EP1722013A1 - GALVANOPLASTIE EN PRESENCE DE CO sb 2 /sb - Google Patents

GALVANOPLASTIE EN PRESENCE DE CO sb 2 /sb Download PDF

Info

Publication number
EP1722013A1
EP1722013A1 EP05710181A EP05710181A EP1722013A1 EP 1722013 A1 EP1722013 A1 EP 1722013A1 EP 05710181 A EP05710181 A EP 05710181A EP 05710181 A EP05710181 A EP 05710181A EP 1722013 A1 EP1722013 A1 EP 1722013A1
Authority
EP
European Patent Office
Prior art keywords
fluorine
ocf
nonionic compound
plating
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP05710181A
Other languages
German (de)
English (en)
Other versions
EP1722013A4 (fr
Inventor
T. Daikin Environmental Laboratory Ltd. Nagai
K. Daikin Environmental Laboratory Ltd. Fujii
H. Daikin Environmental Laboratory Ltd. Asai
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Daikin Industries Ltd
Original Assignee
Daikin Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Daikin Industries Ltd filed Critical Daikin Industries Ltd
Publication of EP1722013A1 publication Critical patent/EP1722013A1/fr
Publication of EP1722013A4 publication Critical patent/EP1722013A4/fr
Withdrawn legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • 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

Definitions

  • the present invention relates to an environmental technology using CO 2 as an alternative to conventional solvent. More specifically, the present invention relates to a technique for improving the efficiency of electrochemical reaction by using CO 2 as a solvent, and an electroplating technique employing such technique.
  • the technique disclosed therein provides plated films having excellent microthrowing and covering properties without pinholes and a highly increased hardness due to the small particle diameter of the crystals formed, and therefore this technique makes it possible to obtain plated films having a higher quality than known electroplating techniques.
  • a polyoxyethylene blockcopolymer or polyoxyethylene alkylether which is a hydrocarbon-based surfactant
  • these surfactants have a low surface activity in a CO 2 -water system, and therefore a large amount of surfactant, i.e., 3 to 6 wt% of a metal salt-containing aqueous solution (hereunder referred to as a plating solution), is used (Patent Document 1 and Non-Patent Documents 1 and 2). Therefore, in order to put these techniques into practical use, problems in removing the surfactant and plating solution that adhere to the surface of the plated film and drying the surface of the plated film must be resolved.
  • Patent Document 2 a very limited number of surfactants have been known to function in CO 2 (Patent Document 2, and Non-Patent Document 3).
  • Patent Document 1 WO02/16673
  • Patent Document 2 Japanese Unexamined Patent Publication No.10-36680
  • Non-Patent Document 1 Yoshida, et al., MONTHLY MATERIAL STAGE, Vol.1, No.9, 2001, page 70
  • Non-Patent Document 2 Yoshida, et al., Surface and Coatings Technology, Vol.173, 2003, page 285
  • Non-Patent Document 3 Ohtake, et at., Hyomen (Surface), 2002, Vol. 40, page 353
  • An object of the present invention is to provide a technique that can improve the efficiency of electrochemical reaction using CO 2 as a solvent, and an electroplating technique employing such a technique.
  • the efficiency of an electroplating reaction can be improved and excellent metal films can be formed by using a nonionic compound having a CO 2 -affinitive moiety, the nonionic compound having an excellent ability to emulsify CO 2 with an aqueous solution of an electrolyte (e.g., metal salt), which is a plating solution, having an excellent ability to remove or defoam bubbles formed during operations, and having a preferable wettability between a substrate, plating solution and CO 2 .
  • an electrolyte e.g., metal salt
  • the present invention can simplify the preprocessing and postprocessing conducted before and after plating and significantly improve throughput.
  • nonionic compound of the present invention achieves prompt separation between carbon dioxide and a metal-containing aqueous solution after stirring. This reliably prevents the problems of known techniques, such as bubbles of a metal-containing aqueous solution and carbon dioxide entering pipes and metal salts clogging pipes.
  • the nonionic compound of the present invention exhibits a cleaning ability in supercritical carbon dioxide, it is effective for degreasing conducted prior to plating and washing conducted after plating. Therefore, the present invention greatly contributes to reducing alkaline and acidic waste liquids produced during preprocessing and metal waste liquids produced during washing in postprocessing, which are serious problems in prior art techniques.
