, Ni, Si, and Al, or oxides thereof (including cobalt oxides).
  • the present inventors particularly note that particles having a particle size of 0.5 ⁇ m or more do not dissolve in the electrolyte solution and are easily taken into the plating film, so that abnormal precipitation of the plating easily occurs.
  • the number density of particles having a diameter and controlling the number density to 6000 pieces / g or less generation of particles in a plating film produced by electroplating can be suppressed very well, As a result, it has been found that the occurrence of abnormal plating deposition can be suppressed.
  • the detected particles have a negative effect on the plating process, and in particular, the Co wiring formed using the Co anode is a fine wiring.
  • the number of particles having a particle diameter of 0.5 ⁇ m or more is controlled.
  • the number of particles having a particle diameter of 0.5 ⁇ m or more is preferably 5000 / g or less, and more preferably 4000 / g or less.
  • the particle size of the particles is obtained by measuring with a “light scattering automatic particle counter for liquid” (manufactured by Kyushu Lion Co., Ltd.). This measurement method selects the size of particles in a liquid and measures the particle concentration and the number of particles, and is based on JIS B 9925 (in the present invention, this measurement is referred to as “liquid particle counter”). Called). The procedure for carrying out the particle counter in the liquid will be described in detail. 1 g is sampled, slowly dissolved with 150 ml of dilute nitric acid (nitric acid concentration 20 mass% aqueous solution) so that the particles do not dissolve, and left for 24 hours.
  • dilute nitric acid nitric acid concentration 20 mass% aqueous solution
  • This is diluted with pure water to 500 ml, and 10 ml is taken and measured with the particle counter in liquid.
  • 10 ml is taken and measured with the particle counter in liquid.
  • the number of particles is 1000 / ml, 0.02 g of sample is measured in 10 ml, so the number of particles is 500,000 / g.
  • the number of particles is not limited to the measurement using the liquid particle counter, and may be measured using other means as long as the same number of particles can be measured.
  • the Co anode according to the embodiment of the present invention preferably has a purity of 3N or more. If the purity of the Co anode is 3N (purity 99.9% by mass) or more, the generation of particles in the plating film produced by electroplating using the Co anode can be more effectively suppressed, and as a result, plating is performed. The occurrence of abnormal precipitation can be further suppressed.
  • the Co anode according to the embodiment of the present invention preferably has a purity of 4N (purity 99.99 mass%) or more, and more preferably 5N (purity 99.999 mass%) or more.
  • purity in the present invention for example, purity 5N (99.999%) means that the Co ingot after dissolution is analyzed by glow discharge mass spectrometry (GDMS: Glow Discharge Mass Spectrometry) and is below the lower limit of detection.
  • All metal elements other than element and Co such as Be, Na, Mg, Al, Si, P, S, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Zr, Mo , Cd, Sn, Sb, Hg, Pb, Bi, Th, U means less than 10 ppm.
  • the number of particles is not necessarily small if it is “high purity”, and the higher purity Co anode is less than the lower purity Co anode.
  • the number of particles shown in the invention may be large.
  • the Fe concentration is preferably controlled to 10 ppm or less. Since Fe is difficult to dissolve in an acidic solution, particles are easily formed when Fe is mixed in the Co anode.
  • the Co anode in which the Fe concentration is controlled to 10 ppm or less has fewer particles generated in the plating film than the Co anode in which the Fe concentration exceeds 10 ppm, As a result, the occurrence of abnormal plating deposition can be further suppressed.
  • the Fe concentration is more preferably controlled to 8 ppm or less, even more preferably 5 ppm or less, even more preferably 3 ppm or less, even more preferably 1 ppm or less, and even more preferably 0 ppm. ing.
  • Co as a raw material is dissolved in a predetermined container.
  • Co raw material to be used for example, Co having a purity of 3N (purity 99.9% by mass) or more can be used.
  • particles that are problematic during electroplating are particles of a compound such as Fe, Mg, Cr, Ni, Si, and Al, and these particles cause particles generated in the plating film.
  • the surface roughness of the portion in contact with the Co raw material in the container, piping, and mold may be controlled.
  • Electro-Co plating method By performing electro-Co plating using the Co anode according to the embodiment of the present invention, the generation of particles in the produced plating film can be suppressed extremely well, and as a result, the occurrence of abnormal deposition of plating is suppressed. can do.
  • an appropriate amount of cobalt sulfate: 10 to 30 g / L (Co) or cobalt chloride 5 to 15 g / L may be used as a plating solution. it can.
  • the pH is 2.5 to 3.5.
  • the plating bath temperature can be 25 to 60 ° C.
  • the cathode current density is 0.5 to 10 A / dm 2
  • the anode current density is 0.5 to 10 A / dm 2 , but it is not necessarily limited to these conditions. Absent.
  • the plating bath may contain a brightener, a complexing agent, a pH buffer, a surfactant and the like.
  • FIG. 1A shows Example 5 (purity: 3N, magnification: 300 times)
  • FIG. 1B shows Example 3 (purity: 4N, magnification: 300 times)
  • FIG. 1C shows Example 1 (purity: 5N, (Magnification: 300 times) SEM image.
  • FIG. 2A shows Example 5 (purity: 3N, magnification: 15000 times)
  • FIG. 2B shows Example 3 (purity: 4N, magnification: 30000 times)
  • FIG. 2C shows Example 1 (purity: 5N, magnification: 15000 times).
