EP3312308A1 - Nickelplattierungslösung - Google Patents

Nickelplattierungslösung Download PDF

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Publication number
EP3312308A1
EP3312308A1 EP17197736.6A EP17197736A EP3312308A1 EP 3312308 A1 EP3312308 A1 EP 3312308A1 EP 17197736 A EP17197736 A EP 17197736A EP 3312308 A1 EP3312308 A1 EP 3312308A1
Authority
EP
European Patent Office
Prior art keywords
nickel
sulfamate
ions
electroplating composition
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP17197736.6A
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English (en)
French (fr)
Inventor
Masaaki Imanari
Yil-Hak LEE
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rohm and Haas Electronic Materials Korea Ltd
Rohm and Haas Electronic Materials LLC
Original Assignee
Rohm and Haas Electronic Materials Korea Ltd
Rohm and Haas Electronic Materials LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rohm and Haas Electronic Materials Korea Ltd, Rohm and Haas Electronic Materials LLC filed Critical Rohm and Haas Electronic Materials Korea Ltd
Publication of EP3312308A1 publication Critical patent/EP3312308A1/de
Withdrawn legal-status Critical Current

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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
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/12—Semiconductors
    • C25D7/123—Semiconductors first coated with a seed layer or a conductive layer

Definitions

  • the present invention relates to a boric-acid free nickel plating composition which does not include organic carboxylic acid but has high bath pH stability.
  • the nickel plating composition provides a nickel plating film suitable for the use of electronic materials such as under bump metal (UBM).
  • UBM under bump metal
  • Nickel electroplating has been conventionally used for electronic materials because of its good properties of the resulting film such as anti-corrosion and electrical conductivity.
  • Conventional nickel plating composition comprises boric acid as a pH buffer, to maintain the pH value of a nickel plating bath around 3 to 5.
  • boric acid is considered as one of environmental harmful chemicals.
  • boric acid is listed as a controlled chemical of the Water Pollution Prevention Act in Japan, as well as a potential chemical of Registration, Evaluation, Authorization and Restriction of Chemicals (REACH) in the EU. Therefore, boric acid free nickel electroplating composition is desired.
  • Some boric acid free nickel electroplating baths are disclosed, for example, JP2012126951A , JP2004265253A , JP2001172790A and JP2010267208A .
  • the nickel electroplating compositions disclosed in these patent documents include organic carboxylic acids such as citric acid or gluconic acid, or other organic compounds as pH buffer.
  • boric acid free nickel plating bath comprising organic carboxylic acids
  • the bath pH is not stable
  • boric acid free nickel electroplating composition with good bath pH stability and good nickel plating film properties is still desired.
  • Inventors of this invention found that when sulfamic acid or its salt is used in a nickel electroplating composition instead of boric acid, a nickel electroplating bath using the composition has good pH stability.
  • the nickel plating film formed from the nickel electroplating composition with sulfamic acid or its salt has similar internal stress to the one formed from the conventional nickel electroplating compositions comprising boric acid. It means that the nickel plating film formed from the composition comprising sulfamic acid or its salt can be an alternative of the conventional nickel electroplating compositions used for electronic materials.
  • one embodiment of the invention is a nickel electroplating composition
  • a nickel electroplating composition comprising 0.8 to 2.8 mol/L of nickel ions, 0.06 to 1.5 mol/L of halogen ions and 1.6 to 5.1 mol/L of sulfamate ions; the total amount as mol/L of sulfamate ions and halogen ions are larger than the twice of mol/L of nickel ions; the nickel electroplating composition has a pH value of 3 to 5 and the nickel electroplating composition is substantially free of boric acid and organic carboxylic acids.
  • Another embodiment of the invention is a nickel electroplating composition formed from 100 g/L to 650 g/L of nickel sulfamate, 2 g/L to 100 g/L of nickel halide, 5 g/L to 130 g/L of sulfamic compound selected from sulfamic acid, sodium sulfamate, potassium sulfamate and ammonium sulfamate, water and optionally surfactants, pH adjustor, wetting agent and grain refiner; the nickel electroplating composition has a pH value of 3 to 5 and the nickel electroplating composition is substantially free of boric acid and organic carboxylic acids.
  • a further embodiment of the invention is a nickel electroplating composition consisting of one or more sources of nickel ions, one or more sources of halogen ions, one or more sources of sulfamate ions selected from sulfamic acid, sodium sulfamate, potassium sulfamate and ammonium sulfamate, water and one or more optional compounds selected from surfactants, pH adjustor, wetting agent and grain refiner; the nickel electroplating composition having a pH value of 3 to 5 and wherein the nickel electroplating composition is substantially free of boric acid and organic carboxylic acids.
