WO2015108784A1 - Procédé pour dépôt de placage de cuivre à grains fins sur un substrat métallique - Google Patents

Procédé pour dépôt de placage de cuivre à grains fins sur un substrat métallique Download PDF

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Publication number
WO2015108784A1
WO2015108784A1 PCT/US2015/010855 US2015010855W WO2015108784A1 WO 2015108784 A1 WO2015108784 A1 WO 2015108784A1 US 2015010855 W US2015010855 W US 2015010855W WO 2015108784 A1 WO2015108784 A1 WO 2015108784A1
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WIPO (PCT)
Prior art keywords
copper
cyanide
substrate
bath
potassium
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PCT/US2015/010855
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English (en)
Inventor
Ali A. FARVID
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The Board Of Trustees Of The Leland Stanford Junior University
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Publication of WO2015108784A1 publication Critical patent/WO2015108784A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00—Electrolytic etching or polishing
    • C25F3/16—Polishing
    • 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
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • C25D3/40—Electroplating: Baths therefor from solutions of copper from cyanide baths, e.g. with Cu+
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/18—Electroplating using modulated, pulsed or reversing current
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/615—Microstructure of the layers, e.g. mixed structure
    • C25D5/617—Crystalline layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00—Electrolytic etching or polishing
    • C25F3/16—Polishing
    • C25F3/22—Polishing of heavy metals
    • C25F3/24—Polishing of heavy metals of iron or steel
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces

Definitions

  • the current invention relates generally to metal deposition. More specifically, the invention relates to a method of forming an adherent oxygen-free electronic (OFE) copper plated layer on a metal substrate.
  • OFE oxygen-free electronic
  • Copper and its alloys are being used very widely in the electronics industry on account of the unique properties that these materials present to the user.
  • impurity level, grain size, and porosity are critical parameters that must be stringently controlled.
  • Copper deposited from an electrolytic plating solution act as thermal expansion barriers by absorbing the stress produced when metals with different thermal expansion coefficients undergo temperature changes.
  • Most vacuum devices are made of stainless steel, which needs to be copper plated or brazed together for different reasons and applications.
  • the mechanical properties of electroplated copper vary widely depending on factors such as solution composition, current density, temperature, impurities and addition agents. What is needed is method of forming an adherent oxygen-free electronic (OFE) copper plated layer over non-ferrous metals, and ferrous metals such as stainless steel, for brazing and vacuum applications and operations.
  • OFE oxygen-free electronic
  • a method of depositing an oxygen-free electronic copper layer on a metal substrate includes cleaning a surface of the substrate, electropolishing the substrate surface, activating the substrate surface, depositing nickel on the substrate, and depositing copper on the substrate using a cyanide copper strike bath and a cyanide copper plate bath, where a periodic pulse and a reverse periodic pulse current is applied using a pulse periodic reverse current power supply, where the deposited oxygen- free copper includes a fine-grained, equiaxed structure having a uniform surface geometry and less than 10% thickness variation across all surfaces.
  • cleaning the substrate includes using a solvent degreaser, a detergent cleaner, a potassium permanganate solution dip, and a combined nitric acid and hydrofluoric acid dip.
  • the solvent degreaser includes a liquid and vapor solvent degreaser capable of removing oil and soil from the substrate, where the vapor solvent includes a hot vapor degreaser with temperature in a range of 100 to 140°F and an ultrasonic cleaner.
  • the electropolishing includes using a phosphoric acid bath having a preset current density of 0.5 to 2 ampere per square inch of the substrate surface for a predetermined time.
  • the activation of the substrate surface includes a two part process having an anodic treatment in a sulfuric acid comprising a concentration in a range of 10 to 50% by volume, and a cathodic treatment in a sulfuric acid comprising a concentration in a range of 10 to 50% by volume for a predetermined duration.
  • the deposition of nickel includes a Watt nickel strike bath includes nickel chloride, hydrochloric acid and water having a current density of more than 40 amperes per square foot.