  • particles (inclusions) having a particle size of 0.5 ⁇ m or more are shown surrounded by a frame line.
  • FIG. 3A shows a graph of the EDX spectrum of Example 5
  • FIG. 3B shows Example 3
  • Example 1 a Co anode having a particle diameter of 0.5 ⁇ m or more and 6000 particles / g or less could be produced.
  • Comparative Example 1 a Co anode in which the number of particles having a particle size of 0.5 ⁇ m or more exceeded 6000 / g was obtained.
  • Example 1 and Example 2, Example 3 and Example 4, Example 5 and Comparative Example 1 use Co anodes of the same purity, but the Fe concentration is different, so the particle size is different. There is a difference in the number of particles of 0.5 ⁇ m or more.
  • Example 4 having a purity of 4N
  • the number of particles having a particle diameter of 0.5 ⁇ m or more was larger than that in Example 5 having a purity of 3N.
  • the relationship is not necessarily that the number of particles is small if it is “high purity”, and a higher purity Co anode may have more particles shown in the present invention than a lower purity Co anode. is there.
  • the Co plating films formed using the Co anodes of Examples 1 to 5 had 0 abnormal electrodepositions, and the plating defects were well suppressed. In the Co plating film formed using the Co anode of Comparative Example 1, abnormal electrodeposition was confirmed, and plating failure occurred.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

Provided is a novel electroplating anode that replaces a Cu anode and is capable of suppressing plating defects. In this Co anode, the number of particles having a particle diameter of 0.5 μm or more is 6000 particles/g or less, as measured by a counter for particles in liquid according to JIS B 9925, after the Co anode is dissolved in a dilute nitric acid (nitric acid concentration of 20 mass%).

Description

Ｃｏアノード及びＣｏアノードを用いた電気Ｃｏめっき方法Co anode and electro-co plating method using Co anode
　本発明は、Ｃｏアノード及びＣｏアノードを用いた電気Ｃｏめっき方法に関する。 The present invention relates to a Co anode and an electric Co plating method using the Co anode.
　一般に、電気Ｃｕめっきは、ＰＷＢ（プリント配線板）等においてＣｕ配線形成に使用されているが、最近では半導体のＣｕ配線形成にも使用されている。Ｃｕ配線を形成するための電気Ｃｕめっきのアノードとしては純Ｃｕアノード又は含リンＣｕアノードが使用されている。 Generally, electric Cu plating is used for forming Cu wiring in PWB (printed wiring board) or the like, but recently, it is also used for forming Cu wiring for semiconductors. A pure Cu anode or a phosphorus-containing Cu anode is used as an anode of electric Cu plating for forming a Cu wiring.
　電気Ｃｕめっきに使用する純Ｃｕアノード又は含リンＣｕアノードについては、例えば特許文献１に記載されており、純度を所定範囲に制御し、且つ、不純物の含有量を所定値以下に制御することで、当該純Ｃｕアノード又は含リンＣｕアノードを用いて製造した半導体ウェハへのパーティクルの付着を抑制することができると記載されている。 A pure Cu anode or a phosphorus-containing Cu anode used for electric Cu plating is described in, for example, Patent Document 1, and the purity is controlled within a predetermined range and the impurity content is controlled below a predetermined value. It is described that adhesion of particles to a semiconductor wafer manufactured using the pure Cu anode or phosphorus-containing Cu anode can be suppressed.
　また、同様に含リンＣｕアノードを用いて製造した半導体ウェハへのパーティクルの付着を抑制する技術として、特許文献２には半導体ウェハへの電気Ｃｕめっきを行うに際し、予め含リンＣｕアノードの表面に結晶粒径が所定の範囲に制御された微細結晶層を形成する技術が記載されている。 Similarly, as a technique for suppressing the adhesion of particles to a semiconductor wafer manufactured using a phosphorus-containing Cu anode, Patent Document 2 discloses that the surface of the phosphorus-containing Cu anode is preliminarily applied when performing electro Cu plating on the semiconductor wafer. A technique for forming a fine crystal layer in which the crystal grain size is controlled within a predetermined range is described.
特許第５０６６５７７号公報Japanese Patent No. 5066577 特許第４０７６７５１号公報Japanese Patent No. 4076751
　近年、半導体デバイスの高性能化、低消費電力化が求められ、配線の微細化が進むにつれ、配線の信頼性に影響を与えるエレクトロマイグレーション（ＥＭ）の劣化対策や信号遅延の原因となる配線抵抗の低抵抗化が課題となっている。特許文献１や特許文献２に記載されている技術は、前述の通り電気ＣｕめっきでＣｕ配線等を形成する際に生じるパーティクルを抑制することで、めっき不良を改善し、微細配線に有用なＣｕ配線等を得ようとするものであるが、このような従来のＣｕアノードを使用した電気めっきでは、ＥＭ耐性や配線抵抗の低抵抗化の点で改善の余地がある。そのため、Ｃｕアノードに代わる新たな電気めっきのアノードであって、さらに従来の課題であるめっき不良を抑制することが可能なアノードの開発が待ち望まれている。 In recent years, high performance and low power consumption of semiconductor devices have been demanded, and as wiring miniaturization progressed, wiring resistance that causes deterioration of electromigration (EM) and causes signal delay, which affects wiring reliability. Lowering the resistance is a challenge. As described above, the techniques described in Patent Document 1 and Patent Document 2 improve the plating defects by suppressing particles generated when Cu wiring or the like is formed by electric Cu plating, and are useful for fine wiring. Although it is going to obtain wiring etc., in the electroplating using such a conventional Cu anode, there exists room for improvement in the point of EM tolerance or the reduction of wiring resistance. Therefore, the development of a new electroplating anode to replace the Cu anode and capable of suppressing plating defects, which is a conventional problem, is awaited.