  • the present inventors concluded that, in order to obtain such properties, having affinity for CO 2 as well as a certain degree of hydrophilicity is important, and therefore using a compound that does not contain any group bearing an electrical charge (i.e., is nonionic) but has a CO 2 -affinitive moiety would be effective for achieving this object.
  • the present inventors concretely examined the plating operation as described below and found that only nonionic compounds exhibit excellent abilities. In contrast, when an anionic or cationic surfactant was used, no plated film was formed or serious problems arose during the operation (see Comparative Examples).
  • the nonionic compounds effective in the present invention have the ability to effectively disperse CO 2 in the plating solution or to form a turbid condition or emulsion, to readily remove or defoam the bubbles formed on a substrate during a plating operation, and to provide preferable wettability between the plating solution, CO 2 , and substrate.
  • preferable wettability which is an essential property, is attributable to the above-mentioned nonionic compounds, and the most preferable compounds can be selected considering various parameters required of the surfactant.
  • a preferable embodiment of the present invention is a nonionic compound having a CO 2 -affinitive moiety comprising a CO 2- affinitive moiety and a hydrophilic moiety (a moiety having a low affinity for CO 2 ).
  • these two moieties may be linked to each other through a linking group X.
  • examples of (1) homopolymers, bicopolymers and tricopolymers selected from the group consisting of polyoxypropylene, polyoxybutylene and polyoxyethylene include polyoxypropylenes, polyoxybutylenes, polyoxyethylenes, polyoxyethylene-polyoxypropylene copolymers, polyoxyethylene-polyoxybutylene copolymers, polyoxypropylene-polyoxybutylene copolymers, and polyoxyethylene-polyoxypropylene-polyoxybutylene copolymers.
  • Such copolymers may be random copolymers, block copolymers, and graft copolymers; however, block copolymers are preferable.
  • the nonionic compound used in the present invention comprises at least one CO 2 -affinitive moiety (R f ), and it may be a compound consists of a CO 2 -affinitive moiety (R f ), or a compound comprising a CO 2 -affinitive moiety (R f ) and a hydrophilic moiety (R h ) linked to each other through a linking group (X).
  • the method of the present invention is such that electroplating is conducted in the presence of a metal salt-containing aqueous solution and CO 2 .
  • the method is characterized in that the CO 2 is liquid, subcritical or supercritical, and a nonionic compound having a CO 2 -affinitive moiety is added to the system in which the aqueous solution and CO 2 coexist.
  • a nonionic compound having a CO 2 -affinitive moiety is added to the system in which the aqueous solution and CO 2 coexist
  • electroplating is conducted using a plating solution containing three components, i.e., CO 2 (the first component), a metal salt-containing aqueous solution (the second component), and a nonionic compound (the third component).
  • a nonionic compound may be added to a plating solution comprising CO 2 and a metal salt-containing aqueous solution to obtain a plating solution comprising the three components. It is also possible to obtain a plating solution comprising the three components by mixing a nonionic compound with CO 2 in advance and adding a metal salt-containing aqueous solution to the mixture. Alternatively, a metal salt-containing aqueous solution and a nonionic compound may be mixed in advance and CO 2 may be added to the mixture to obtain a plating solution comprising the three components.
  • the CO 2 -affinitive moiety (R f ) is at least one member selected from the group consisting of:
  • a particularly preferable CO 2 -affinitive moiety is one of 1) to 4) below:
  • hydrophilic moieties include compounds that do not contain any groups bearing electrical charges therein but contain at least one group selected from hydrocarbon, (poly)ether, and hydroxy groups (alcohols).
  • R h is a straight or branched chain hydrocarbon group that may incorporate a heteroatom (e.g., oxygen, nitrogen, or sulfur atom) therein.
  • Preferable R h is a polyoxyalkylene group.
  • polyoxyalkylene groups include polyoxypropylene, polyoxybutylene polyoxyethylene and like polyether groups. Some polyoxyalkylene groups having a certain chain length also function as CO 2 -affinitive groups.