  • the cyanide copper strike bath includes Rochelle salt, copper cyanide and potassium cyanide with controlled free cyanide concentration in a solution with a temperature range from 120 to 150°F and a high current density between 30 to 60 ampere per square foot.
  • the copper plate bath includes controlled free cyanide, potassium hydroxide and potassium carbonate concentrations at predetermined levels, where the copper bath further includes copper cyanide, potassium cyanide, potassium hydroxide, and potassium-sodium tartrate.
  • the periodic pulse and reverse periodic pulse may each have durations ranging between 0 and 500 seconds.
  • the metal substrate includes a ferrous metal.
  • the substrate includes titanium, copper-based alloys, nickel, cobalt, zinc, tungsten, or aluminum, where the copper-based alloys includes brass or Glidcop.
  • the metal includes a ferrous metal.
  • the substrate includes stainless steel or steel.
  • FIG. 1 is a flow diagram of the deposition process, according to one embodiment of the invention.
  • a method for application of an adherent oxygen-free electronic (OFE) copper plate to stainless steel or non-ferrous metal substrates in general includes surface preparation, electropolishing, activation and deposition of nickel from a plating solution and deposition of copper from a cyanide solution.
  • the standard definition of oxygen-free electronic copper is 99.99% pure copper with 0.0005%> oxygen content [American Society for Testing and Materials (ASTM) Unified Numbering System (UNS) database number C 10100].
  • Non-ferrous metal substrates include, but are not limited to titanium, copper- based alloys (such as brass, Glidcop), nickel, cobalt, zinc, tungsten, and aluminum.
  • the surface preparation includes using a solvent degreaser, a detergent cleaner, a potassium permanganate solution dip, a nitric acid/hydrofluoric acid dip, electropolishing in a phosphoric acid solution, a two step activation process in sulfuric acid solutions and deposition of a nickel strike.
  • the copper plating step includes using a cyanide copper strike and a cyanide copper plate with a pulse periodic reverse current power supply.
  • the copper plated according to the current invention results in a fine- grained, equiaxed structure with no voids during heat treatment to 1000°C, that has a uniform surface geometry and less than 10% thickness variation across all surfaces.
  • the level of the charge of the electrolyte layer is controlled, and the final electrical energy that participates in the absorption process at the cathodic surface is controlled.
  • the use of the reverse, forward and OFF time controls the boundary layer with the main target being the control over metal concentration variation at the cathodic surface.
  • the duty cycle (ON/OFF ratio) of the power supply is integrated with the polarization control and with the effective average current of rate of deposition. According to one embodiment, by decreasing the duty cycle finer grains are produced while maintaining the same plating time.
  • surface preparation includes using a liquid and vapor solvent degreaser to remove all oil and soil from the part or substrate, where the part or substrate is placed into a hot vapor degreaser having ultrasonic agitation with a preset temperature in a range of 100 to 140°F and an ultrasound timer.
  • Detergent cleaning using a potassium permanganate solution and nitric/HF dip are part of cleaning and descaling process.
  • the electropolish bath includes using a solution made up with phosphoric acid and a preset current density of 0.5 to 2 Ampere per square inch of the substrate surface for a predetermined time.
  • the activation of a stainless steel substrate is a two-part process, which includes using anodic treatment in a sulfuric acid having a concentration of 10 to 50% by volume, followed by a cathodic treatment in a sulfuric acid having a concentration of 10 to 50% by volume for a preset time duration.
  • the deposition of the nickel is done using a Watt nickel strike that includes nickel chloride, hydrochloric acid and water with a current density of more than 40 amperes per square foot.
  • the cyanide copper strike includes Rochelle salt, potassium cyanide, and copper cyanide with a controlled free cyanide concentration in a solution with a temperature range from 120 to 150°F and a high current density between 30 to 60 ampere per square foot.
  • a cyanide copper strike bath is used to deposit a thin, adherent layer that can completely cover an active metal surface such as zinc or steel prior to further plating operations. Because of the bath's low plating efficiency, plating time, and thus the deposit's thickness, is often determined by the time needed to just obtain complete coverage.