　そこで本発明の実施形態は、Ｃｕアノードに代わる新たな電気めっきのアノードであって、且つ、めっき不良を抑制することが可能なアノードを提供することを課題とする。 Therefore, it is an object of an embodiment of the present invention to provide an anode for electroplating that replaces a Cu anode and that can suppress plating defects.
　本発明者らは、このような問題を解決するため種々の検討を行った結果、微細配線形成の技術分野において、狭配線かつ比較的配線距離が短い最先端ローカル配線等においてはＣｕからＣｏ配線への置き換えが行われようとしていることに着目した。Ｃｏ配線はＣｕ配線に対してＥＭ耐性が良好で、バリアメタル層が薄くできる分、配線距離が短い場合は配線抵抗もＣｕ配線より低く抑えることができることがわかっている。 As a result of various studies to solve such problems, the present inventors have found that, in the technical field of fine wiring formation, Cu to Co wiring is used in the cutting-edge local wiring having a narrow wiring and a relatively short wiring distance. Focused on the fact that the replacement is going to be done. It is known that the Co wiring has good EM resistance with respect to the Cu wiring, and the wiring resistance can be suppressed lower than that of the Cu wiring when the wiring distance is short because the barrier metal layer can be thinned.
　そこで、従来のＣｕアノードに代えて、Ｃｏアノードを作製し、且つ、当該Ｃｏアノードにおける所定の粒径以上のパーティクルの数を制御することで、めっき不良を抑制することが可能な電気めっきのアノードが得られることを見出した。 Therefore, in place of the conventional Cu anode, a Co anode is manufactured, and the number of particles having a predetermined particle diameter or more in the Co anode is controlled to suppress plating defects. It was found that can be obtained.
　上記知見を基礎にして完成した本発明の実施形態は一側面において、硝酸濃度２０質量％の希硝酸で溶解した後、液中パーティクルカウンターによってＪＩＳ Ｂ ９９２５に基づいて測定した、粒径が０．５μｍ以上のパーティクルの数が、６０００個/ｇ以下であるＣｏアノードである。 In one aspect, the embodiment of the present invention completed on the basis of the above knowledge is dissolved in dilute nitric acid having a nitric acid concentration of 20% by mass, and then measured with a particle counter in liquid based on JIS B9925. A Co anode in which the number of particles of 5 μm or more is 6000 particles / g or less.
　また、本発明の実施形態は他の一側面において、本発明の実施形態に係るＣｏアノードを用いた電気Ｃｏめっき方法である。 In another aspect, the embodiment of the present invention is an electric Co plating method using the Co anode according to the embodiment of the present invention.
　本発明の実施形態によれば、Ｃｕアノードに代わる新たな電気めっきのアノードであって、且つ、めっき不良を抑制することが可能なアノードを提供することができる。 According to the embodiment of the present invention, it is possible to provide an anode for electroplating that is a new electroplating substitute for the Cu anode and that can suppress plating defects.
（ａ）実施例５（純度：３Ｎ、倍率：３００倍）、（ｂ）実施例３（純度：４Ｎ、倍率：３００倍）、（ｃ）実施例１（純度：５Ｎ、倍率：３００倍）のＳＥＭ像である。(A) Example 5 (purity: 3N, magnification: 300 times), (b) Example 3 (purity: 4N, magnification: 300 times), (c) Example 1 (purity: 5N, magnification: 300 times) It is a SEM image of. （ａ）実施例５（純度：３Ｎ、倍率：１５０００倍）、（ｂ）実施例３（純度：４Ｎ、倍率：３００００倍）、（ｃ）実施例１（純度：５Ｎ、倍率：１５０００倍）のＳＥＭ像である。(A) Example 5 (purity: 3N, magnification: 15000 times), (b) Example 3 (purity: 4N, magnification: 30000 times), (c) Example 1 (purity: 5N, magnification: 15000 times) It is a SEM image of. 実施例５のＥＤＸスペクトルのグラフである。6 is a graph of an EDX spectrum of Example 5. 実施例３のＥＤＸスペクトルのグラフである。10 is a graph of an EDX spectrum of Example 3. 実施例１のＥＤＸスペクトルのグラフである。2 is a graph of an EDX spectrum of Example 1.