  • a polyoxyalkylene group functioning as R h has a chain length such that the polyoxyalkylene group is not CO 2 -affinitive but rather is hydrophilic (e.g., having 1 to 15 repeating units when R f is F- (CF(CF 3 )CF 2 O) n CF(CF 3 )).
  • nonionic compounds having a CO 2 -affinitive moiety (R f ) and hydrophilic moiety (R h ) are as below: R f -X-R h , R f -A-X-R h , R f -X-A-R h , R h -X-R f -X-R h , and R f -X-R h -X-R f , wherein R f , R h , and X are as defined above, and A represents a straight or branched chain alkylene group that may be fluorinated.
  • the compound effective in the present invention is a nonionic compound having a CO 2 -affinitive moiety.
  • R f CO 2 -affinitive moiety
  • R h hydrophilic group
  • Such a balance can be expressed by the number of carbons of each group (i.e., R f to R h ), and the ratio thereof is preferably as below.
  • R f : R h is preferably 20 : 1 to 1 : 2 (10 : 1 to 1 : 1 is particularly preferable).
  • R f : R h is preferably 20 : 1 to 1 : 1 (5 : 1 to 2 : 1 is particularly preferable).
  • the number of carbons thereof means the total number of carbons of the two R h or R f groups.
  • fluorinated compounds function in CO 2 better than hydrocarbon-based compounds, and therefore, in the plating operation of the present invention, they significantly contribute to reducing the amount of added compound necessary to emulsify the CO 2 and the plating solution. Furthermore, because nonionic compounds having a CO 2 -affinitive moiety have low water-solubilities, they are not easily soluble in plating solutions, and therefore the time necessary for separating CO 2 from the plating solution can be reduced. This shows that a nonionic compound having a CO 2 -affinitive moiety is a more effective additive than known hydrocarbon-based surfactants.
  • a nonionic compound having a CO 2 -affinitive moiety achieves excellent function because of its adequate hydrophilic properties.
  • a carboxylate which is an anionic surfactant
  • the carboxylate formed insoluble salts with the metal contained in the plating solution (an aqueous metal salt-containing solution), and this became an obstacle to forming desirable plated films and conducting postprocessing after plating.
  • sulfonate among anionic surfactants was used, micelles did not disappear in postprocessing as fast as when a nonionic compound was used (the plating solution separation was insufficient), and therefore pipes became clogged due to bubbles containing the plating solution.
  • a cationic surfactant such as an ammonium salt was used, although electricity flowed, a plated film was not formed, probably because the surfactant adhered to the cathode (see the Comparative Examples).
  • ether-based compounds, ester-based compounds, alcohol-based compounds, polyalkylsiloxanes, fluorinated hydrocarbons, and fluorine-containing polymer compounds are exemplified as nonionic compounds having CO 2 -affinitive moieties.
  • ether-based and ester-based compounds are particularly preferable.
  • fluorine-containing compounds exemplified in 1) to 6) below exhibit excellent effects:
  • ether-based or ester-based compounds represented by the above structural formulae are compounds listed below.
  • various compounds may be effective as long as they satisfy the above-explained balance between the CO 2 -affinitive moiety and hydrophilic moiety that can be determined by the number of carbons contained in each moiety.
  • Such compounds make it possible to form excellent plated films, because of the wettability between the substrate, plating solution and CO 2 , and because defoamation of hydrogen generated can be controlled in the most efficient manner.
  • ether-based and ester-base partially fluorinated compounds include:
  • alcohol-based compounds which are one exemplary embodiment of a nonionic compound, include:
  • polyalkylsiloxanes which are one exemplary embodiment of a nonionic compound, include:
  • fluorinated hydrocarbon which is one exemplary embodiment of nonionic compound, is as below:
  • fluorine-containing polymers which are one exemplary embodiment of a nonionic compound, include:
  • Nonionic compounds having CO 2 -affinitive moieties used in the present invention are commercially available or can be readily produced by persons of skill in the art.