  • the invention relates to a method for electroplating a nickel layer on a semiconductor wafer comprising: providing a semiconductor wafer comprising a plurality of conductive bonding features, contacting the semiconductor wafer with the any composition disclosed above and applying sufficient current density to deposit a nickel layer on the conductive bonding features.
  • the invention relates to a nickel under bump metal formed from the composition any of disclosed above.
  • the nickel electroplating composition of the invention is substantially free of boric acid and organic carboxylic acids, and comprises sulfamic acid or salt thereof to maintain bath pH value from 3 to 5.
  • the nickel electroplating composition of the invention is free of boric acid and organic carboxylic acids, and comprises sulfamic acid or salt thereof to maintain bath pH value from 3 to 5.
  • the nickel electroplating composition can be formed from nickel sulfamate, nickel halide, sulfamic compound, water and optionally additives used in traditional nickel electroplating compositions.
  • nickel sulfamate can be used.
  • the amount of nickel sulfamate in the nickel electroplating composition is from 100 to 650 g/L, preferably from 200 to 500 g/L.
  • Nickel sulfamate forms nickel ion and sulfamate ion in a nickel electroplating composition.
  • nickel halide examples include nickel chloride and nickel bromide.
  • Commercially available nickel halide can be used.
  • nickel halide is nickel chloride.
  • the amount of nickel halide in the nickel electroplating composition is from 2 to 100 g/L, preferably from 5 to 50 g/L. When nickel halide is nickel chloride, its preferable amount is from 4 to 20 g/L.
  • Nickel halide forms nickel ion and halogen ion in a nickel electroplating composition. Halogen ion helps dissolution of nickel anode.
  • Sulfamic compound is a compound which forms sulfamate ions in an aqueous solution.
  • Sulfamic compound comprises sulfamic acid and sulfamate salts such as sodium sulfamate, potassium sulfamate and ammonium sulfamate.
  • the sulfamate salts are water soluble.
  • sulfamic compound is selected from sulfamic acid, sodium sulfamate, potassium sulfamate and ammonium sulfamate. The combination of two or more of sulfamic compounds can be used.
  • the sulfamic compound is a mixture of sulfamic acid and sulfamate salts.
  • the molar ratio of sulfamic acid and sulfamate salts is from 1 : 3 to 1 : 300. More preferably, the molar ratio of sulfamic acid and sulfamate salts is from 1 : 5 to 1 : 200.
  • the amount of sulfamic compound in the nickel electroplating composition is 5 g/L or more, preferably 10 g/L or more, more preferably 20 g/L or more. At the same time, the amount of sulfamic compound in the nickel electroplating composition is 600g/L or less, preferably 300 g/L or less, more preferably 200 g/L or less, the most preferably 130 g/L or less. Sulfamic compound forms sulfamate ion and counter cation in a nickel electroplating composition.
  • the nickel electroplating composition of the invention comprises larger amount of sulfamate ions than a conventional nickel electroplating composition.
  • Sulfamate ions in the nickel electroplating composition are came from nickel sulfamate and sulfamate compound.
  • the nickel electroplating composition comprises 0.5 to 3.0 mol/L of nickel ions, 0.03 to 2.0 mol/L of halogen ions and 1.0 to 6.5 mol/L of sulfamate ions. More preferably, the nickel electroplating composition of the invention comprises 0.8 to 2.8 mol/L of nickel ions, 0.06 to 1.5 mol/L of halogen ions and 1.6 to 5.1 mol/L of sulfamate ions.
  • the total amount as mol/L of sulfamate ions and chloride ions are larger than twice the amount (in mol/L) of nickel ions.
  • the pH value of a plating bath will gradually increase during its operation.
  • the pH value of the nickel electroplating bath is lower than 3, the depositing speed of nickel metal would be decreased.
  • the pH value of the nickel electroplating bath is higher than 5, the internal stress of deposited nickel metal would be increased. Therefore, it is important to maintain the pH value of a nickel electroplating bath between 3 and 5.
  • the specific amount of sulfamate ions work like a pH buffer in a nickel electroplating bath, to maintain the pH value of a nickel plating bath between 3 to 5.
  • sulfamate ions act like a pH buffer by controlling generation of hydrogen in a bath, same as a boric acid in a bath. Therefore, the nickel electroplating composition of the invention has high pH-stability without including boric acid or organic carboxylic acids.
  • the nickel electroplating composition optionally comprises surfactant, pH adjustor, wetting agent and grain refiner.
  • Such optional additives are well-known to those skills in the art.
  • the additive of the nickel electroplating composition does not include organic carboxylic acids and boric acid, because the nickel electroplating composition of the invention is substantially free of boric acid and organic carboxylic acids, and preferably free of boric acid and organic carboxylic acids.
  • the solvent of the nickel electroplating composition is normally water. Tap water, deionized water, or distilled water can be used.
  • One aspect of the invention is a nickel electroplating composition consisting of one or more sources of nickel ions, one or more sources of halogen ions, one or more sources of sulfamate ions selected from sulfamic acid, sodium sulfamate, potassium sulfamate and ammonium sulfamate, water and one or more optional compounds selected from surfactants, pH adjustor, wetting agent and grain refiner.