　〔Ｃｏアノードの構成〕
　本発明の実施形態に係るＣｏアノードは、硝酸濃度２０質量％の希硝酸で溶解した後、液中パーティクルカウンターによってＪＩＳ Ｂ ９９２５に基づいて測定した、粒径が０．５μｍ以上のパーティクルの数が、６０００個/ｇ以下である。ＣｏアノードはＣｕアノードに対してＥＭ耐性が良好で、バリアメタル層が薄くできる分、配線距離が短い場合は配線抵抗もＣｕ配線より低く抑えることができる。また、粒径が０．５μｍ以上のパーティクルの数が６０００個/ｇ以下に制御されているため、Ｃｏアノードを用いて電気めっきを行うとき、めっきの異常析出の発生が抑制され、その結果めっき不良を良好に抑制することができる。 [Co anode configuration]
In the Co anode according to the embodiment of the present invention, the number of particles having a particle diameter of 0.5 μm or more was measured based on JIS B 9925 using a liquid particle counter after being dissolved in dilute nitric acid having a nitric acid concentration of 20 mass%. 6000 pieces / g or less. The Co anode has good EM resistance with respect to the Cu anode, and the wiring resistance can be suppressed lower than that of the Cu wiring when the wiring distance is short because the barrier metal layer can be thinned. In addition, since the number of particles having a particle size of 0.5 μm or more is controlled to 6000 particles / g or less, the occurrence of abnormal deposition of plating is suppressed when electroplating is performed using a Co anode. Defects can be suppressed satisfactorily.
　パーティクルは、Ｃｏアノードの組織の中に存在する固形の介在物であり、後述する液中パーティクルカウンターの実施において希硝酸に溶解しないものを意味する。Ｃｏアノードの不純物としては、希硝酸に溶解する物質（例えば、イオン化傾向が強い金属）も含まれる。ただし、このような物質は、たとえＣｏアノードの中に粗大な組織として存在していても、電気めっきの過程でイオン化されるため、めっき膜にはイオンレベルの非常に微細な形態で取り込まれる。一方、希硝酸に溶解しない介在物（パーティクル）は、電気化学的に安定であるため、Ｃｏアノードの中に存在していたときと近い形態を維持したまま、めっき膜の中に取り込まれる。このため、たとえ同じ純度のＣｏアノードであったとしても、不純物の中でパーティクルが占める割合が大きい方が、めっき膜に取り込まれる不純物の大きさが大きくなり、めっき不良が生じやすくなる。本発明ではこの点に着目し、希硝酸に溶解しない固形の介在物であるパーティクルについて、所定粒径以上のものの数が制御されたＣｏアノードを提供している。 Particles are solid inclusions present in the structure of the Co anode, and mean particles that do not dissolve in dilute nitric acid in the implementation of the liquid particle counter described later. The impurities of the Co anode also include substances that dissolve in dilute nitric acid (for example, metals that have a strong ionization tendency). However, even if such a substance exists as a coarse structure in the Co anode, it is ionized in the process of electroplating, so that it is taken into the plating film in a very fine form at the ion level. On the other hand, since inclusions (particles) that do not dissolve in dilute nitric acid are electrochemically stable, they are taken into the plating film while maintaining a form close to that in the Co anode. For this reason, even if the Co anodes have the same purity, the larger the proportion of particles in the impurities, the larger the size of the impurities taken into the plating film, and the more likely the plating failure occurs. The present invention pays attention to this point and provides a Co anode in which the number of particles that are solid inclusions that are not dissolved in dilute nitric acid is controlled to a predetermined number or more.
　パーティクルは、主にＣｏ原料に含まれていた不純物や、製造工程で混入した不純物又は生成物に起因する。パーティクルは、例えば、金属、金属酸化物、炭素、炭素化合物、塩素化合物からなる群から選択された１種以上である。また、パーティクルは、Ｆｅ、Ｍｇ、Ｃｒ、Ｎｉ、Ｓｉ、Ａｌからなる群から選択された１種以上の金属又はその酸化物（コバルト酸化物も含む）であってもよい。 Particles are mainly caused by impurities contained in the Co raw material, impurities or products mixed in the manufacturing process. The particles are, for example, one or more selected from the group consisting of metals, metal oxides, carbon, carbon compounds, and chlorine compounds. The particles may be one or more metals selected from the group consisting of Fe, Mg, Cr, Ni, Si, and Al, or oxides thereof (including cobalt oxides).
　また、本発明者らは、特に、粒径が０．５μｍ以上のパーティクルは電解液に溶け出さず、めっき膜に取り込まれることでめっきの異常析出が発生しやすくなることから、このような粒径のパーティクルの個数密度に着目し、且つ、当該個数密度を６０００個/ｇ以下に制御することで、電気めっきで作製されるめっき膜中のパーティクルの発生を極めて良好に抑制することができ、その結果めっきの異常析出の発生を抑制することができることを見出した。また、不純物がパーティクルとして検出されない場合と、検出される場合とを比較すると、検出されるパーティクルの方がめっき工程に悪影響を及ぼすこと、特にＣｏアノードを用いて形成されるＣｏ配線は微細配線として利用されることが多くこのような悪影響が顕著となってしまうことを見出し、そのような観点からも粒径が０．５μｍ以上のパーティクルの数を制御している。本発明の実施形態に係るＣｏアノードは、粒径が０．５μｍ以上のパーティクルの数が５０００個/ｇ以下であるのが好ましく、４０００個/ｇ以下であるのがより好ましい。 In addition, the present inventors particularly note that particles having a particle size of 0.5 μm or more do not dissolve in the electrolyte solution and are easily taken into the plating film, so that abnormal precipitation of the plating easily occurs. By paying attention to the number density of particles having a diameter and controlling the number density to 6000 pieces / g or less, generation of particles in a plating film produced by electroplating can be suppressed very well, As a result, it has been found that the occurrence of abnormal plating deposition can be suppressed. Further, comparing the case where impurities are not detected as particles with the case where they are detected, the detected particles have a negative effect on the plating process, and in particular, the Co wiring formed using the Co anode is a fine wiring. In many cases, it is found that such an adverse effect becomes remarkable, and from such a viewpoint, the number of particles having a particle diameter of 0.5 μm or more is controlled. In the Co anode according to the embodiment of the present invention, the number of particles having a particle diameter of 0.5 μm or more is preferably 5000 / g or less, and more preferably 4000 / g or less.