  • the amount of nonionic compound having a CO 2 affinitive moiety used in the present invention is generally about 0.001 to 10 wt%, preferably about 0.01 to 5 wt%, and more preferably about 0.1 to 1 wt% of the metal salt-containing aqueous solution. Because of its excellent abilities, the amount of nonionic compound having a CO 2 -affinitive moiety necessary for achieving satisfactory results is very small, for example, about 0.1 wt%. The nonionic compound having a CO 2 affinitive moiety is superior to hydrocarbon-based compounds in this respect as well.
  • organic solvents co-solvent
  • examples of usable organic solvents include methanol, ethanol, propanol, butanol, pentanol and like alcohols; acetone and like ketones; acetonitrile; ethyl acetate and like esters; ethyl ether and like ethers; and chlorofluorocarbons, methylene chloride, chloroform and like halides.
  • organic solvents include methanol, ethanol, propanol, butanol, pentanol and like alcohols; acetone and like ketones; acetonitrile; ethyl acetate and like esters; ethyl ether and like ethers; and chlorofluorocarbons, methylene chloride, chloroform and like halides.
  • low molecular weight low toxicity compounds are preferable.
  • CO 2 is used in a form of liquid, subcritical, or supercritical. Because the thus-obtained system is biphasic, agitation is necessary. Such agitation includes magnetic stirring, mechanical stirring, and mixing using ultrasonic irradiation, etc.
  • the surfactant of the present invention promotes formation of excellent plated films by making mixing the plating solution with CO 2 easy, and stabilizing the micelles formed during the mixing procedure. Therefore, the effects of the surfactant of the present invention are not limited by the order of placing the surfactant, plating solution, and CO 2 in the apparatus, the method for mixing these components, and the agitation method.
  • the Examples disclosed in the present specification were conducted using small-scale experimental methods; however, there are suitable ways of mixing and/or stirring the components in largescale experiments according to the scale, and therefore the most desirable method of introducing the surfactant should be considered for each operation. Such a method can be easily selected by a person having ordinary skill in the art. Regardless of how CO 2 is mixed with the plating solution, the surfactant of the present invention provides better plated films than when plating is conducted using hydrocarbon-based or ionic surfactants.
  • electroplating in addition to electroplating itself, the concept of electroplating includes electrolytic oxidation, electrolytic reduction and like electrode reactions; electrochemical analysis, corrosion, corrosion prevention, and passivation of metals, etc.
  • the temperature of the electroplating reaction of the present invention is about 10 to 100°C.
  • the pressure is generally about 0.1 to 30 MPa, preferably about 1 to 20 MPa, and more preferably about 5 to 15 MPa.
  • the number of revolutions is generally 100 to 100000 rpm and preferably 400 to 1000 rpm, and when ultrasonic irradiation is employed, the frequency may be, for example, 20 kHz to 10 MHz.
  • an electrolyte in particular an electrolyte containing one or more types of metal, is dissolved in an aqueous phase.
  • metals contained in such electrolyte include Ni, Co, Cu, Zn, Cr, Sn, W, Fe, Ag, Cd, Ga, As, Cr, Se, Mn, In, Sb, Te, Ru, Rh, Pd, Au, Hg, Tl, Pb, Bi, Po, Re, Os, Ir, Pt, etc.
  • electrolyte examples include aqueous chlorides, bromides, iodides and like halides of such metals; nitrates, sulfates, sulfamates, acetates and like organic salts of such metals; cyanides, oxides, hydroxides, and complex of such metals, etc.
  • the time from stopping stirring (stirring conducted at 10 MPa, 50°C, and 500 r.p.m.) to completion of defoamation is generally not longer than 10 minutes, and preferably not longer than 5 minutes.
  • the plated film obtained in the present invention has
  • the diameter of the metal particles of the plated film obtained in the present invention is naturally smaller than that obtained by using known plating techniques as well as smaller than that obtained by using supercritical CO 2 plating techniques wherein hydrocarbon-based surfactants are used. It is reported that the diameter of crystals obtained by typical glossy plating is about 1 ⁇ m and that obtained by known supercritical plating techniques is about 100 nm ( Yoshida et al, Surface and Coatings Technology, 2003, Vol. 173, page 285 ). In contrast, when the additive of the present invention is used, the diameter of the metal particles of the plated film is about 10 nm (see the Reference Example). Therefore, the metal film obtained in the present invention is very densely packed and expected to have high wear resistance.
