US20140166492A1 - Sn ALLOY PLATING APPARATUS AND METHOD - Google Patents

Sn ALLOY PLATING APPARATUS AND METHOD Download PDF

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Publication number
US20140166492A1
US20140166492A1 US14/103,767 US201314103767A US2014166492A1 US 20140166492 A1 US20140166492 A1 US 20140166492A1 US 201314103767 A US201314103767 A US 201314103767A US 2014166492 A1 US2014166492 A1 US 2014166492A1
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anolyte
anode
anode chamber
alloy plating
chamber
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US14/103,767
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English (en)
Inventor
Masashi Shimoyama
Jumpei Fujikata
Yuji Araki
Masamichi Tamura
Toshiki Miyakawa
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Ebara Corp
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Ebara Corp
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Assigned to EBARA CORPORATION reassignment EBARA CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ARAKI, YUJI, FUJIKATA, JUMPEI, MIYAKAWA, TOSHIKI, SHIMOYAMA, MASASHI, TAMURA, MASAMICHI
Publication of US20140166492A1 publication Critical patent/US20140166492A1/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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/12—Process control or regulation
    • C25D21/14—Controlled addition of electrolyte components
    • 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
    • C25D17/002—Cell separation, e.g. membranes, diaphragms
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/10—Agitating of electrolytes; Moving of racks
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/16—Regeneration of process solutions
    • C25D21/18—Regeneration of process solutions of electrolytes
    • 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
    • C25D3/30—Electroplating: Baths therefor from solutions of tin
    • 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
    • C25D5/003—Electroplating using gases, e.g. pressure influence
    • 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
    • C25D17/001—Apparatus specially adapted for electrolytic coating of wafers, e.g. semiconductors or solar cells
    • 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
    • C25D17/008—Current shielding devices

Definitions

  • the present invention relates to an Sn alloy plating apparatus and method useful for forming a metal film of an alloy of Sn and a metal which is nobler than Sn (e.g., a lead-free Sn—Ag alloy having good soldering properties) on a substrate surface.
  • a metal which is nobler than Sn e.g., a lead-free Sn—Ag alloy having good soldering properties
  • a plating film of an alloy of Sn (tin) and a metal which is nobler than Sn e.g., an Sn—Ag alloy which is an alloy of Sn and silver
  • Sn—Ag alloy plating is typically carried out by applying a voltage between an anode and a substrate surface, which are disposed opposite to each other and immersed in an Sn—Ag alloy plating solution containing Sn ions and Ag ions, thereby forming an Sn—Ag alloy film on the substrate surface.
  • an Sn—Cu alloy which is an alloy of Sn and Cu (copper)
  • an Sn—Bi alloy which is an alloy of Sn and Bi (bismuth), and the like
  • Sn and a metal which is nobler than Sn.
  • An insoluble anode is often used in plating of such an alloy of Sn and a metal which is nobler than Sn. This is because, if a soluble anode made of Sn (i.e., Sn anode) is used, displacement deposition of the nobler metal on the surface of the Sn anode will occur, leading to unstable concentration of metal component and contamination of the plating solution.
  • Sn anode a soluble anode made of Sn
  • a plating method which involves separating an anode chamber, in which an Sn anode is disposed, from a plating bath by using an anion exchange membrane, and putting an Sn plating solution and an acid or a salt thereof into the anode chamber and putting an Sn alloy plating solution into the plating bath (see Japanese Patent No. 4441725).
  • the Sn ion-containing solution in the anode chamber can be supplied through a supply line to the Sn alloy plating solution in the plating bath.
  • a plating method has been proposed which comprises carrying out plating of a plating object in a plating bath by using an Sn anode which is isolated by an anode bag or box formed of a cation exchange membrane (see Japanese Patent No. 3368860).
  • an Sn—Ag alloy plating method which involves providing a plating bath with an auxiliary cell, having a cathode chamber and an anode chamber which are separated by a diaphragm so that a substance that can cause deterioration of a plating solution will not diffuse into the cathode chamber, and supplying Sn ions to the plating solution (anolyte) in the anode chamber in the auxiliary bath (see Japanese Patent Laid-Open Publication No. H11-21692).
  • Japanese Patent No. 4441725 describes the method including the steps of separating an anode chamber and a cathode chamber by an anion exchange membrane, putting an Sn anode into an electrolytic solution (anolyte) containing Sn ions and an acid or a salt thereof, held in the anode chamber, to allow dissolution of Sn ions from the Sn anode into the anolyte, and supplying the Sn ion in the anode chamber to the cathode chamber.
  • an electrolytic solution anolyte
  • the present invention has been made in view of the above situation. It is therefore an object of the present invention to provide an Sn alloy plating apparatus and method which appropriately control a concentration of Sn ions and a concentration of an acid that forms a complex with a divalent Sn ion in an anolyte to be supplied to an Sn alloy plating solution, to thereby enable relatively easy control of the Sn alloy plating solution and simplified construction of the apparatus.
  • An Sn alloy plating apparatus for electrodepositing an An Sn alloy plating apparatus for electrodepositing an alloy of Sn and a metal which is nobler than Sn on a surface of a substrate comprises: a plating bath whose interior is separated by an anion exchange membrane into a cathode chamber for holding therein an Sn alloy plating solution in which the substrate, serving as a cathode, is to be immersed and an anode chamber for holding therein an anolyte containing Sn ions and an acid that forms a complex with a divalent Sn ion; an Sn anode located in the anode chamber; and an electrolytic solution supply line configured to supply an electrolytic solution containing the acid into the anode chamber such that a Sn ion concentration of the anolyte in the anode chamber is kept not less than a predetermined value and a concentration of the acid in the anolyte is kept not less than a predetermined acceptable value, the electrolytic solution supply line being configured to
  • the Sn ion concentration of the anolyte and the concentration of the acid that forms a complex with a divalent Sn ion are controlled appropriately, the anolyte, having a high Sn ion concentration and in which divalent Sn ions exist stably, is supplied to the Sn alloy plating solution. Therefore, it is possible to supply Sn ions to the Sn alloy plating solution stably.
  • the electrolytic solution supply line is configured to supply the electrolytic solution into the anode chamber to increase an amount of the anolyte in the anode chamber to thereby cause the anolyte to overflow the anode chamber into the Sn alloy plating solution.
  • the anolyte having a high Sn ion concentration and in which divalent Sn ions exist stably, can be supplied to the Sn alloy plating solution without use of any power.
  • the Sn alloy plating apparatus further includes: an overflow bath configured to store the Sn alloy plating solution that has overflowed the cathode chamber; and a plating solution circulation line configured to return the Sn alloy plating solution in the overflow bath to the cathode chamber to thereby circulate the Sn alloy plating solution.
  • the Sn alloy plating solution in the cathode chamber circulates through the plating solution circulation line, so that the plating solution can be agitated.
  • the Sn alloy plating apparatus further includes a pure water supply line configured to supply pure water into the anode chamber.
  • the concentration of the acid in the anolyte can be controlled in a preferable range.
  • the Sn alloy plating apparatus further comprises an acid concentration measuring device for measuring the concentration of the acid in the anolyte in the anode chamber.
  • the Sn alloy plating apparatus further comprises a dialysis cell configured to draw out a part of the Sn alloy plating solution from the cathode chamber, remove at least a part of the acid from the Sn alloy plating solution, and then return the Sn alloy plating solution to the cathode chamber.
  • the concentration of the acid in the Sn alloy plating solution is too high, at least a part of the acid can be removed from the Sn alloy plating solution by the dialysis cell so as to adjust the acid concentration to a preferable range.
  • the Sn alloy plating apparatus further comprises an N 2 gas supply line configured to supply nitrogen gas into the anolyte in the anode chamber to form nitrogen gas bubbles in the anolyte.
  • the anolyte in the anode chamber can be sufficiently agitated with the bubbles of the nitrogen gas, so that Sn ions and the acid can be uniformly distributed in the anolyte.
  • the bubbles of the nitrogen gas can prevent oxidation of the Sn ions in the anolyte.
  • the Sn alloy plating apparatus further comprises an auxiliary electrolytic cell configured to supply an anolyte having an increased concentration of Sn ions to the Sn alloy plating solution.