  • the nickel electroplating composition has a pH value of 3 to 5 and the nickel electroplating composition is substantially free of boric acid and organic carboxylic acids.
  • the source of nickel ions is nickel sulfamate.
  • the concentration of one or more sources of sulfamate ions are in amounts of from 5 to 130 g/L.
  • Such nickel electroplating composition is free of boric acid and organic carboxylic acids.
  • the nickel electroplating composition of the invention is useful for electronic materials.
  • One aspect of the invention relates to a method of electroplating a nickel layer on a semiconductor wafer comprising: providing a semiconductor wafer comprising a plurality of conductive bonding features, contacting the semiconductor wafer with any composition disclosed above and applying sufficient current density to deposit a nickel layer on the conductive bonding features.
  • Examples of the semiconductor wafer include, but are not limited to, silicon wafer, glass and organic substrates.
  • Conductive bonding features are normally formed by the following steps: forming a conductive layer on the surface of the semiconductor wafer, forming a resist layer on the conductive layer of the semiconductor wafer, then removing at least a part of the resist layer to make openings on the conductive layer. Copper is normally used as the conductive layer.
  • the conductive layer can be formed any known methods, such as sputtering or electroless metal plating.
  • the semiconductor wafer with conductive layer is contacted with the composition disclosed above by any known methods to deposit nickel on the conductive layer of the semiconductor wafer. Normally, the semiconductor wafer is immersed in the nickel plating solution and current applied.
  • Nickel metal can be used as an anode, but an insoluble electrode such as a platinum-plated titanium plate can be used in some cases.
  • the current densities are in the range of from 0.5 to 40 A/dm 2 , preferably from 5 to 20 A/dm 2 .
  • the temperature of the nickel plating composition is basically from 10 to 80 °C, preferably 30 to 65 °C.
  • Plating time depends on current density and required plating thickness. For example, if current density is 1 A/dm 2 and the required thickness of Ni layer is 3 micrometer, the plating time is about 15 minutes.
  • the nickel layer formed from the method of the present invention has 40 MPa or less of internal stress. More preferably, the internal stress is 30 MPa or less, and the most preferably, the internal stress is 25 MPa or less. Internal stress was measured by deposit stress analyzer. Since the internal stress formed from a conventional nickel electroplating bath comprising boric acid is around 10 to 40 MPa, the nickel electroplating composition of the invention provides nickel deposition with similar internal stress with the conventional bath.
  • the nickel plating composition of the invention can be used to form an under layer of gold plating and a barrier layer of copper surface.
  • the nickel plating composition of the invention is also useful to form an under bump metal (UBM).
  • UBM is a protection buffer layer between a seed metal (around 2000 ⁇ of copper) and a solder.
  • the nickel plating composition of the invention can be used to form a bump (pillar) on a substrate to connect between a substrate and an electronic component electrically.
  • Test sample Silicon wafer provided by IMAT Co. was used as a test sample (Test Sample).
  • Test sample is 60 mm x 50 mm size of silicon wafer which has titanium layer (under layer) and copper layer (upper layer) on the surface of the silicon wafer, then resist layer was formed on the copper layer and ten holes with 75 micrometers of diameters were formed through the resist layer.
  • Titanium layer was formed by sputtering of 1,000 ⁇ of titanium particles while copper layer was formed by sputtering of 3,000 ⁇ of copper particles.
  • Test Sample was immersed in a nickel plating solution (disclosed below) and electroplated. Anode was nickel metal. Current density was 6 A/dm 2 , and temperature of the nickel plating solution was 60 °C. The targeted plating thickness was 3 ⁇ m.
  • Test Sample was washed with DI water. After that, the resist was removed by dipping in Shipley BPR stripper (Available from Rohm and has Electronic Materials, Marlborough, Massachusetts, USA) at 60 °C for 5 minutes.
  • Ten nickel depositions (nickel under bump metal) were formed in the holes on Test Sample. The surface of the nickel depositions were observed by SEM. The internal stress of the nickel depositions were measured by the deposit stress analyzer provided by Electrochemical co. ltd. The bath pH stability was checked and the result is shown in Fig. 3 .
  • pH buffer For pH buffer, the compounds written in Tables 1 and 2 were used. Table 1 Inventive Examples pH buffer 1 2 3 Sulfamic acid 20 g/L 1 g/L Sodium sulfamate 20 g/L 125 g/L Internal stress 18MPa 20MPA 20MPa Table 2 Comparative Examples pH buffer 1 2 3 Malic acid 20 g/L Maleic acid 20 g/L Boric acid 40 g/L Internal stress 60MPa 160MPa 20MPa
  • FIG. 1 A SEM of a UBM obtained by Example 2 is shown in Fig. 1 (magnification is 1500 times) and SEM photograph of a UBM obtained by Example 3 is shown in Fig. 2 (magnification is 1000 times).
EP17197736.6A 2016-10-24 2017-10-23 Nickelplattierungslösung Withdrawn EP3312308A1 (de)