　パーティクルの粒径は、「液体用光散乱式自動粒子計数器」（九州リオン株式会社製）で測定されて得られる。この測定法は、液中で粒子のサイズを選別し、その粒子濃度や粒子数を測定するもので、ＪＩＳ Ｂ ９９２５に基づくものである（本発明において、この測定を「液中パーティクルカウンター」と称する）。
　液中パーティクルカウンターの実施手順を具体的に説明すると、１ｇをサンプリングし、パーティクルが溶解しないように、ゆっくりと１５０ｍｌの希硝酸（硝酸濃度２０質量％水溶液）で溶解し、２４時間放置後、さらにこれを５００ｍｌになるように、純水で希釈し、この１０ｍｌを取り、前記液中パーティクルカウンターで測定するものである。例えば、パーティクルの個数が１０００個／ｍｌの場合では、１０ｍｌの中には０．０２ｇのサンプルが測定されることになるので、パーティクルは５０００００個／ｇとなる。
　なお、パーティクルの個数は、液中パーティクルカウンターによる測定に限られず、同様の個数の測定が可能であれば、他の手段を用いて測定しても良い。 The particle size of the particles is obtained by measuring with a “light scattering automatic particle counter for liquid” (manufactured by Kyushu Lion Co., Ltd.). This measurement method selects the size of particles in a liquid and measures the particle concentration and the number of particles, and is based on JIS B 9925 (in the present invention, this measurement is referred to as “liquid particle counter”). Called).
The procedure for carrying out the particle counter in the liquid will be described in detail. 1 g is sampled, slowly dissolved with 150 ml of dilute nitric acid (nitric acid concentration 20 mass% aqueous solution) so that the particles do not dissolve, and left for 24 hours. This is diluted with pure water to 500 ml, and 10 ml is taken and measured with the particle counter in liquid. For example, when the number of particles is 1000 / ml, 0.02 g of sample is measured in 10 ml, so the number of particles is 500,000 / g.
Note that the number of particles is not limited to the measurement using the liquid particle counter, and may be measured using other means as long as the same number of particles can be measured.
　本発明の実施形態に係るＣｏアノードは、純度が３Ｎ以上であるのが好ましい。Ｃｏアノードの純度が３Ｎ（純度９９．９質量％）以上であれば、Ｃｏアノードを用いた電気めっきで作製されるめっき膜中のパーティクルの発生をより良好に抑制することができ、その結果めっきの異常析出の発生をより抑制することができる。本発明の実施形態に係るＣｏアノードは、純度が４Ｎ（純度９９．９９質量％）以上であるのがより好ましく、５Ｎ（純度９９．９９９質量％）以上であるのが更により好ましい。なお、本発明における「純度」について、例えば純度５Ｎ（９９．９９９％）とは、溶解後のＣｏインゴットをグロー放電質量分析法（ＧＤＭＳ：Ｇｌｏｗ　Ｄｉｓｃｈａｒｇｅ　Ｍａｓｓ　Ｓｐｅｃｔｒｏｍｅｔｒｙ）にて分析し、検出下限以下の元素及びＣｏ以外の全ての金属元素、例えばＢｅ、Ｎａ、Ｍｇ、Ａｌ、Ｓｉ、Ｐ、Ｓ、Ｋ、Ｃａ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｎｉ、Ｃｕ、Ｚｎ、Ａｓ、Ｚｒ、Ｍｏ、Ｃｄ、Ｓｎ、Ｓｂ、Ｈｇ、Ｐｂ、Ｂｉ、Ｔｈ、Ｕの合計が、１０ｐｐｍ未満であることを意味する。 The Co anode according to the embodiment of the present invention preferably has a purity of 3N or more. If the purity of the Co anode is 3N (purity 99.9% by mass) or more, the generation of particles in the plating film produced by electroplating using the Co anode can be more effectively suppressed, and as a result, plating is performed. The occurrence of abnormal precipitation can be further suppressed. The Co anode according to the embodiment of the present invention preferably has a purity of 4N (purity 99.99 mass%) or more, and more preferably 5N (purity 99.999 mass%) or more. As for “purity” in the present invention, for example, purity 5N (99.999%) means that the Co ingot after dissolution is analyzed by glow discharge mass spectrometry (GDMS: Glow Discharge Mass Spectrometry) and is below the lower limit of detection. All metal elements other than element and Co, such as Be, Na, Mg, Al, Si, P, S, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Zr, Mo , Cd, Sn, Sb, Hg, Pb, Bi, Th, U means less than 10 ppm.
　なお、後述の実施例及び比較例で示すように、必ずしも「高純度」であればパーティクルの数が少ないという関係にはならず、純度が高いＣｏアノードの方が、純度が低いＣｏアノードより本発明で示すパーティクルの数が多い場合もある。 As shown in the examples and comparative examples described later, the number of particles is not necessarily small if it is “high purity”, and the higher purity Co anode is less than the lower purity Co anode. The number of particles shown in the invention may be large.
