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WO2005118917A1 - Solution de depot electrolytique pour alliages d'or et d'etain - Google Patents

Solution de depot electrolytique pour alliages d'or et d'etain Download PDF

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Publication number
WO2005118917A1
WO2005118917A1 PCT/US2004/017040 US2004017040W WO2005118917A1 WO 2005118917 A1 WO2005118917 A1 WO 2005118917A1 US 2004017040 W US2004017040 W US 2004017040W WO 2005118917 A1 WO2005118917 A1 WO 2005118917A1
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WO
WIPO (PCT)
Prior art keywords
gold
solution
tin
electroplating
electroplating solution
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.)
Ceased
Application number
PCT/US2004/017040
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English (en)
Inventor
Ronald J. Morrissey
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.)
Technic Inc
Original Assignee
Technic Inc
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 Technic Inc filed Critical Technic Inc
Priority to PCT/US2004/017040 priority Critical patent/WO2005118917A1/fr
Publication of WO2005118917A1 publication Critical patent/WO2005118917A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/62—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of gold

Definitions

  • the present invention relates to an electroplating solution that can more efficiently and effectively deposit gold tin alloys, and to methods for providing such deposits.
  • Alloys of gold and tin are useful as solders for the interconnection of electronic components.
  • gold-tin alloy solder materials are available as thermally processed performs, it is generally acknowledged that the ability to electroplate such materials allows the flexibility to deposit overall or in selected areas at will, and to adjust deposit thicknesses as required. For these reasons, much effort has been made to develop workable electroplating systems for these alloys, and numerous references are provided in the literature about such systems. For many years, the trend in electronic device fabrication has been toward increasingly larger arrays and increasing complexity of such arrays.
  • the invention relates to an electroplating solution for providing a deposit of an alloy of gold and tin.
  • This solution advantageously comprises gold in the form of a solution soluble cyanide complex, tin in the form of a solution soluble organotin complex; and an aqueous solvent.
  • 2,2'-dipyridyl is present as an additive that allows the codeposition of useful gold-tin alloy compositions at current densities lower than would be possible in its absence, given the concentrations of the individual metallic components in the solution.
  • This additive is generally used at a concentration of 0.1 to 1 grams per liter for imparting significant enhancements in providing gold-tin alloy deposits.
  • the electroplating solution typically includes the gold complex as monovalent gold cyanide or trivalent gold cyanide.
  • the organotin complex is preferably stannous citrate, stannous oxalate, or stannous iminodiacetate, and can be formed either pre- manufactured as the desired complex or in situ by addition of a stannous salt and a tin- complexing organic ligand.
  • Useful aqueous solvents for these solutions are aqueous solutions of organic acids. In particular, citric acid and citrates are preferred since these chemicals form desirable complexes with the metals that are to be deposited. If desired, various additives can be included to impart further benefits to the solution.
  • the invention also relates to a process for the codeposition of useful gold-tin alloy compositions.
  • An additive of 2,2'-dipyridyl is present in the electroplating solutions of the invention in an amount that allows codeposition to occur at current densities lower than would be possible in its absence, given the concentrations of the individual metallic components in the solution.
  • This additive is generally used at a concentration of 0.1 to 1 grams per liter as noted above, and an alloy deposit of gold and tin is provided on the metallic portions of a substrate by electroplating from one of the solutions disclosed herein.
  • electroplating solutions of the invention are capable of operating over a wide and useful range of current densities, and are capable of depositing alloys the appearance of which, as well as the composition, is as uniform as possible over the useful range of current densities.
  • the deposition potentials of gold and tin are closer to each other in the presence of the dipyridyl additive than in its absence.
  • gold is contained in the form of a soluble cyanide complex, and tin in the form of a complex of stannous ion with a suitable organic ligand.
  • an operating pH in the range of about 3.5 to 4 was found to be most advantageous.
  • the pH can range from between about 3 and 5.
  • the invention also works with auric gold in the pH range of about 3 to 4, with aurous gold forming spontaneously in the system
  • organic acid electrolytes such as those based on citrates, are highly soluble and well buffered in this pH range and are desirable for this reason Stannous ion is known to be complexed by various organic ligands.
  • citrate is the ligand of choice, both for stability and for compatibility with the electrolyte system
  • the bath matrix or electrolyte preferred for the present invention employs citric acid and/or salts thereof
  • Other organic acids such as formic acid, lactic acid, malic acid, succinic acid, gluconic acid, glycolic acid, or combinations thereof may also be utilized in concentrations ranging from about 75 to 300 g/1, and preferably from about 100 to 200 g/1
  • this additive allows the codeposition of useful gold-tin alloy compositions at current densities lower than would be possible in its absence, given the concentrations of the individual metallic components in the solution.
  • the Examples show this enhancement
  • the examples also show that the composition of alloy deposits plated from the solutions without the additive are not a linear function of current density
  • the addition of a small quantity of the additive, e g , 2,2'-dipyridyl provides a linear variation, and also expands the range of current densities over which homogeneous alloys can be deposited
  • additions of small quantities of thallium, lead, or arsenic in addition to the dipyridyl compound are helpful in obtaining alloy deposits of highly uniform appearance
  • the gold-tin deposits generally contain between 60 and 95% gold and preferably between 75 and 85%, with the balance being essentially tin.