  • the auxiliary electrolytic cell includes an auxiliary anode chamber for holding an anolyte therein, an auxiliary cathode chamber for holding a catholyte therein, an anion exchange membrane separating the auxiliary anode chamber and the auxiliary cathode chamber from each other, an auxiliary Sn anode located in the auxiliary anode chamber, an auxiliary cathode located in the auxiliary cathode chamber, and an auxiliary power source configured to apply a voltage between the auxiliary Sn anode and the auxiliary cathode when the auxiliary Sn anode is immersed in the anolyte and the auxiliary cathode is immersed in the catholyte to produce the anolyte having the increased concentration of Sn ions.
  • the shortage can be compensated for by the supply of the anolyte, having a high Sn ion concentration, from the auxiliary anode chamber.
  • An Sn alloy plating method of electrodepositing an alloy of Sn and a metal which is nobler than Sn on a surface of a substrate comprising: providing a plating bath whose interior is separated by an anion exchange membrane into a cathode chamber and an anode chamber; supplying an Sn alloy plating solution into the cathode chamber; immersing the substrate in the Sn alloy plating solution; supplying an anolyte, containing Sn ions and an acid that forms a complex with a divalent Sn ion, into the anode chamber to immerse an Sn anode in the anolyte; supplying an electrolytic solution containing the acid into the anode chamber such that a Sn ion concentration of the anolyte in the anode chamber is kept not less than a predetermined value and a concentration of the acid in the anolyte is kept not less than a predetermined acceptable value; and applying a voltage between the Sn anode and the substrate serving as
  • the supplying the electrolytic solution into the anode chamber to increase an amount of the anolyte in the anode chamber and the supplying the anolyte into the Sn alloy plating solution by the increased amount comprises supplying the electrolytic solution into the anode chamber to increase an amount of the anolyte in the anode chamber to thereby cause the anolyte to overflow the anode chamber into the Sn alloy plating solution.
  • the Sn alloy plating method further includes circulating the Sn alloy plating solution in the cathode chamber.
  • the Sn alloy plating method further includes controlling an amount of the electrolytic solution or pure water to be supplied into the anode chamber based on the concentration of the acid in the anolyte held in the anode chamber.
  • the Sn alloy plating method further includes determining the concentration of the acid in the anolyte from an initial acid concentration of the anolyte, a quantity of electricity and a current efficiency at the Sn anode, an amount of the electrolytic solution supplied, and a permeability of the anion exchange membrane with respect to methanesulfonic acid that passes through the anion exchange membrane and migrates from the cathode chamber into the anode chamber.
  • the Sn alloy plating method further includes drawing out a part of the Sn alloy plating solution from the cathode chamber; removing at least a part of the acid from the Sn alloy plating solution that has been drawn out; and then returning the Sn alloy plating solution to the cathode chamber.
  • the Sn alloy plating method further includes supplying nitrogen gas into the anolyte in the anode chamber to form nitrogen gas bubbles in the anolyte.
  • the Sn alloy plating method further includes immersing an auxiliary Sn anode in an anolyte held in an auxiliary anode chamber; immersing an auxiliary cathode in a catholyte held in an auxiliary cathode chamber that is separated from the auxiliary anode chamber by an anion exchange membrane; applying a voltage between the auxiliary Sn anode and the auxiliary cathode to produce the anolyte having an increased concentration of Sn ions; and supplying the anolyte having the increased concentration of Sn ions into the Sn alloy plating solution.
  • the electrolytic solution containing the acid that forms a complex with a divalent Sn ion is supplied into the anode chamber so that the Sn ion concentration of the anolyte in the anode chamber is kept not less than a predetermined value and the concentration of the acid does not become lower than an acceptable value.
  • the concentration of Sn ions and the concentration of the acid in the anolyte can thus be appropriately controlled.
  • the anolyte, whose amount has been increased by the supply of the electrolytic solution, in the anode chamber is supplied to the Sn alloy plating solution.
  • the anolyte having a high Sn ion concentration and in which divalent Sn ions exist stably, is supplied to the Sn alloy plating solution. This makes it possible to stably replenish the Sn alloy plating solution with Sn ions.
  • FIG. 1 is a schematic view of an Sn alloy plating apparatus according to an embodiment
  • FIG. 2 is a perspective view of an exemplary anode bath configured to cause an anolyte to overflow the bath;
  • FIG. 3 is a cross-sectional view of a main portion of another exemplary anode bath configured to cause an anolyte to overflow the bath;
  • FIG. 4 is a perspective view of a main portion of yet another exemplary anode bath configured to cause an anolyte to overflow the bath;
  • FIG. 5 is a schematic perspective view of a substrate holder shown in FIG. 1 ;
  • FIG. 6 is a plan view of the substrate holder shown in FIG. 1 ;
  • FIG. 7 is a right side view of the substrate holder shown in FIG. 1 ;
  • FIG. 8 is an enlarged view of the portion A of FIG. 7 ;
  • FIG. 9 is a diagram illustrating a main portion of the Sn alloy plating apparatus when performing the plating process.
  • FIG. 10 is a graph showing a theoretical Sn ion concentration of an anolyte in an anode chamber, calculated from a quantity of electricity, in comparison with actually measured Sn ion concentration of the anolyte;
  • FIG. 11 is a schematic view of another example of a plating bath
  • FIG. 12 is a schematic view of an Sn alloy plating apparatus according to another embodiment.
  • FIG. 13 is a schematic view of an Sn alloy plating apparatus according to yet another embodiment
  • FIG. 14 is a schematic view of an Sn alloy plating apparatus according to yet another embodiment.
  • FIG. 15 is a schematic view of an Sn alloy plating apparatus according to yet another embodiment.
  • the following embodiment illustrates an exemplary case where Ag (silver) is used as a metal which is nobler than Sn (tin) and a film of an Sn—Ag alloy is formed on a substrate surface.
  • Methanesulfonic acid is used as an acid that forms a complex with a divalent Sn ion.
  • an Sn—Ag alloy plating solution which contains tin methanesulfonate as a source of Sn ions (Sn 2+ ) and silver methanesulfonate as a source of Ag ions (Ag + ). It is also possible to use silver alkylsulfonate as a source of Ag ions (Ag + ).
  • FIG. 1 is a schematic view of an Sn alloy plating apparatus according to an embodiment.
  • the Sn alloy plating apparatus includes a plating bath 16 in which a box-shaped anode bath 10 is disposed.
  • the interior of the plating bath 16 is divided by the anode bath 10 into a cathode chamber 12 and an anode chamber 14 which is defined in the anode bath 10 .
  • the cathode chamber 12 is coupled via an overflow bath 36 , which will be described later, to a plating solution supply line 20 extending from a plating solution supply source 18 .
  • the cathode chamber 12 is configured to hold an Sn—Ag alloy plating solution (hereinafter referred to simply as a plating solution) Q therein.
  • a substrate W which is detachably held by a substrate holder 22 and serves as a cathode during plating thereof, is put at a predetermined position in the cathode chamber 12 and immersed in the plating solution Q when plating of the substrate W is performed.
  • An anolyte supply line 23 , an electrolytic solution supply line 24 , a pure water supply line 26 , and a liquid discharge line 28 are coupled to the anode chamber 14 .
  • the anode chamber 14 is configured to hold an anolyte E therein.
  • a soluble Sn anode 32 which is made of Sn and held by an anode holder 30 , is disposed at a predetermined position in the anode chamber 14 and immersed in the anolyte E.
  • an N 2 gas supply line 33 for supplying nitrogen gas into the anolyte E to form nitrogen gas bubbles in the anolyte E is provided at a bottom of the anode chamber 14 .
  • a solution, containing Sn ions and methanesulfonic acid that forms a complex with a divalent Sn ion and not containing Ag ions, is used as the anolyte E.
  • a part of methanesulfonate ions in the anolyte E surrounds the divalent Sn ion to form the complex with the Sn ion, while the other part of methanesulfonate ions exists as a free acid in the anolyte E.
  • the methanesulfonic acid concentration herein refers to the concentration of the free acid unless otherwise stated.