  • the copper strike serves only as a protective layer for further plating, typically with copper or nickel.
  • the low-metal and high-cyanide levels in the copper strike are responsible for the low efficiency, but these same properties ensure against a non-adhering immersion layer of copper that forms on the surface being plated.
  • This formulation also produces the desired excellent covering and throwing powers.
  • the Rochelle salt bath is used for similar purposes. But, it may also be used to provide thicker deposits than can be obtained with cyanide strike baths, according to one embodiment.
  • the cyanide copper plate bath electrolyte includes copper cyanide, potassium cyanide, potassium hydroxide and potassium-sodium tartrate.
  • the cyanide copper plate bath comprises controlled free cyanide, potassium hydroxide, and potassium carbonate concentrations at predetermined levels to keep the plating process at optimum.
  • the copper cyanide forms a complex with the potassium cyanide in the plating solution, which holds the copper metal in solution and provides the vehicle by which the copper metal is plated out.
  • Free cyanide (the cyanide not combined with copper) is necessary to the success of cyanide copper plating. The free cyanide promotes anode corrosion and controls the bath performance.
  • Free cyanide permits higher cathode current densities, while high free cyanide improves brightness in the low-current areas.
  • Free cyanide is essential in all cyanide copper plating solutions in order to obtain good corrosion of the copper anodes. If it is too low, the anodes polarize and become coated with an insulating film. The concentration of the free cyanide increases at higher temperatures, since lower complexes are formed and free cyanide is thereby liberated. Free cyanide concentration is determined by titrating a sample of the solution with silver nitrate at or below room temperature using potassium iodide as an indicator.
  • Potassium hydroxide enhances the solution electrical conductivity, the throwing power and the overall deposit brightness.
  • Potassium-sodium tartrate is used to form a temporary complex with copper by reacting with products of electrolysis produced in the anode film. Tartrate contributes to the plating solution operates with lower free cyanide and at higher current densities and efficiencies without impairing anode corrosion.
  • Potassium carbonate is formed in solution due to the hydrolysis of free cyanide and the oxidation occurring at the anode.
  • the carbonate exerts a strong buffer action at pH of 10.8 to 11.5 and facilitates pH control. It also reduces anode polarization. It is formed by oxidation of the cyanide radical at the surface of polarized anodes or insoluble anodic metal surfaces. Absorption of carbon dioxide from air by caustic alkali in the solution and by hydrolysis of the cyanide are other sources of carbonates formed in the solution. An increase in the carbonate content is associated with a reduction in the maximum current for efficient copper deposition.
  • the concentration of the carbonate will be less than 100 g/1 and a new bath will be made when concentration of carbonate reaches 100 g/1.
  • the anodes are high-purity, oxygen free copper bars.
  • the power supply is a pulse periodic reverse power supply with a variable frequency and bipolar pulse waveform to enhance the quality and copper distribution over all surfaces.
  • the grain size is controlled without the use of additives by adjusting the duty cycle, where unwanted additives may co-deposit with copper and deteriorate brazing or vacuum application processes. Smaller grains reduce porosity and have higher tensile strength and hardness than larger grains. The tensile strength is inversely proportional to the square root of the grain size. Fine-grained deposits have a higher hardness and usually higher ductility. Since fine-grained deposits pack together better, they have lower porosity and stress. This kind of copper deposit is very desirable in industries specially in brazing operations.
  • the plating characteristic of the plating solution is improved by utilizing current manipulation techniques as well as current interruption cycles.
  • One of the advantages gained by employing periodic current reversal or interrupted cycles is improved leveling.
  • the degree of leveling is greatest using periodic current reversal, particularly with relatively long reversal cycles.
  • Plating deposited according to the current invention shows a laminar structure, whereas plating using conventional direct current methods is columnar.
  • the leveling obtained with current interruption is less than with current reversal, but it is adequate for covering minor surface marks.
  • the uniformity of distribution of the copper on irregularly shaped parts is also improved with current reversal operations, according to the current invention.
  • the method according to the invention prevents excessive buildup of copper on high-current-density areas and yields saving in anode consumption.