Applications Claiming Priority (1)

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JP2016208151A JP2018070907A (ja) 2016-10-24 2016-10-24 ニッケルめっき液

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EP3312308A1 true EP3312308A1 (de) 2018-04-25

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EP17197736.6A Withdrawn EP3312308A1 (de) 2016-10-24 2017-10-23 Nickelplattierungslösung

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US (1) US20180112319A1 (de)
EP (1) EP3312308A1 (de)
JP (1) JP2018070907A (de)
KR (1) KR20180044824A (de)
CN (1) CN107974698A (de)
TW (1) TW201816191A (de)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111926352B (zh) * 2018-06-12 2023-04-07 北京航空航天大学 一种镀镍溶液
KR102496247B1 (ko) * 2021-01-06 2023-02-06 와이엠티 주식회사 전기 도금 용액 첨가제 및 이를 포함하는 고속 도금 가능한 고전류 전기 니켈 도금 용액
JP7197933B2 (ja) * 2021-05-27 2022-12-28 石原ケミカル株式会社 アンダーバリアメタルとソルダー層とを含む構造体

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001172790A (ja) 1999-12-16 2001-06-26 Tokyo Metropolis 電気ニッケルめっき浴。
JP2004265253A (ja) 2003-03-03 2004-09-24 Matsushita Electric Works Ltd 遠隔監視制御装置
JP2008285732A (ja) * 2007-05-21 2008-11-27 Meltex Inc ニッケルめっき液及びそのニッケルめっき液を用いた電気めっき方法並びにその電気めっき方法でニッケルめっき皮膜を形成したチップ部品
JP2010267208A (ja) 2009-05-18 2010-11-25 Irf:Kk 逆走防止装置
JP2012126951A (ja) 2010-12-14 2012-07-05 Meltex Inc ニッケルめっき液及びニッケルめっき方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020135069A1 (en) * 2000-11-03 2002-09-26 Wood Robert L. Electroplating methods for fabricating microelectronic interconnects
GB2393037B (en) * 2002-09-11 2007-05-23 Tera View Ltd Method of enhancing the photoconductive properties of a semiconductor and method of producing a seminconductor with enhanced photoconductive properties

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001172790A (ja) 1999-12-16 2001-06-26 Tokyo Metropolis 電気ニッケルめっき浴。
JP2004265253A (ja) 2003-03-03 2004-09-24 Matsushita Electric Works Ltd 遠隔監視制御装置
JP2008285732A (ja) * 2007-05-21 2008-11-27 Meltex Inc ニッケルめっき液及びそのニッケルめっき液を用いた電気めっき方法並びにその電気めっき方法でニッケルめっき皮膜を形成したチップ部品
JP2010267208A (ja) 2009-05-18 2010-11-25 Irf:Kk 逆走防止装置
JP2012126951A (ja) 2010-12-14 2012-07-05 Meltex Inc ニッケルめっき液及びニッケルめっき方法

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CN107974698A (zh) 2018-05-01
KR20180044824A (ko) 2018-05-03
US20180112319A1 (en) 2018-04-26
JP2018070907A (ja) 2018-05-10
TW201816191A (zh) 2018-05-01

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