  • An aqueous solution containing methanesulfonic acid i.e., an aqueous methanesulfonic acid solution
  • an electrolytic solution which is supplied into the anode chamber 14 through the electrolytic solution supply line 24 .
  • the Sn anode 32 When carrying out plating of the substrate W, the Sn anode 32 is electrically connected to a positive pole of a plating power source 34 , and a conductive layer (not shown), such as a seed layer, formed on the surface of the substrate W is electrically connected to a negative pole of the plating power source 34 .
  • a metal film of an Sn—Ag alloy is formed on the surface of the conductive layer. This metal film may be used for lead-free solder bumps.
  • the plating bath 16 is provided with the overflow bath 36 which is located adjacent to the cathode chamber 12 .
  • the plating solution Q is allowed to overflow the top of the cathode chamber 12 into the overflow bath 36 .
  • One end of a plating solution circulation line 46 is coupled to the bottom of the overflow bath 36 , and the other end of the plating solution circulation line 46 is coupled to the bottom of the cathode chamber 12 .
  • the plating solution circulation line 46 is provided with a pump 38 , a heat exchanger (temperature regulator) 40 , a filter 42 , and a flow meter 44 .
  • the plating solution supply line 20 extending from the plating solution supply source 18 is coupled to the top of the overflow bath 36 .
  • a regulation plate 50 for regulating a distribution of electric potential in the cathode chamber 12 is disposed in the cathode chamber 12 .
  • This regulation plate 50 is located between the substrate holder 22 , disposed in the cathode chamber 12 , and the Sn anode 32 .
  • the regulation plate 50 is made of vinyl chloride, which is a dielectric material, and has a central hole 50 a having such a size as to sufficiently restrict spreading of an electric field.
  • a lower end of the regulation plate 50 reaches the bottom plate of the cathode chamber 12 .
  • a vertically-extending agitating paddle 52 serving as an agitating tool is disposed in the cathode chamber 12 at a position between the substrate holder 22 , disposed in the cathode chamber 12 , and the regulation plate 50 .
  • This agitating paddle 52 is configured to make a reciprocating movement parallel to the substrate W so as to agitate the plating solution Q that exists between the substrate holder 22 and the regulation plate 50 .
  • An anion exchange membrane 54 is incorporated in a cathode-chamber-side wall 10 a of the anode bath 10 which divides the interior of the plating bath 16 into the cathode chamber 12 and the anode chamber 14 .
  • the cathode chamber 12 and the anode chamber 14 are isolated by the anion exchange membrane 54 .
  • a commercially-available product AAV manufactured by AGC Engineering Co., Ltd., for example, can be used as the anion exchange membrane 54 .
  • the number of anion exchange membranes 54 and their arrangement may be arbitrarily adjusted depending on the necessary membrane area and an amount of permeation of water molecules, which will be described later.
  • the anion exchange membrane 54 is incorporated into the wall 10 a in a liquid-tight manner, e.g., by use of an O-ring so that the plating solution Q in the cathode chamber 12 will not enter the anode chamber 14 .
  • the wall 10 a and the anion exchange membranes 54 are arranged between the Sn anode 32 and the substrate W.
  • the wall 10 a functions as an overflow weir which stems the anolyte E in the anode chamber 14 and allows the anolyte E to overflow the top of the wall 10 a into the cathode chamber 12 .
  • the anolyte E is stemmed by the wall (overflow weir) 10 a and stored in the anode chamber 14 at a predetermined liquid level H (see FIG. 9 ). After the liquid level H is reached, the anolyte E overflows the top of the wall 10 a into the anode chamber 14 .
  • This plating solution supply pipe 64 is located downstream of the flow meter 44 .
  • a plating solution discharge pipe 66 extending from the dialysis cell 62 , is coupled to a top of the overflow bath 36 .
  • the plating solution supply pipe 64 and the plating solution discharge pipe 66 constitute a plating solution dialysis line 68 that is coupled to the plating solution circulation line 46 and takes in a part of the plating solution Q from the plating solution circulation line 46 to cause the plating solution Q to circulate therethrough.
  • a pure water supply line 70 for supplying pure water into the dialysis cell 62 and a pure water drainage line 72 for discharging the pure water from the dialysis cell 62 are coupled to the dialysis cell 62 .
  • the plating solution Q flowing through the plating solution dialysis line 68 , is supplied into the dialysis cell 42 , where at least a part of the methanesulfonic acid as a free acid is removed by dialysis using the anion exchange membrane 60 .
  • the plating solution Q after dialysis is returned to the overflow bath 36 .
  • the methanesulfonic acid that has been removed from the plating solution Q by the dialysis diffuses into the pure water supplied into the dialysis cell 62 through the pure water supply line 70 , and is discharged to the exterior of the dialysis cell 62 through the pure water drainage line 72 .
  • the anion exchange membrane 60 used in this embodiment is DSV manufactured by AGC Engineering Co., Ltd.
  • An arbitrary number of anion exchange membranes 60 may be incorporated in the dialysis cell 62 depending on the amount of the plating solution to be dialyzed (i.e., the amount of the methanesulfonic acid to be removed).
  • At least a part of the methanesulfonic acid as a free acid in the plating solution Q is removed by using the dialysis cell 62 that employs the diffusion dialysis. It is also possible to remove at least a part of the methanesulfonic acid from the plating solution Q by using a free-acid removal cell that employs electrodialysis or an ion-exchange resin method.
  • the plating solution circulation line 46 is provided with an Sn ion concentration measuring device 74 for measuring the Sn ion concentration of the plating solution Q flowing through the plating solution circulation line 46 .
  • the plating solution circulation line 46 is further provided with a methanesulfonic acid concentration measuring device 76 for measuring the methanesulfonic acid concentration of the plating solution Q flowing through the plating solution circulation line 46 .
  • the output of the Sn ion concentration measuring device 74 and the output of the methanesulfonic acid concentration measuring device 76 are inputted into the plating solution supply source 18 and a controller 80 .
  • FIG. 2 is a perspective view of the anode bath 10 .
  • a cutout portion 10 b which serves as an outlet for allowing the anolyte E to overflow the anode chamber 14 .
  • the liquid level H (see FIG. 9 ) of the anolyte E held in the anode chamber 14 is determined by the position of a lower end of the cutout portion 10 b.
  • the electrolytic solution supply line 24 extends downward along the side of the anode bath 10 .
  • the electrolytic solution supply line 24 has at its lower end an electrolytic solution supply outlet 24 a for supplying the electrolytic solution (aqueous methanesulfonic acid solution) into the anode chamber 14 .
  • This electrolytic solution supply outlet 24 a reaches the bottom of the anode bath 10 and opens in a horizontal direction.
  • the pure water supply line 26 extends downward along the side of the anode bath 10 .
  • the pure water supply line 26 has at its lower end a pure water supply outlet 26 a for supplying pure water into the anode chamber 14 .
  • This pure water supply outlet 26 a reaches the bottom of the anode bath 10 and opens in a horizontal direction.
  • the electrolytic solution supply outlet 24 a and the pure water supply outlet 26 a may open in a downward direction.
  • the electrolytic solution supply outlet 24 a and the pure water supply outlet 26 a are diagonally opposite to the cutout portion 10 b of the wall 10 a so that when the pure water or the electrolytic solution is supplied into the anode chamber 14 through the pure water supply line 26 or the electrolytic solution supply line 24 , the anolyte E containing Sn ions is agitated sufficiently by the supplied pure water or electrolytic solution and then overflows the cutout portion 10 b into the cathode chamber 12 .
  • the N 2 gas supply line 33 extends downward along the side of the anode bath 10 to reach the bottom of the anode bath 10 , and further extends horizontally over approximately the entire length of the anode bath 10 in its longitudinal direction. Nitrogen gas is released or ejected upward through jet orifices 33 a , which are provided in the N 2 gas supply line 33 , to cause the anolyte E to bubble, thereby sufficiently agitating the anolyte E in the anode chamber 14 .
  • the bubbles of the nitrogen gas can promote uniform distribution of the Sn ions and the methanesulfonic acid throughout the anolyte E in the anode chamber 14 and, in addition, can prevent oxidation of the Sn ions in the anolyte E.