　本発明の実施形態に係るＣｏアノードは、Ｆｅ濃度が１０ｐｐｍ以下に制御されているのが好ましい。Ｆｅは酸性溶液に溶解し難いため、ＦｅがＣｏアノード中に混入しているとパーティクルを形成しやすくなる。同程度の純度のＣｏアノード間で比較すると、Ｆｅ濃度が１０ｐｐｍ以下に制御されているＣｏアノードの方が、Ｆｅ濃度が１０ｐｐｍを超えるＣｏアノードよりめっき膜中に発生するパーティクルの数が少なくなり、その結果めっきの異常析出の発生をより抑制することができる。本発明の実施形態に係るＣｏアノードは、Ｆｅ濃度が、より好ましくは８ｐｐｍ以下、更により好ましくは５ｐｐｍ以下、更により好ましくは３ｐｐｍ以下、更により好ましくは１ｐｐｍ以下、更により好ましくは０ｐｐｍに制御されている。 In the Co anode according to the embodiment of the present invention, the Fe concentration is preferably controlled to 10 ppm or less. Since Fe is difficult to dissolve in an acidic solution, particles are easily formed when Fe is mixed in the Co anode. When compared between Co anodes of similar purity, the Co anode in which the Fe concentration is controlled to 10 ppm or less has fewer particles generated in the plating film than the Co anode in which the Fe concentration exceeds 10 ppm, As a result, the occurrence of abnormal plating deposition can be further suppressed. In the Co anode according to an embodiment of the present invention, the Fe concentration is more preferably controlled to 8 ppm or less, even more preferably 5 ppm or less, even more preferably 3 ppm or less, even more preferably 1 ppm or less, and even more preferably 0 ppm. ing.
　〔Ｃｏアノードの製造方法〕
　本発明の実施形態に係るＣｏアノードの製造方法について詳述する。まず、原料であるＣｏを所定の容器内で溶解する。使用するＣｏ原料は、例えば、純度３Ｎ（純度９９．９質量％）以上のＣｏを使用することができる。
　前述のように、電気めっき時に問題となるパーティクルは、Ｆｅ、Ｍｇ、Ｃｒ、Ｎｉ、Ｓｉ、Ａｌ等の化合物の粒子であり、これら粒子がめっき膜中に発生するパーティクルの原因となる。これらの粒子がＣｏアノードに混入しないように制御するためには、容器、配管及び鋳型において、Ｃｏ原料と接する部分の表面粗さを制御してもよい。また、これら粒子はスラグ側に浮きやすいという知見から、溶湯の撹拌時間を多くすることで、Ｆｅ、Ｍｇ、Ｃｒ、Ｎｉ、Ｓｉ、Ａｌの化合物の粒径０．５μｍを超える粒子をスラグ側へ分配させてもよい。 [Method for producing Co anode]
A method for producing a Co anode according to an embodiment of the present invention will be described in detail. First, Co as a raw material is dissolved in a predetermined container. As the Co raw material to be used, for example, Co having a purity of 3N (purity 99.9% by mass) or more can be used.
As described above, particles that are problematic during electroplating are particles of a compound such as Fe, Mg, Cr, Ni, Si, and Al, and these particles cause particles generated in the plating film. In order to control so that these particles do not enter the Co anode, the surface roughness of the portion in contact with the Co raw material in the container, piping, and mold may be controlled. Further, from the knowledge that these particles are likely to float on the slag side, by increasing the stirring time of the molten metal, particles exceeding the particle size of 0.5 μm of the compound of Fe, Mg, Cr, Ni, Si, Al are moved to the slag side. It may be distributed.
　次に、溶解したＣｏ原料を鋳型に供給して鍛造した後、圧延、熱処理を行い、さらに表面の切削加工を行うことにより、Ｃｏアノードを作製する。 Next, after supplying the molten Co raw material to the mold and forging, rolling and heat treatment are performed, and further, the surface is cut to produce a Co anode.
　〔電気Ｃｏめっき方法〕
　本発明の実施形態に係るＣｏアノードを用いて電気Ｃｏめっきを行うことで、作製されるめっき膜中のパーティクルの発生を極めて良好に抑制することができ、その結果めっきの異常析出の発生を抑制することができる。
　本発明の実施形態に係る電気Ｃｏめっき方法では、特に限定されないが、例えばめっき液として、硫酸コバルト：１０～３０ｇ／Ｌ（Ｃｏ）、又は、塩化コバルト５～１５ｇ／Ｌを適量使用することができる。ｐＨは２．５～３．５とする。
　その他、めっき浴温２５～６０℃、陰極電流密度０．５～１０Ａ／ｄｍ2、陽極電流密度０．５～１０Ａ／ｄｍ2とすることができるが、必ずしもこれらの条件に制限される必要はない。めっき浴には、光沢剤・錯化剤・ｐＨ緩衝剤、界面活性剤等を含んでもよい。 [Electrical Co plating method]
By performing electro-Co plating using the Co anode according to the embodiment of the present invention, the generation of particles in the produced plating film can be suppressed extremely well, and as a result, the occurrence of abnormal deposition of plating is suppressed. can do.
In the electro-Co plating method according to the embodiment of the present invention, although not particularly limited, for example, an appropriate amount of cobalt sulfate: 10 to 30 g / L (Co) or cobalt chloride 5 to 15 g / L may be used as a plating solution. it can. The pH is 2.5 to 3.5.