  • Current interruption and periodic reverse are beneficial in high-efficiency processes, since they help provide brighter and smoother deposits.
  • the current interruption cycle is approximately 10 sec on and one sec off.
  • the PR cycles require 10-60 sec direct current followed by 2-20 sec of reverse current.
  • current interruption mixed with periodic reversal optimizes the copper plate quality.
  • some applications may achieve similar high quality with current interruption alone (i.e. when the reversal duration is set to zero duration).
  • Step 1 Some exemplary processes for stainless steel substrates are described herein. Step 1 :
  • Step 2 Alkaline cleaning is done using Enthone-OMI Corporation Enprep Q (527), at a concentration of 7 oz/gal, at a temperature of 150°F, for a duration of 5 minutes.
  • Scale and oxide conditioner uses Diversey Wyandotte Diverscale 299 alkaline potassium permanganate solution, having a concentration of 20 oz/gal, at a temperature of 190°F, for a duration of 60 minutes.
  • Step 5 Rinse with cold water for 1 minute.
  • Step 6 Step 6:
  • Scale removal is done using Diversey Wyandotte Everite II having a concentration 50% by volume, at room temperature, for a duration of 30 seconds.
  • Step 7 Rinse with cold water for 1 minute.
  • Step 8
  • Stainless steel pickle is a mixture of nitric acid at a concentration of 11.5% by volume, hydrofluoric acid at a concentration of 13% by volume, and water balance at room temperature for a duration of 60 Seconds.
  • Stainless steel electropolish is done using a mixture of 25% by volume of ElectroGlo 300 (ElectroGlo, Inc.) and 75% by volume phosphoric acid (85%) at a temperature of 140°F with agitation for a duration of 3 minutes, while subject to 8 Volts using anodic current.
  • ElectroGlo 300 ElectroGlo, Inc.
  • phosphoric acid 85%
  • the anodic treatment is done using sulfuric acid having a concentration of 25% by volume, at room temperature, while subject to 6 Volts anodic (reverse) current for a duration of one minute, using lead anodes and agitation.
  • Cathodic treatment includes using sulfuric acid having a concentration of 30% by volume at room temperature, using cathodic (direct) current at 6 Volts for a duration of one minute from lead anodes under agitation, where the solution in step 12 is not used.
  • Step 16 Nickel strike is done using nickel chloride having a nickel concentration as nickel metal of 7 to 8 oz/gal, hydrochloric acid having a concentration of 12 to 16 Fl.oz/Gal, using water balance at room temperature for 6 minutes, while subject to 40 to 60 Amperes per square foot from a rolled depolarized nickel anode at a current density of 40 to 60 Amperes per square foot, while using agitation.
  • Copper strike is done using potassium copper cyanide having a concentration of 5 to 6 oz/gal, potassium cyanide having a free potassium cyanide concentration of 2 oz/gal, sodium-potassium tartrate having a concentration of 7 to 8 oz/gal at a temperature of 110°F for a duration of two minutes, while subjecting it to 40 Amperes per square foot using an OFE copper anode, while subject to moderate agitation and 1 micron continuous filtration.
  • Copper plate is done using copper cyanide having a concentration of 7 to 9 oz/gal, potassium cyanide having a concentration of free cyanide of 2 oz/gal, potassium hydroxide having a concentration of 2-3 oz/gal, and potassium-sodium tartrate, 4 H 2 0, having a concentration of 6 oz/gal, at a temperature of 140°F for a duration that achieves the desired thickness using OFE copper (bagged) anodes subject to moderate agitation and 1 micron continuous filtration, with free cyanide having a concentration of 2 oz/gal, potassium hydroxide having a concentration of 2.2 oz/gal, potassium carbonate having a maximum concentration of 100 g/1, and using pulse periodic reverse with a direct plating time having a duration of 30 seconds, OFF for 5 seconds, and ON for 25 seconds, where the reverse plating time has a duration of 8 seconds, OFF for 2 second, and ON for 6 seconds, with a forward current density of 20 Amperes per square foot, and a reverse
  • Step 21
  • Copper electropolish is done using a mixture of 25% by volume of ElectroGlo 200 (ElectroGlo Inc.) and 75% by volume phosphoric acid (85%) at a temperature of 90°F, subject to agitation for a duration of 3 minutes and 8 Volts using anodic (reverse).