  • the nitrogen gas is preferably supplied into the anolyte E at the bottom of the anode chamber 14 to cause the bubbling of the anolyte E from the bottom of the anode chamber 14 .
  • This enables the anolyte E, containing Sn ions in a sufficiently dispersed state, to overflow the wall 10 a into the cathode chamber 12 while preventing the anolyte E from being excessively diluted with the pure water or the electrolytic solution supplied.
  • a liquid level detection sensor 82 for detecting the liquid level of the anolyte E in the anode chamber 14 is provided above the anode chamber 14 .
  • the pure water may be supplied into the anolyte E in the anode chamber 14 through the pure water supply line 26 . This makes it possible to keep the anolyte E in the anode chamber 14 at a constant liquid level. Further, it is possible to control the amount of Sn ions to be supplied to the cathode chamber 12 with the amount of the pure water or the electrolytic solution to be supplied into the anode chamber 14 .
  • a mechanical structure may be used to cause the anolyte E in the anode chamber 14 to overflow into the cathode chamber 12 .
  • a float 84 may be put on the anolyte E in the anode chamber 14 and may be submerged into the anolyte E so as to cause the anolyte E to overflow into the cathode chamber 12 with an amount corresponding to a volume of the float 84 .
  • This structure involves no supply of pure water or the electrolytic solution, and thus no introduction of water into the anolyte E. Therefore, the anolyte E can be supplied into the cathode chamber 12 without dilution of the anolyte E.
  • a vertically movable weir 86 may be provided in a rectangular cutout portion 10 c that is formed in the top of the wall 10 a that serves as the overflow weir.
  • the anolyte E can be supplied into the cathode chamber 12 by lowering the movable weir 86 .
  • This structure also has the advantage of no dilution of the anolyte E when supplied into the cathode chamber 12 .
  • an auxiliary electrolytic cell 100 for replenishment of the Sn ions is provided separately from the plating bath 16 .
  • a box-shaped cathode bath 102 is disposed in the auxiliary electrolytic cell 100 , whereby the interior of the auxiliary electrolytic cell 100 is divided into an anode chamber (i.e., auxiliary anode chamber) 104 and a cathode chamber (i.e., auxiliary cathode chamber) 106 defined in the cathode bath 102 .
  • An anion exchange membrane 108 is incorporated in an anode-chamber-side wall 102 a of the cathode bath 102 which divides the interior of the auxiliary electrolytic cell 100 into the anode chamber 104 and the cathode chamber 106 .
  • the anode chamber 104 and the cathode chamber 106 are isolated by the anion exchange membrane 108 .
  • An anolyte supply line 110 for supplying an anolyte A containing Sn ions and methanesulfonic acid and not containing Ag ions, and an electrolytic solution supply line 112 for supplying an electrolytic solution comprising an aqueous solution containing methanesulfonic acid (i.e., aqueous methanesulfonic acid solution) are coupled to the anode chamber 104 .
  • An Sn anode (i.e., auxiliary Sn anode) 118 which is held by an anode holder 116 , is disposed in the anode chamber 104 and immersed in the anolyte A.
  • One end of an Sn ion replenishing line 114 is coupled to the anode chamber 104 , and the other end of the Sn ion replenishing line 114 is coupled to the top of the overflow bath 36 of the plating bath 16 .
  • the Sn ion replenishing line 114 is provided with a pump 120 .
  • a catholyte supply line 122 for supplying a catholyte B comprising an aqueous solution containing methanesulfonic acid (i.e., aqueous methanesulfonic acid solution), and a liquid discharge line 124 for discharging the catholyte B are coupled to the cathode chamber 106 .
  • a cathode (i.e., an auxiliary cathode) 128 which is made of e.g. SUS and held by a cathode holder 126 , is disposed in the cathode chamber 106 and immersed in the catholyte B.
  • the above-described wall 102 a and the anion exchange membrane 108 are located between the Sn anode 118 and the cathode 128 .
  • the anolyte A containing Sn ions at a high concentration (e.g. 220 g/L to 350 g/L) and methanesulfonic acid and not containing Ag ions, is supplied into the anode chamber 104 through the anolyte supply line 110 , thereby immersing the Sn anode 118 in the anolyte A.
  • the catholyte B containing an aqueous methanesulfonic acid solution is supplied into the cathode chamber 106 through the catholyte supply line 122 , thereby immersing the cathode 128 in the catholyte B.
  • a positive pole and a negative pole of an auxiliary power source 130 are electrically connected to the Sn anode 118 and the cathode 128 , respectively, to start electrolysis.
  • the Sn ion concentration of the anolyte A increases as a result of the dissolution of Sn ions from the Sn anode 118 .
  • the anode chamber 104 and the cathode chamber 106 are isolated by the anion exchange membrane 108 , the Sn ions do not migrate into the cathode chamber 106 and therefore the cathode 128 is not plated.
  • the anolyte A does not contain Ag ions, displacement deposition of Ag on the surface of the Sn anode 118 does not occur.
  • the Sn ions in the anolyte A are supplied through the anolyte supply line 110 before the start of electrolysis, while the Sn ions are supplied by the dissolution from the Sn anode 118 after the start of electrolysis.
  • the pump 120 is driven to supply the anolyte A into the overflow bath 36 of the plating bath 16 through the Sn ion replenishing line 114 .
  • the amount of the anolyte A in the anode chamber 104 decreases as a result of the supply of the anolyte A to the overflow bath 36 .
  • the electrolytic solution in an amount that compensates for the decrease in the amount of the anolyte A, is supplied into the anode chamber 104 through the electrolytic solution supply line 112 .
  • the Sn ion concentration of the anolyte A is preferably as high as possible from the viewpoint of decreasing the amount of waste liquid discharged from the entire system.
  • Methanesulfonate ions contained in the catholyte B in the cathode chamber 106 pass through the anion exchange membrane 108 and migrate into the anode chamber 104 . Accordingly, the conductivity of the catholyte B in the cathode chamber 106 decreases with time. Therefore, a fresh catholyte B is supplied into the cathode chamber 106 through the catholyte supply line 122 , while discharging the catholyte B from the cathode chamber 106 to the exterior through the liquid discharge line 124 so that the catholyte B does not overflow.
  • the substrate holder 22 includes a first holding member 154 having a rectangular plate shape and made of e.g., vinyl chloride, and a second holding member 158 rotatably coupled to the first holding member 154 through a hinge 156 which allows the second holding member 158 to open and close with respect to the first holding member 154 .
  • the second holding member 158 is configured to be openable and closable through the hinge 156 , it is also possible to dispose the second holding member 158 opposite to the first holding member 154 and to move the second holding member 158 away from and toward the first holding member 154 to thereby open and close the second holding member 158 .
  • the second holding member 158 includes a base portion 160 and a ring-shaped seal holder 162 .
  • the seal holder 162 is made of vinyl chloride so as to enable a retaining ring 164 , which will be described later, to slide well.
  • An annular substrate-side sealing member 166 (see FIGS. 7 and 8 ) is fixed to an upper surface of the seal holder 162 . This substrate-side sealing member 166 is placed in pressure contact with a periphery of the surface of the substrate W to seal a gap between the substrate W and the second holding member 158 when the substrate W is held by the substrate holder 22 .
  • An annular holder-side sealing member 168 (see FIGS.
  • This holder-side sealing member 168 is placed in pressure contact with the first holding member 154 to seal a gap between the first holding member 154 and the second holding member 158 .
  • the holder-side sealing member 168 is located outwardly of the substrate-side sealing member 166 .
  • the substrate-side sealing member 166 is sandwiched between the seal holder 162 and a first mounting ring 170 a which is secured to the seal holder 162 by fastening tools 169 a , such as bolts.
  • the holder-side sealing member 168 is sandwiched between the seal holder 162 and a second mounting ring 170 b which is secured to the seal holder 162 by fastening tools 169 b , such as bolts.
  • the seal holder 162 of the second holding member 158 has a stepped portion at a periphery thereof, and the retaining ring 164 is rotatably mounted to the stepped portion through a spacer 165 .
  • the retaining ring 164 is inescapably held by an outwardly projecting retaining plates 172 (see FIG. 6 ) mounted to a side surface of the seal holder 162 .