  • the gold-tin plating processes of the present invention are eminently suitable for plating gold-tin alloys on wafers and printed circuit boards. As these components grow larger and more complex, the better control of gold-tin alloy co-deposition is necessary for obtaining improved results. Today, twelve-inch wafers are in use and deep-tank boards are 24 by 30 inches or larger. The present process provides a practical approach to obtaining uniform deposits over really large arrays by allowing codeposition at quite low current densities and in different types of plating systems.
  • Example 1 (Comparative) Sufficient water was employed to form one liter of a solution containing the following:
  • the pH as made up was 3.8.
  • a 267 ml aliquot of this solution was plated in a Hull cell at 0.5 ampere for 5 minutes at 120° F with moving-vane agitation.
  • the deposit as plated showed a bright grayish-yellow (gold-rich) region extending about halfway across the panel (to about 6 amperes per square foot indicated) from the low current density edge.
  • a gray matte (tin-rich) area that extended to the high current density edge was observed.
  • Readings of the deposit composition were obtained by energy-dispersive x-ray analysis using a scanning electron microscope (SEM/EDX) over a range from 3 to 7.5 amperes per square foot indicated, with results as follows: Current Density amps/square foot Percent Gold 3 93.34 4 89.62 5 89.56 6 89.49 7.5 81.98
  • Example 2 The solution of Example 1 was repeated, except that it additionally contained about 0.16 grams of 2,2'-dipyridyl. The solution gradually turned pink in color. A test panel was plated from this solution in a Hull cell under conditions identical to those cited in Example 1. In this case, the transition from yellowish to grayish color of the deposit occurred at about 3 amperes per square foot, and the transition in color was less abrupt than was noted in Example 1. The deposit was analyzed by SEM/EDX as described previously, with results as follows:
  • Example 1 Compared to Example 1, the tin content of the deposits had been increased overall, and the discharge potential of tin has been displaced closer to that of gold.
  • Example 3 (Comparative) A solution was made up as in Example 1, except that the tin was added in the form of stannous oxalate. A test panel was plated from this solution in a Hull cell with moving- vane agitation at 0.5 ampere for 5 minutes at 1 10° F, yielding a deposit showing a bright grayish-yellow (gold-rich) region extending somewhat more than halfway across the panel (to about 10 amperes per square foot indicated) from the low current density edge. At current densities above 10 amperes per square foot, a gray matte (tin-rich) area extended to the high current density edge was observed.
  • Example 4 An electroplating solution was made up identically to that of Example 3, except additionally containing about 0.16 grams of 2,2'-dipyridyl. A test panel was plated in a Hull cell from this solution under identical conditions to those of Example 3. The deposit obtained in this experiment showed a bright grayish-yellow region extending to about 3 amperes per square foot indicated from the low current density edge. Above 3 amperes per square foot a bright gray ring extended to about 5 amperes per square foot, and above that a matte gray area extended to the high current density edge.
  • Example 5 (Comparative) An electroplating solution was made up as in Example 1, except that only 3 grams of tin were added, in the form of stannous iminodiacetate. A test panel was plated from this solution in a Hull cell with moving- vane agitation at 0.5 ampere for 5 minutes at 130° F. The resulting deposit showed a bright grayish-yellow (gold-rich) region extending from the low current density edge to about 7.5 amperes per square foot indicated. Above 7.5 amperes per square foot a matte gray (tin-rich) region extended to about 17.5 amperes per square foot, above which a semi-bright grayish region extended up to the high current density edge. SEM EDX measurements were obtained from this deposit over the current density range from about 3 to 7.5 amperes per square foot indicated, with results as follows:
  • Example 6 An electroplating solution was made up as in Example 5 except additionally containing about 0.16 grams of 2,2'-dipyridyl. A test panel was plated from this solution in a Hull cell with moving-vane agitation at 0.5 ampere for 5 minutes at 130°F. The deposit produced exhibited a bright grayish-yellow (gold-rich) region to about 3 amperes per square foot indicated. Above 3 amperes per square foot, a dull-to-smooth matte gray region extended up to about 20 amperes per square foot, above which the deposit was burnt. SEM/EDX measurements were obtained over the current density range from about 3 to 7.5 amperes per square foot, with results as follows:
  • Example 7 An electroplating solution was made up as in Example 2, except that the gold was introduced in the form of potassium auricyanide, KAu(CN) . Coupon samples were plated from this solution at 100° F, with results as follows:
  • Example 8 An electroplating solution was formed as in Example 1. Aliquot portions of this solution were plated separately in a Hull cell with moving- vane agitation at 0.5 ampere for 5 minutes at 120° F with additions of 2,2'-dipyridyl of 0.16, 0.32, and 0.80 grams per liter. The resulting set of test panels were of essentially identical appearance. On the basis of these experiments, a useful range of concentration of 2,2'-dipyridyl for the purpose of this invention is estimated to be from about 0.1 to 1.0 gram per liter. In Examples 2, 4, 6, 7, and 8, the deposits obtained containing gold in the range of about 70-80 percent by weight are generally of a matte to semi-matte gray appearance.
  • Example 9 An electroplating solution was made up as in Example 2, except additionally containing about 100 parts per million thallium, added as thallous sulfate. A test panel was plated from this solution in a Hull cell with moving-vane agitation for 5 minutes at 0.5 ampere at 120° F. The test panel obtained was of an appearance similar to that obtained in Example 2, but having somewhat higher luster and greater uniformity.
  • Example 10 An electroplating solution was made up as in Example 2, except additionally containing about 100 parts per million lead, added as plumbous acetate. A test panel was plated from this solution in a Hull cell with moving- vane agitation for 5 minutes at 0.5 ampere at 120° F. The test panel obtained was of an appearance similar to that obtained in Example 2, but having somewhat higher luster and greater uniformity.
  • Example 1 1 An electroplating solution was made up as in Example 2, except additionally containing about 30 parts per million arsenic, added as sodium arsenite. A test panel was plated from this solution in a Hull cell with moving-vane agitation for 5 minutes at 0.5 ampere at 120° F. The test panel obtained was of an appearance similar to that obtained in Example 2, but having somewhat higher luster and greater uniformity.