  • ElectroGlo 200 ElectroGlo Inc.
  • phosphoric acid 85%
  • Step 23 Rinse with cold water for 2 minute until all chemicals are removed.
  • Copper anti-tarnish is done using Rohm & Haas Advantage 2000 OXYBAN 60 having a concentration of 1% by volume at room temperature for a duration of 3 minutes, under agitation.
  • Step 27 Rinse with cold DI water for 1 minute.
  • Step 28 Rinse with cold DI water for one minute. (Minimum resistivity 1,000,000 ohms cm)
  • Step 29 :
  • Step 31 Dry with dry nitrogen blast.
  • the current invention provides a method of plating copper on a metal substrate, where the copper is oxygen free (high purity), fine grain, and has excellent adhesion.
  • the oxygen free aspect is achieved by the selection of the materials for the chemical bath. It is critical to minimize the species types by choosing the appropriate electrolyte type chemistry and avoiding additives such as organic impurities and addition agents. Organic impurities cause degradation of copper plating baths and together with addition agents that degrade the deposition quality via co-depositing organic materials in the copper plated layer.
  • One of the principal reasons for using oxygen free copper in critical applications is its low oxygen content and its contaminant freedom from hydrogen embrittlement. Organic impurities and addition agents will not result in an OFE copper plated layer.
  • the fine grain aspect is accomplished via pulse and reverse pulse processing. Without the use of addition agents, cyanide electrolytes produces harder coating than acid baths. Hardness of the electrodeposit is generally associated with fine grain. Leveling has a significant effect on the appearance of the copper coating.
  • the high concentration potassium cyanide electrolytes produce excellent leveling when interrupted current or periodic reversal is used during plating.
  • the combination of cyanide electrolytes and pulse/reverse pulse processing achieves levelling without additives.
  • the pulse plating allows much faster plating without surface burning, produces finer grain deposits and increases throwing power and distribution.
  • the improved adhesion property is accomplished by proper surface preparation of the substrate.
  • Different substrates have different surface preparation processes.
  • Substrates that can be used include, but are not limited to, stainless steel, titanium, copper-based alloys (such as brass, Glidcop), steel, nickel, cobalt, zinc, tungsten and aluminum.

Abstract

L'invention porte sur un procédé de dépôt d'une couche de cuivre électronique, exempt d'oxygène, sur un substrat métallique, qui comprend le nettoyage d'une surface de substrat, le polissage électrolytique de la surface du substrat, l'activation de la surface du substrat, le dépôt de nickel sur le substrat et le dépôt de cuivre sur le substrat à l'aide d'un bain d'amorçage au cyanure de cuivre et d'un bain de placage au cyanure de cuivre, un courant pulsé périodique et un courant pulsé périodique inverse étant appliqués à l'aide d'une alimentation électrique à courant inverse, périodique et pulsé, le cuivre exempt d'oxygène déposé comportant une structure de grains fins isométriques ayant une géométrie de surface uniforme et moins de 10% de variation d'épaisseur sur toutes les surfaces.
PCT/US2015/010855 2014-01-15 2015-01-09 Procédé pour dépôt de placage de cuivre à grains fins sur un substrat métallique WO2015108784A1 (fr)

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US201461927637P 2014-01-15 2014-01-15
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CN107858711A (zh) * 2017-11-28 2018-03-30 歌尔股份有限公司 金属基体电镀方法
US11898264B2 (en) * 2020-09-21 2024-02-13 Hutchinson Technology Incorporated Treatment methods and solutions for improving adhesion of gold electroplating on metal surfaces
CN113789513A (zh) * 2021-08-19 2021-12-14 上海富乐华半导体科技有限公司 一种基于正负脉冲的陶瓷基板表面镀铜方法

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