  • This retaining ring 164 is made of a material (e.g., titanium) having high rigidity and excellent acid and alkali corrosion resistance and the spacer 165 is made of a material having a low friction coefficient, for example PTFE, so that the retaining ring 164 can rotate smoothly.
  • Inverted L-shaped clampers 174 each having an inwardly projecting portion and located outside of the retaining ring 164 , are provided on the first holding member 154 at equal intervals along a circumferential direction of the retaining ring 164 .
  • the retaining ring 164 has outwardly projecting portions 164 b arranged along the circumferential direction of the retaining ring 164 at positions corresponding to positions of the dampers 174 .
  • a lower surface of the inwardly projecting portion of each damper 174 and an upper surface of each projecting portion 164 b of the retaining ring 164 are tapered in opposite directions along the rotational direction of the retaining ring 164 .
  • a plurality (e.g., three) of upwardly protruding dots 164 a are provided on the retaining ring 164 in predetermined positions along the circumferential direction of the retaining ring 164 .
  • the retaining ring 164 can be rotated by pushing and moving each dot 164 a from a lateral direction by means of a rotating pin (not shown).
  • the substrate W is inserted into the central portion of the first holding member 154 , and the second holding member 158 is then closed through the hinge 156 .
  • the retaining ring 164 is rotated clockwise so that each projecting portion 164 b of the retaining ring 164 slides into the inwardly projecting portion of each damper 174 .
  • the first holding member 154 and the second holding member 158 are fastened to each other and locked by engagement between the tapered surfaces of the retaining ring 164 and the tapered surfaces of the dampers 174 .
  • the lock of the second holding member 158 can be released by rotating the retaining ring 164 counterclockwise and to disengage the projecting portions 164 b of the retaining ring 164 from the inverted L-shaped dampers 174 .
  • the downwardly-protruding portion of the substrate-side sealing member 166 is placed in pressure contact with the periphery of the surface of the substrate W.
  • the substrate-side sealing member 166 is pressed uniformly against the substrate W to thereby seal the gap between the periphery of the surface of the substrate W and the second holding member 158 .
  • the downwardly-protruding portion of the holder-side sealing member 168 is placed in pressure contact with the surface of the first holding member 154 .
  • the sealing holder-side sealing member 168 is uniformly pressed against the first holding member 154 to thereby seal the gap between the first holding member 154 and the second holding member 158 .
  • a pair of T-shaped holder hangers 190 are provided on end portions of the first holding member 154 . These holder hangers 190 serve as a support when the substrate holder 22 is transported and when the substrate holder 22 is held in a suspended state.
  • a protruding portion 182 is formed on the upper surface of the first holding member 154 so as to protrude in a ring shape corresponding to a size of the substrate W.
  • the protruding portion 182 has an annular support surface 180 which is placed in contact with the periphery of the substrate W to support the substrate W.
  • the protruding portion 182 has recesses 184 arranged at predetermined positions along a circumferential direction of the protruding portion 182 .
  • a plurality of electrical conductors (electrical contacts) 186 (e.g., 12 conductors as illustrated), coupled respectively to wires extending from external contacts (not shown) provided in the holder hanger 190 , are disposed in the recesses 184 of the protruding portion 182 .
  • electrical conductors 186 resiliently contact the lower portions of the electrical contacts 188 shown in FIG. 8 .
  • the electrical contacts 188 which are to be electrically connected to the electrical conductors 186 , are secured to the seal holder 162 of the second holding member 158 by fastening tools 189 , such as bolts.
  • the electrical contacts 188 each have a leaf spring-like contact portion lying outside the substrate-side sealing member 166 and projecting inwardly. This contact portion is springy and bends easily.
  • the contact portions of the electrical contacts 188 make elastic contact with the peripheral surface of the substrate W supported on the support surface 180 of the first holding member 154 .
  • the second holding member 158 is opened and closed by a not-shown pneumatic cylinder and by the weight of the second holding member 158 itself. More specifically, the first holding member 154 has a through-hole 154 a , and a pneumatic cylinder is provided so as to face the through-hole 154 a . The second holding member 158 is opened by extending a piston rod of the pneumatic cylinder through the through-hole 154 a to push up the seal holder 162 of the second holding member 158 . The second holding member 158 is closed by its own weight when the piston rod is retracted.
  • the pump 38 is set in motion to circulate the plating solution Q in the cathode chamber 12 through the plating solution circulation line 46 to thereby agitate the plating solution Q.
  • the substrate W held by the substrate holder 22 , is put at the predetermined position in the cathode chamber 12 and immersed in the plating solution Q.
  • the anode chamber 14 is filled with the initial anolyte E so that the Sn anode 32 is immersed in the anolyte E.
  • the Sn anode 32 is electrically connected to the positive pole of the plating power source 34 , and a conductive layer, such as a seed layer, formed on the surface of the substrate W is electrically connected to the negative pole of the plating power source 34 to start plating of the surface of the substrate W.
  • the agitating paddle (agitating tool) 52 reciprocates or oscillates parallel to the substrate W, as necessary, to agitate the plating solution Q in the cathode chamber 12 .
  • the nitrogen gas is supplied into the anolyte E through the N 2 gas supply line 33 to form the bubbles of the nitrogen gas in the anolyte E in the anode chamber 14 .
  • Sn ions dissolve from the Sn anode 32 into the anolyte E in the anode chamber 14 as shown in FIG. 9 .
  • the dissolution of the Sn ions occurs every time plating of a substrate is performed, and therefore the Sn ion concentration of the anolyte E in the anode chamber 14 increases.
  • the volume of the anolyte E in the anode chamber 14 increases when the electrolytic solution or the pure water is supplied into the anode chamber 14 from the electrolytic solution supply line 24 or the pure water supply line 26 .
  • the anolyte E in the anode chamber 14 rises over the predetermined liquid level H by ⁇ H, the anolyte E overflows the cutout portion 10 b (see FIG. 2 ) formed in the wall 10 a of the anode chamber 14 and flows into the cathode chamber 12 by an amount corresponding to the increase ⁇ H in the liquid level. Therefore, some of the Sn ions in the anode chamber 14 are supplied into the cathode chamber 12 , and can compensate for the shortage of the Sn ions that have been consumed in plating of the substrate W.
  • the plating solution Q is discharged in advance by an amount corresponding to the amount of the anolyte E supplied into the cathode chamber 12 .
  • the methanesulfonic acid in the cathode chamber 12 passes through the anion exchange membrane 54 into the anode chamber 14 .
  • This migration also increases the amount of the anolyte E in the anode chamber 14 , and as a result the anolyte E overflows the wall 10 a into the cathode chamber 12 by an amount exceeding the predetermined liquid level H. In this manner, the Sn ions in the anode chamber 14 can be supplied into the cathode chamber 12 .
  • the present inventors have verified through experiments the fact that the concentration of methanesulfonic acid as a free acid in the anolyte E in the anode chamber 14 is important for stabilizing the Sn ions that have dissolved from the Sn anode.
  • an experiment was conducted in which an anolyte of an aqueous methanesulfonic acid solution, initially having a methanesulfonic acid concentration of 100 g/L, was supplied in an anode chamber at the start of electrolysis. In this case, the anolyte in the anode chamber was found to become cloudy as the electrolysis was continued. This indicates that Sn ions cannot exist stably as divalent ions in the anolyte, and precipitate as metal Sn or tetravalent Sn ions are generated.
  • the anolyte in the anode chamber did not become cloudy during the electrolysis.
  • the Sn ion concentration of the anolyte agreed with a calculation value that was determined on condition that Sn has dissolved as divalent Sn ions. This indicates that because of the presence of a sufficient amount of methanesulfonate ions in the anolyte, divalent Sn ions exist stably in the form of a complex surrounded by methanesulfonate ions.
  • the methanesulfonic acid concentration of the anolyte should preferably be controlled in such a range as to allow the divalent Sn ions to exist stably in the anolyte.
  • the anolyte E in the anode chamber 14 can overflow into the cathode chamber 12 to supply Sn ions to the cathode chamber 12 .
  • the plating apparatus of this embodiment is also provided with the electrolytic solution supply line 24 for supplying the electrolytic solution (the aqueous methanesulfonic acid solution) into the anode chamber 14 . This is because of the following reasons.