In addition, the plating bath temperature can be 25 to 60 ° C., the cathode current density is 0.5 to 10 A / dm 2 , and the anode current density is 0.5 to 10 A / dm 2 , but it is not necessarily limited to these conditions. Absent. The plating bath may contain a brightener, a complexing agent, a pH buffer, a surfactant and the like.
　以下、本発明及びその利点をより良く理解するための実施例を提供するが、本発明はこれらの実施例に限られるものではない。 Hereinafter, examples for better understanding of the present invention and its advantages will be provided, but the present invention is not limited to these examples.
　〔Ｃｏアノードの作製〕
　実施例１～５、比較例１として、所定の純度のＣｏ原料を真空溶解してインゴットを作成し溶解させた。なお、純度が３ＮのＣｏ原料は市販コバルト材を使用し、純度が４Ｎ及び５ＮのＣｏ原料は電解精製により得た。
　次に、溶解したＣｏ原料を鋳型に供給して鍛造した後、３０～５０％の圧下率で圧延を行い、続いて３００℃～６００℃の熱処理を行い、さらに表面の切削加工を行うことにより、Ｃｏアノードを作製した。 [Production of Co anode]
As Examples 1 to 5 and Comparative Example 1, a Co raw material having a predetermined purity was melted in a vacuum to prepare and melt an ingot. The Co raw material having a purity of 3N used a commercially available cobalt material, and the Co raw materials having a purity of 4N and 5N were obtained by electrolytic purification.
Next, the molten Co raw material is supplied to the mold and forged, and then rolled at a reduction rate of 30 to 50%, followed by heat treatment at 300 ° C. to 600 ° C., and further cutting the surface. A Co anode was prepared.
　〔評価〕
　（パーティクルの評価）
　パーティクルの粒径及び個数は、「液体用光散乱式自動粒子計数器」（九州リオン株式会社製）で測定した。具体的には、Ｃｏアノード１ｇをサンプリングし、パーティクルが溶解しないように、ゆっくりと１５０ｍｌの希硝酸（硝酸濃度２０質量％水溶液）で溶解し、２４時間放置後、さらにこれを５００ｍｌになるように純水で希釈し、この１０ｍｌを取り、前記液中パーティクルカウンターで測定した。これを３回繰り返した平均値をパーティクルの数とした。また、パーティクルの粒径はＳＥＭ像で評価した。図１（ａ）に実施例５（純度：３Ｎ、倍率：３００倍）、（ｂ）に実施例３（純度：４Ｎ、倍率：３００倍）、（ｃ）に実施例１（純度：５Ｎ、倍率：３００倍）のＳＥＭ像を示す。また、図２（ａ）に実施例５（純度：３Ｎ、倍率：１５０００倍）、（ｂ）に実施例３（純度：４Ｎ、倍率：３００００倍）、（ｃ）に実施例１（純度：５Ｎ、倍率：１５０００倍）のＳＥＭ像を示す。また、図１において、粒径が０．５μｍ以上のパーティクル（介在物）が枠線で囲まれて示されている。 [Evaluation]
(Evaluation of particles)
The particle diameter and the number of particles were measured with a “light scattering automatic particle counter for liquid” (manufactured by Kyushu Lion Co., Ltd.). Specifically, 1 g of Co anode was sampled and dissolved slowly with 150 ml of diluted nitric acid (nitric acid concentration 20% by weight aqueous solution) so that the particles would not dissolve, and after standing for 24 hours, this was further adjusted to 500 ml. The solution was diluted with pure water, 10 ml of this was taken, and measured with the particle counter in liquid. The average value obtained by repeating this three times was defined as the number of particles. The particle size of the particles was evaluated with an SEM image. FIG. 1A shows Example 5 (purity: 3N, magnification: 300 times), FIG. 1B shows Example 3 (purity: 4N, magnification: 300 times), FIG. 1C shows Example 1 (purity: 5N, (Magnification: 300 times) SEM image. FIG. 2A shows Example 5 (purity: 3N, magnification: 15000 times), FIG. 2B shows Example 3 (purity: 4N, magnification: 30000 times), and FIG. 2C shows Example 1 (purity: 5N, magnification: 15000 times). In FIG. 1, particles (inclusions) having a particle size of 0.5 μm or more are shown surrounded by a frame line.
　（Ｆｅ濃度の評価）
　Ｃｏアノードに含まれるＦｅ濃度は、ＧＤＭＳにより評価した。また、パーティクルの粒径及び個数を測定した際にフィルタ上に残存したパーティクル成分については、エネルギー分散型Ｘ線分析（ＥＤＸ：Ｅｎｅｒｇｙ　Ｄｉｓｐｅｒｓｉｖｅ　Ｘ－ｒａｙ　Ｓｐｅｃｔｒｏｍｅｔｒｙ）を用いて評価した。図３（ａ）に実施例５、（ｂ）に実施例３、（ｃ）に実施例１のＥＤＸスペクトルのグラフをそれぞれ示す。 (Evaluation of Fe concentration)
The Fe concentration contained in the Co anode was evaluated by GDMS. Further, the particle components remaining on the filter when the particle diameter and the number of particles were measured were evaluated by using energy dispersive X-ray spectroscopy (EDX: Energy Dispersive X-ray Spectrometry). FIG. 3A shows a graph of the EDX spectrum of Example 5, FIG. 3B shows Example 3 and FIG.