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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)

Abstract

La présente invention concerne une solution de dépôt électrolytique permettant d'appliquer un dépôt d'un alliage d'or et d'étain. Cette solution comprend un solvant aqueux dans lequel l'or est présent sous forme d'un complexe de cyanure soluble en solution et l'étain est présent sous forme d'un complexe d'organo-étain soluble en solution. Du 2,2'-dipyridyle est présent sous forme d'un additif permettant le dépôt simultané de compositions d'alliage d'or-étain utiles à des densités de courant inférieures à celles possibles en son absence, étant donné les concentrations des composants métalliques individuels dans la solution. Cet additif est généralement utilisé à une concentration de 0,1 à 1 grammes par litre afin d'apporter des améliorations importantes concernant les dépôts d'alliages or-étain.
PCT/US2004/017040 2004-06-01 2004-06-01 Solution de depot electrolytique pour alliages d'or et d'etain Ceased WO2005118917A1 (fr)

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PCT/US2004/017040 WO2005118917A1 (fr) 2004-06-01 2004-06-01 Solution de depot electrolytique pour alliages d'or et d'etain

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PCT/US2004/017040 WO2005118917A1 (fr) 2004-06-01 2004-06-01 Solution de depot electrolytique pour alliages d'or et d'etain

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015002691A1 (fr) * 2013-07-05 2015-01-08 The Boeing Company Procédés et appareils pour atténuer la croissance de barbe d'étain sur des surfaces d'étain et étamées par dopage de l'étain par de l'or
CN105483779A (zh) * 2015-12-01 2016-04-13 深圳市瑞世兴科技有限公司 Au-Sn合金电镀液及其电镀方法
CN113285009A (zh) * 2021-05-26 2021-08-20 杭州大和热磁电子有限公司 一种通过沉积金锡焊料组装的tec及制备方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002180259A (ja) * 2000-12-12 2002-06-26 Shipley Co Llc めっき液における金属析出促進化合物および該化合物を含むめっき液

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002180259A (ja) * 2000-12-12 2002-06-26 Shipley Co Llc めっき液における金属析出促進化合物および該化合物を含むめっき液

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015002691A1 (fr) * 2013-07-05 2015-01-08 The Boeing Company Procédés et appareils pour atténuer la croissance de barbe d'étain sur des surfaces d'étain et étamées par dopage de l'étain par de l'or
CN105378151A (zh) * 2013-07-05 2016-03-02 波音公司 通过将锡与金掺杂减轻锡和镀锡表面上的锡须生长的方法和装置
US10260159B2 (en) 2013-07-05 2019-04-16 The Boeing Company Methods and apparatuses for mitigating tin whisker growth on tin and tin-plated surfaces by doping tin with gold
CN105378151B (zh) * 2013-07-05 2020-08-28 波音公司 通过将锡与金掺杂减轻锡和镀锡表面上的锡须生长的方法和装置
CN105483779A (zh) * 2015-12-01 2016-04-13 深圳市瑞世兴科技有限公司 Au-Sn合金电镀液及其电镀方法
CN113285009A (zh) * 2021-05-26 2021-08-20 杭州大和热磁电子有限公司 一种通过沉积金锡焊料组装的tec及制备方法

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