  • the methanesulfonic acid in the anolyte 14 flows into the cathode chamber 12 , and therefore the methanesulfonic acid concentration of the anolyte E in the anode chamber 14 decreases.
  • the methanesulfonic acid in the cathode chamber 12 passes through the anion exchange membrane 54 and migrates into the anode chamber 14 by forming an electric field between the Sn anode 32 and the substrate W as a cathode.
  • the transference number of methanesulfonic acid is not 100%, but can be 50% to 90% due to a loss, although it depends on conditions.
  • a ratio of the mol concentration of the methanesulfonic acid that passes through the anion exchange membrane 54 into the anode chamber 14 to the mol concentration of Sn ions that dissolve from the Sn anode 32 into the anolyte E in the anode chamber 14 will deviate from 1:2. Consequently, the methanesulfonic acid concentration of the anolyte E in the anode chamber 14 will decrease, whereby Sn ions in the anode chamber 14 may become unstable as described above.
  • the anolyte E In order to operate the plating apparatus efficiently, it is desirable to supply the anolyte E into the cathode chamber 12 by causing the anolyte E to overflow the anode chamber 14 while keeping the Sn ion concentration of the anolyte E in the anode chamber 14 as high as possible. If the anolyte E with a low Sn ion concentration is supplied into the cathode chamber 12 , a larger amount (overflow amount) of the anolyte E needs to be supplied from the anode chamber 14 in order to supply a certain amount of Sn ions into the cathode chamber 12 . As a result, a larger amount of the plating solution Q should be discharged from the circulation system including the cathode chamber 12 , making the plating process uneconomical.
  • the Sn ion concentration of the anolyte E in the anode chamber 14 is controlled typically in the range of 80 g/L to 500 g/L, preferably in the range of 200 g/L to 400 g/L, more preferably in the range of 220 g/L to 350 g/L.
  • the Sn ion concentration of the anolyte E can be determined from the Sn ion concentration of a fresh anolyte E which has been put into the anode chamber 14 before the start of plating and the Sn ion concentration converted from the quantity of electricity at the Sn anode 32 after the start of plating.
  • the Sn ion concentration of the anolyte E is of significant importance for controlling the concentration of Sn ions in the entire plating bath.
  • the Sn ion concentration of the Sn—Ag plating solution Q is usually 50 g/L to 80 g/L.
  • the amount of the plating solution Q in the cathode chamber 12 usually decreases due to evaporation of the solution, etc.
  • the anolyte E in the anode chamber 14 is supplied to the plating solution Q in the cathode chamber 12 in an amount more than the decrease in the amount of the plating solution Q, the excess amount of the plating solution Q needs to be finally discharged from the cathode chamber 12 .
  • the Sn ion concentration of the anolyte E cannot be increased to a value more than a saturation concentration of tin methanesulfonate. Further, the Sn ion concentration of the anolyte E should be kept less than the saturation concentration in order for the Sn ions to exist stably.
  • the pure water supply line 26 is used not only for supplying the pure water into the anode chamber 14 when replenishing the anode chamber 14 with water by an amount corresponding to the amount of evaporated water, but also for causing the anolyte E in the anode chamber 14 to overflow the wall 10 a so as to supply the Sn ions to the cathode chamber 12 when the methanesulfonic acid concentration of the anolyte E in the anode chamber 14 is sufficiently high. Further, the pure water supply line 26 is used for supplying the pure water into the anode chamber 14 so as to adjust the concentration of a component of the anolyte E in the anode chamber 14 .
  • the anolyte E containing Sn ions at a high concentration (e.g., 220 g/L to 350 g/L) and methanesulfonic acid, is supplied into the anode chamber 14 to fill the anode chamber 14 with the anolyte E.
  • a high concentration e.g., 220 g/L to 350 g/L
  • methanesulfonic acid is supplied into the anode chamber 14 to fill the anode chamber 14 with the anolyte E.
  • the pump 38 is actuated to circulate the plating solution Q in the cathode chamber 12 through the plating solution circulation line 46 , thereby agitating the plating solution Q in the cathode chamber 12 .
  • a substrate W which is held by the substrate holder 22 , is put at a predetermined position in the cathode chamber 12 and immersed in the plating solution Q.
  • the Sn anode 32 is electrically connected to the positive pole of the plating power source 34 , and a conductive layer, such as a seed layer, formed on the surface of the substrate W is electrically connected to the negative pole of the plating power source 34 to start plating of the surface of the substrate W.
  • the agitating paddle (agitating tool) 52 is caused to make a reciprocating movement parallel to the substrate W, as necessary, so as to agitate the plating solution Q in the cathode chamber 12 .
  • the nitrogen gas is supplied into the anolyte E in the anode chamber 14 through the N 2 gas supply line 33 to form nitrogen gas bubbles in the anolyte E.
  • the Sn ion concentration of the plating solution Q is measured by the Sn ion concentration measuring device 74 , and a signal of the measurement results (i.e., a measurement value) is sent to the controller 80 .
  • the controller 80 estimates the methanesulfonic acid concentration of the anolyte E in the anode chamber 14 and, based on the estimated value, determines whether to supply the electrolytic solution into the anode chamber 14 through the electrolytic solution supply line 24 or to supply the pure water into the anode chamber 14 through the pure water supply line 26 , or to supply both the electrolytic solution and the pure water.
  • the electrolytic solution containing the methanesulfonic acid
  • the electrolytic solution supply line 24 so that the methanesulfonic acid concentration of the anolyte E does not become lower than a lower limit value.
  • the pure water is supplied into the anode chamber 14 through the pure water supply line 26 .
  • the supply of the pure water into the anode chamber 14 causes the anolyte E to overflow into the cathode chamber 12 , thereby supplying Sn ions to the plating solution Q in the cathode chamber 12 .
  • the concentration of methanesulfonic acid as a free acid contained in the anolyte E in the anode chamber 14 is controlled to be not less than 30 g/L, so that the Sn ions at a high concentration, e.g., 220 g/L to 350 g/L, can exist stably as divalent ions.
  • the methanesulfonic acid concentration of the anolyte E is high, the supply of the anolyte E to the plating solution Q can appreciably increase the methanesulfonic acid concentration of the plating solution Q in the cathode chamber 12 , which may result in poor film-thickness uniformity in the plating process as will be described later. Therefore, the methanesulfonic acid concentration of the plating solution Q is controlled so as not to exceed a particular value which is determined by taking the actual operating conditions of the apparatus into consideration.
  • the concentration of methanesulfonic acid as a free acid in the plating solution Q in the cathode chamber 12 varies with the quantity of electricity and the current efficiency at the Sn anode 32 , the amount of the anolyte E that has overflowed into the plating solution Q, the amount of waste liquid (drain-out) discharged from the plating solution circulation line 46 , and the permeability of the anion exchange membrane 54 with respect to the methanesulfonic acid.
  • the film-thickness uniformity in plating of the substrate tends to be poor when the methanesulfonic acid concentration of the plating solution Q in the cathode chamber 12 exceeds about 250 g/L.
  • the methanesulfonic acid concentration measuring device 76 detects that the methanesulfonic acid concentration of the plating solution Q in the cathode chamber 12 exceeds an upper limit value, the plating solution Q is forced to flow into the plating solution dialysis line 68 having the dialysis cell 62 , which removes the methanesulfonic acid from the plating solution Q.
  • the plating solution Q, from which the methanesulfonic acid has been removed, is returned to the overflow bath 36 .
  • the dialysis of the plating solution Q in the dialysis cell 62 can adjust the methanesulfonic acid concentration of the plating solution Q preferably in the range of 60 g/L to 250 g/L, more preferably in the range of 90 g/L to 150 g/L.
  • the concentration of the methanesulfonic acid as a free acid in the anolyte E during operation of the Sn alloy plating apparatus may be controlled based on an estimated value of the methanesulfonic acid concentration of the anolyte E in the anode chamber 14 .