　（異常電着の個数の評価）
　直径３００ｍｍのウェハ（Ｗａｆｅｒ）上に、実施例１～５及び比較例１のＣｏアノードを用いて、それぞれ同条件で電気Ｃｏめっきを行い、厚さ１０ｎｍのＣｏめっき膜を形成し、Ｃｏめっき膜中に生じた欠陥の数（異常電着の個数）を評価した。
　以上の各実施例及び比較例の結果を表１に示す。 (Evaluation of the number of abnormal electrodeposition)
Using a Co anode of Examples 1 to 5 and Comparative Example 1 on a 300 mm diameter wafer, electro-Co plating was performed under the same conditions to form a Co-plated film having a thickness of 10 nm. The number of defects (the number of abnormal electrodepositions) that occurred inside was evaluated.
The results of the above examples and comparative examples are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　（評価結果）
　実施例１～５では、粒径が０．５μｍ以上のパーティクル数が６０００個/ｇ以下であるＣｏアノードを作製することができた。一方、比較例１では粒径が０．５μｍ以上のパーティクル数が６０００個/ｇを超えたＣｏアノードとなった。
　また、実施例１と実施例２、実施例３と実施例４、実施例５と比較例１とは、それぞれ同じ純度のＣｏアノードを使用しているが、Ｆｅ濃度が異なるため、粒径が０．５μｍ以上のパーティクル数に違いが生じている。この結果から、純度が同じであればＦｅ濃度が小さい方が、粒径が０．５μｍ以上のパーティクル数をより低減できることがわかる。
　なお、純度４Ｎである実施例４は、純度３Ｎである実施例５に対し、粒径が０．５μｍ以上のパーティクル数が多かった。このように、必ずしも「高純度」であればパーティクルの数が少ないという関係にはならず、純度が高いＣｏアノードの方が、純度が低いＣｏアノードより本発明で示すパーティクルの数が多い場合もある。
　また、実施例１～５のＣｏアノードを用いて形成したＣｏめっき膜は、異常電着の個数が０であり、めっき不良が良好に抑制されていた。比較例１のＣｏアノードを用いて形成したＣｏめっき膜は、異常電着が確認され、めっき不良が生じた。 (Evaluation results)
In Examples 1 to 5, a Co anode having a particle diameter of 0.5 μm or more and 6000 particles / g or less could be produced. On the other hand, in Comparative Example 1, a Co anode in which the number of particles having a particle size of 0.5 μm or more exceeded 6000 / g was obtained.
In addition, Example 1 and Example 2, Example 3 and Example 4, Example 5 and Comparative Example 1 use Co anodes of the same purity, but the Fe concentration is different, so the particle size is different. There is a difference in the number of particles of 0.5 μm or more. From this result, it can be seen that if the purity is the same, the smaller the Fe concentration, the more the number of particles having a particle size of 0.5 μm or more can be reduced.
In Example 4 having a purity of 4N, the number of particles having a particle diameter of 0.5 μm or more was larger than that in Example 5 having a purity of 3N. In this way, the relationship is not necessarily that the number of particles is small if it is “high purity”, and a higher purity Co anode may have more particles shown in the present invention than a lower purity Co anode. is there.
Further, the Co plating films formed using the Co anodes of Examples 1 to 5 had 0 abnormal electrodepositions, and the plating defects were well suppressed. In the Co plating film formed using the Co anode of Comparative Example 1, abnormal electrodeposition was confirmed, and plating failure occurred.

Claims (7)

  1. 　硝酸濃度２０質量％の希硝酸で溶解した後、液中パーティクルカウンターによってＪＩＳ Ｂ ９９２５に基づいて測定した、粒径が０．５μｍ以上のパーティクルの数が、６０００個/ｇ以下であるＣｏアノード。 A Co anode in which the number of particles having a particle size of 0.5 μm or more is 6000 particles / g or less, measured with a submerged particle counter according to JIS B9925 after being dissolved in dilute nitric acid with a nitric acid concentration of 20 mass%.
  2. 　前記粒径が０．５μｍ以上のパーティクルの数が５０００個/ｇ以下である請求項１に記載のＣｏアノード。 The Co anode according to claim 1, wherein the number of particles having a particle diameter of 0.5 µm or more is 5000 particles / g or less.
  3. 　純度が３Ｎ以上である請求項１又は２に記載のＣｏアノード。 The Co anode according to claim 1 or 2, wherein the purity is 3N or more.
  4. 　純度が４Ｎ以上である請求項３に記載のＣｏアノード。 The Co anode according to claim 3, wherein the purity is 4N or more.
  5. 　Ｆｅ濃度が１０ｐｐｍ以下である請求項３又は４に記載のＣｏアノード。 The Co anode according to claim 3 or 4, wherein the Fe concentration is 10 ppm or less.
  6. 　Ｆｅ濃度が５ｐｐｍ以下である請求項５に記載のＣｏアノード。 The Co anode according to claim 5, wherein the Fe concentration is 5 ppm or less.
  7. 　請求項１～６のいずれか一項に記載のＣｏアノードを用いた電気Ｃｏめっき方法。 An electric Co plating method using the Co anode according to any one of claims 1 to 6.
PCT/JP2018/037118 2018-03-28 2018-10-03 Co anode, and co electroplating method using co anode WO2019187250A1 (en)

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