  • This estimated value of the methanesulfonic acid concentration can be determined theoretically or experimentally from an initial methanesulfonic acid concentration of the anolyte E, the quantity of electricity and the current efficiency at the Sn anode 32 , the amount of the electrolytic solution supplied through the electrolytic solution supply line 24 , the amount of pure water supplied through the pure water supply line 26 , and the permeability of the anion exchange membrane 54 with respect to the methanesulfonic acid that passes through the anion exchange membrane 54 and migrates from the cathode chamber 12 into the anode chamber 14 .
  • the Sn ion concentration and the methanesulfonic acid concentration of the anolyte E in the anode chamber 14 can be estimated from a curve of the amount of dissolved Sn ions associated with the quantity of electricity during plating and from the permeability of the anion exchange membrane with respect to the acid.
  • the anolyte E containing Sn ions at a high concentration (e.g., 220 g/L to 350 g/L) and methanesulfonic acid, is supplied into the anode chamber 14 .
  • a high concentration e.g. 220 g/L to 350 g/L
  • methanesulfonic acid is supplied into the anode chamber 14 .
  • the electrolytic solution is supplied into the anode chamber 14 through the electrolytic solution supply line 24 to cause the anolyte E to overflow the wall 10 a , thereby replenishing the plating solution Q in the cathode chamber 12 with Sn ions.
  • a predetermined threshold value e.g. 300 g/L
  • the Sn ion concentration of the anolyte E in the anode chamber 14 decreases as a result of the supply of the electrolytic solution, the Sn ion concentration increases gradually during plating and eventually reaches the threshold value.
  • Sn ions in the plating solution Q are consumed in plating of the substrate W.
  • the efficiency of electrolysis at the substrate W is equal to the efficiency of electrolysis at the Sn anode 32 and that no Sn ions are discharged out of the system
  • Sn ions will dissolve from the Sn anode 32 in an amount equal to the amount of Sn ions consumed in plating of the substrate W.
  • the amount of Sn ions in the entire system is kept constant.
  • the efficiency of electrolysis decreases with the increase in the Sn ion concentration of the anolyte E in the anode chamber 14 . Accordingly, the amount of Sn ions that are supplied to the anolyte E by the dissolution from the Sn anode 32 becomes smaller than the amount of Sn ions consumed in plating, resulting in a shortage of Sn ions in the entire system.
  • FIG. 10 is a graph showing the theoretical Sn ion concentration of the anolyte E in the anode chamber 14 , calculated from the quantity of electricity, in comparison with the actually measured Sn ion concentration of the anolyte E.
  • the efficiency of electrolysis is approximately 100% when the Sn ion concentration of the anolyte E in the anode chamber 14 is not more than about 130 g/L
  • the electrolysis efficiency decreases when the Sn ion concentration is more than about 150 g/L
  • the electrolysis efficiency decreases to about 80% at an Sn ion concentration of 300 g/L.
  • the Sn alloy plating apparatus of this embodiment includes the auxiliary electrolytic cell 100 for compensating for the shortage of the Sn ions in the entire system.
  • the electrolysis operation of the auxiliary electrolytic cell 100 is started simultaneously with the start of operation of the Sn alloy plating apparatus or at an appropriate time.
  • the pump 120 is driven based on the concentration of Sn ions measured by the Sn ion concentration measuring device 74 to thereby supply the anolyte A having a high Sn ion concentration in the anode chamber 104 to the overflow bath 36 of the plating bath 16 .
  • the supply of Sn ions from the auxiliary electrolytic cell 100 can compensate for the shortage of Sn ions caused by the difference between the electrolytic efficiency of plating on the substrate W and the efficiency of electrolysis at the Sn anode 32 in the anode chamber 14 and by the discharge of the plating solution Q from the plating bath 16 .
  • the Sn ion concentration and the methanesulfonic acid concentration of the anolyte E in the anode chamber 14 may deviate from the estimated concentrations. Therefore, the Sn concentration and the methanesulfonic acid concentration of the plating solution Q are measured by the Sn ion concentration measuring device 74 and the methanesulfonic acid concentration measuring device 76 , and their changes are recorded. If the Sn ion concentration tends to become higher or lower than a concentration as estimated from the operating conditions, then the efficiency of Sn ion dissolution, which is used for the estimation of the concentration, will be changed.
  • the permeability of the anion exchange membrane with respect to the acid will be changed. After changing such a factor(s), control of the Sn concentration and the methanesulfonic acid concentration is continued.
  • the supply of the anolyte E, containing a high concentration of Sn ions, from the anode chamber 14 to the cathode chamber 12 is preferably performed by forcing the anolyte E to overflow the anode chamber 14 , rather than by passing the anolyte E through a pipe using a dedicated pump. This is because of the following reasons.
  • the anolyte E containing Sn ions with a high concentration resides in a pipe for a long time, deposition of a metal (which is abnormal deposition) on an interior surface of the pipe will occur even when the surface of the pipe is made of an insulating material. Once the metal begins to deposit on the interior surface of the pipe, the metal tends to grow continuously on the surface. If the supply of the anolyte E from the anode chamber 14 to the cathode chamber 12 is continued in order to pass the anolyte E continuously through the pipe, then the total amount of the liquid in the cathode chamber increases. As a result, it is necessary to continuously discharge the plating solution Q from the cathode chamber by the same amount as the amount of the anolyte E supplied.
  • the above-described metal deposition in the pipe can be avoided by using the overflow method to supply the anolyte E.
  • the anolyte E in the anode chamber 14 is constantly agitated by bubbling thereof with the supply of the nitrogen gas. This can prevent deposition of a metal on the inner surface of the anode chamber 14 .
  • the anolyte E overflows the anode chamber 14 as a result of the migration of methanesulfonic acid and water molecules caused by the electrolysis.
  • the amount or volume of the anolyte E overflowing into the cathode chamber 12 is exactly equal to the amount or volume of the methanesulfonic acid and the water that have passed through the anion exchange membrane 54 .
  • FIG. 11 schematically shows a plating bath 16 a which is another example.
  • An anode holder 30 holding a disk-shaped Sn anode 32 , is disposed in the anode chamber 14 of the plating bath 16 a .
  • An annular anode mask 200 for restricting a contact area of the Sn anode 32 with anolyte E is mounted to a front surface of the anode holder 30 in a manner such that the annular anode mask 200 hermetically contact a peripheral area of the Sn anode 32 .
  • An opening 10 d is formed in the cathode-chamber-side wall 10 a of the anode bath 10 .
  • Anion exchange membrane 54 is mounted to the wall 10 a along the edge of the opening 10 d , with its peripheral portion held between a mask member 202 and the wall 10 a .
  • the mask member 202 is provided for restricting a contact area of the anion exchange membrane 54 with the plating solution Q. Since the wall 10 a and the mask member 202 hold the anion exchange membrane 54 therebetween to seal a gap along the peripheral portion of the anion exchange membrane 54 , a liquid leakage between the cathode chamber 12 and the anode chamber 14 can be prevented.
  • the anion exchange membrane 54 and the opening 10 d may have a rectangular shape, and the mask member 202 may be a rectangular ring.
  • the opening sizes of the opening 10 d and the mask member 202 may be equal to or larger than the inner diameter of the anode mask 200 .
  • the anion exchange membrane 54 may preferably contact the anolyte E or the plating solution Q at an area larger than an area at which the Sn anode 32 contacts the anolyte E.
  • An electric field shield 204 having approximately the same external shape as that of the mask member 202 and having an opening 204 a of a circular shape similar to the shape of the substrate W, is mounted to the front surface of the mask member 202 .
  • the diameter of the opening 204 a is smaller than the opening size of the mask member 202 .
  • the electric field shield 204 which is provided in the cathode chamber 12 at a position near the Sn anode 32 , can reduce a thickness of a seed layer formed on the substrate, making it possible to make the distribution of the film thickness uniform even in a case where the film thickness would otherwise be relatively large in a peripheral area of the substrate.
  • the electric field shield 204 may have a mechanism to change its opening area in order to control the film-thickness distribution.
  • the diameter of the opening 204 a of the electric field shield 204 is set equal to or smaller than the diameter of the central hole 50 a of the regulation plate 50 which is located between the substrate W and the Sn anode 32 .
  • the regulation plate 50 includes a plate 206 and a cylindrical member 208 mounted to the plate 206 .
  • the Sn alloy plating apparatus of this embodiment has a gas supply unit 210 , which is disposed above the plating bath 16 a , for promoting evaporation of water.
  • the gas supply unit 210 can evaporate water in the cathode chamber 12 with the same amount as the amount of the anolyte E supplied from the anode chamber 14 . This makes it possible to stably keep the concentrations of the components of the plating solution Q in the cathode chamber 12 , thereby eliminating the need of discharging the plating solution Q or reducing the amount of the plating solution Q to be discharged.
  • the plating solution circulation line 46 may be provided with a dewatering device, which can remove only water, so that the plating solution Q passes through the dewatering device.
  • FIG. 12 is a schematic view of the Sn alloy plating apparatus according to another embodiment.
  • the plating bath 16 b of this embodiment includes an inner bath 220 which is integral with the anode bath 10 , and overflow bath 36 provided around the inner bath 220 , and that a wall 10 e , which is adjacent to the overflow bath 36 , of the anode bath 10 functions as an overflow weir which stems the anolyte E in the anode chamber 14 and allows the anolyte E to overflow its top into the overflow bath 36 .
  • the anolyte E is stemmed by the wall (overflow weir) 10 e and held in the anode chamber 14 at a predetermined liquid level H (see FIG. 9 ). After the liquid level H is reached, the anolyte E overflows the top of the wall 10 e and flows into the overflow bath 36 surrounding the plating bath 16 b . Sn ions, which have been thus fed into the overflow bath 36 , are supplied into the cathode chamber 12 via the plating solution circulation line 46 .
  • FIG. 13 is a schematic view of the Sn alloy plating apparatus according to yet another embodiment.
  • This embodiment differs from the embodiment illustrated in FIG. 1 in that the anode bath 10 of this embodiment is provided with an anolyte circulation line 230 for drawing out a part of the anolyte in the anode chamber 14 from the bottom of the anode bath 10 and returning the anolyte to the top of the anode bath 10 .
  • the anolyte circulation line 230 is provided with a pump 232 and a methanesulfonic acid concentration measuring device 234 .
  • the pump 232 is driven to circulate the anolyte E in the anode chamber 14 through the anolyte circulation line 230 , while the methanesulfonic acid concentration measuring device 234 can measure the methanesulfonic acid concentration of the anolyte E continually or periodically.
  • FIG. 14 is a schematic view of the Sn alloy plating apparatus according to yet another embodiment.
  • This embodiment differs from the embodiment illustrated in FIG. 1 in that the liquid discharge line 28 of the plating bath 16 and the electrolytic solution supply line 112 of the auxiliary electrolytic cell 100 , shown in FIG. 1 , are coupled by a connection line 242 which is provided with a pump 240 , and that the Sn ion replenishing line 114 , extending form the anode chamber 104 of the auxiliary electrolytic cell 100 , is coupled to the top of the anode chamber 14 of the plating bath 16 .
  • the anolyte E in the anode chamber 14 of the plating bath 16 can be used as an electrolytic solution to be supplied to the anode chamber 104 of the auxiliary electrolytic cell 100 , while the anolyte A having a high Sn ion concentration in the anode chamber 104 of the auxiliary electrolytic cell 100 can be returned to the anode chamber 14 of the plating bath 16 .
  • the circulating anolyte can compensate for the shortage of Sn ions in the plating system.
  • FIG. 15 is a schematic view of the Sn alloy plating apparatus having a plurality of plating baths, according to yet another embodiment.
  • the Sn alloy plating apparatus includes a plurality of plating baths 250 , each having the same construction as the plating bath 16 shown in FIG. 1 , and a single reservoir bath 252 .
  • the anode chambers of the respective plating baths 250 coupled to the reservoir bath 252 by an anolyte supply line 254 and an anolyte recovery line 256 .
  • the anolyte supply line 254 is provided with a pump 258 a .
  • the anolyte supply line 254 branches into branch lines extending to the plating baths 250 , respectively.
  • Branch points of the anolyte supply line 254 are located downstream of the pump 258 a .
  • Switching valves 260 a are provided at the branch points of the anolyte supply line 254 .
  • the anolyte recovery line 256 is provided with a pump 258 b .
  • the anolyte recovery line 256 branches into branch lines extending to the plating baths 250 , respectively.
  • Branch points of the anolyte recovery line 256 are located upstream of the pump 258 b .
  • Switching valves 260 b are provided at the branch points of the anolyte recovery line 256 .
  • a heater 262 for heating the anolyte is installed in the reservoir bath 252 in order to raise the temperature of the anolyte so as to increase the efficiency of electrolysis.
  • the temperature of the anolyte is controlled e.g., in the range of 26° C. to 40° C.
  • the Sn ion concentration and the methanesulfonic acid concentration of the anolyte can be made equal in all the anode chambers of the plating baths 250 by circulating the anolyte between the anode chambers of the plating baths 250 and the reservoir bath 252 .
  • control of the Sn ion concentration and the methanesulfonic acid concentration of the anolyte can be performed in a considerably simple manner according to this embodiment as compared to the case of controlling these concentrations of the anolyte individually in each of the plating baths 250 .
  • the anolyte circulates between the reservoir bath 252 and one of the plating baths 250 by using the two pumps 258 a , 258 b and operating the switching valves 260 a , 260 b .
  • This enables easy control of the anolyte in the anode chamber of each plating bath 250 .
  • Pumps may be provided for the plating baths 250 , respectively, in order to circulate the anolyte between the anode chambers of the plating baths 250 and the reservoir bath 252 .
  • the circulation of the anolyte between one plating bath 250 and the reservoir bath 252 may be performed independently of the other baths 250 .
  • the reservoir bath 252 may be provided with an auxiliary electrolytic cell, having the same construction as the auxiliary electrolytic cell 100 shown in FIG. 1 , so as to compensate for the shortage of the Sn ions.
  • the Sn alloy plating apparatus may include one outer bath (overflow bath) and a plurality of cathode chambers.
  • An anolyte is supplied from the outer bath into each cathode chamber from a bottom of each cathode chamber by means of a pump, and the liquid in the cathode chamber is returned by overflow to the outer bath.

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  • Chemical & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Automation & Control Theory (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
US14/103,767 2012-12-13 2013-12-11 Sn ALLOY PLATING APPARATUS AND METHOD Abandoned US20140166492A1 (en)

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JP2012272168A JP6022922B2 (ja) 2012-12-13 2012-12-13 Ｓｎ合金めっき装置及び方法

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EP3029180A1 (en) * 2014-11-20 2016-06-08 Ebara Corporation Plating apparatus and plating method
US20160348265A1 (en) * 2015-05-29 2016-12-01 Lam Research Corporation Electrolyte delivery and generation equipment
CN108827992A (zh) * 2018-06-21 2018-11-16 深圳市西凡谨顿科技有限公司 K金电铸镀层成分全自动控制装置和系统
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US20190256997A1 (en) * 2018-02-22 2019-08-22 Ebara Corporation Electroplating device
US11525187B2 (en) * 2019-02-28 2022-12-13 Mitsubishi Materials Corporation High-concentration tin sulfonate aqueous solution and method for producing same

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JP2017137519A (ja) * 2016-02-01 2017-08-10 株式会社荏原製作所 めっき装置
JP2021025092A (ja) * 2019-08-06 2021-02-22 株式会社荏原製作所 基板処理装置

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CN108827992A (zh) * 2018-06-21 2018-11-16 深圳市西凡谨顿科技有限公司 K金电铸镀层成分全自动控制装置和系统
WO2019242033A1 (zh) * 2018-06-21 2019-12-26 深圳市西凡谨顿科技有限公司 K金电铸镀层成分全自动控制装置和系统
US11525187B2 (en) * 2019-02-28 2022-12-13 Mitsubishi Materials Corporation High-concentration tin sulfonate aqueous solution and method for producing same
US11692277B2 (en) 2019-02-28 2023-07-04 Mitsubishi Materials Corporation High-concentration tin sulfonate aqueous solution and method for producing same

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JP2014118578A (ja) 2014-06-30
JP6022922B2 (ja) 2016-11-09
KR101967933B1 (ko) 2019-04-10

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