  • the quality of the metal film obtained in the present invention is almost equal to those of metal films obtained by chemical plating or dry processing, which are nonproductive and require large amounts of energy.
  • the technique of the present invention can provide a method by which metal materials, which used to be provided by dry processing, despite its low productivity, can be obtained in a highly efficient manner.
  • the present invention can achieve the surface treatment of a base material with very small bumps and dips on which a plated film cannot be formed by conventional electrolytic plating techniques.
  • a base material has a structure having a pattern width of the submicronic level and a high aspect ratio.
  • Such a structure corresponds to those of materials used for semiconductors and MEMs.
  • the technique of the present invention can provide a plated film having a uniform thickness over bumps and dips with a pattern width of not greater than 1 ⁇ m and an aspect ratio of not smaller than 3. It is also possible to conduct wiring plating inside the via/trench structure of a semiconductor wafer.
  • the thickness of the plated film can be controlled at a level of several tens of nm by controlling the pressure and current density, and the proportion of carbon dioxide to the plating solution. Therefore, the present invention is very useful in material fields wherein a metal film having a thickness of submicronic order, very small surface roughness, without pinholes, and a high corrosion resistance is required. Specific examples of such materials include those for fuel cells, nozzles for ink-jet printers, electronics industry materials such as magnetic heads, materials for internal combustion engines, and materials for press pumps.
  • the plated film surface roughness can be measured by images taken using a scanning electron microscope.
  • the nonionic compound of the present invention has a cleaning ability in supercritical carbon dioxide, it is effective in degreasing/washing in preprocessing conducted before plating and washing in postprocessing conducted after plating.
  • a plated film having as high a quality as that of the present invention can be formed, without prior degreasing and washing of the substrate, by conducting electroplating after degreasing and washing a substrate using a mixture of the nonionic compound and CO 2 (supercritical, subcritical or liquid), or by conducting degreasing, washing, and plating at the same time using a plating solution comprising the nonionic compound, CO 2 (supercritical, subcritical or liquid), and a metal salt-containing aqueous solution.
  • the plating solution is removed from the surface of the thus-obtained plated film to such an extent that the film can be sufficiently functional without having to remove the plating solution using a large volume of water.
  • formation of a plated film by electroplating and washing of the film can be conducted at the same time.
  • the film after plating may be washed (postprocessing) using a mixture of the nonionic compound and CO 2 (supercritical, subcritical or liquid). Therefore, the present invention significantly contributes to the reduction of alkaline or acid waste waters generated in preprocessing and metal-containing waste waters generated in washing in postprocessing, which have been particular problems in prior art plating process.
  • Fig. 1 illustrates the apparatus used in the Examples of the present invention.
  • a 50 cm 3 high-pressure container 8 were placed 20 cm 3 of nickel plating bath (Watt bath comprising 280 g/L nickel sulfate, 60 g/L nickel chloride, 50 g/L boric acid, and a brightener (q.s.)) and 0.3 wt% of F (CF(CF 3 ) CF 2 O) 3 CF(CF 3 )COO (CH 2 CH 2 O) 2 CH 3 relative to the nickel plating bath.
  • Watt bath comprising 280 g/L nickel sulfate, 60 g/L nickel chloride, 50 g/L boric acid, and a brightener (q.s.)
  • F CF(CF 3 ) CF 2 O
  • CF(CF 3 )COO CH 2 CH 2 O
  • the high-pressure container 8 After attaching a degreased brass plate to the cathode and pure nickel plate to the anode (both having a surface area of 4 cm 2 ), the high-pressure container 8 was sealed, and then heated to 50°C in a thermostat 4. CO 2 was filled in the container using a liquid feeding pump 3 and pressure regulator 10 until the pressure reached 10 MPa. Nickel plating was conducted by stirring the CO 2 -plating solution by rotating a rotor 6 at 500 rpm using a stirrer 5, and passing an electric current at 5 A/dm 2 for 6 minutes. After completion of electric current passage, the high-pressure container 8 was subjected to decompression, the cathode was removed and sufficiently washed with water, and the surface was observed using a scanning electron microscope (SEM). Fig. 2 shows scanning electron microscope photographs.
  • SEM scanning electron microscope
  • Plating was conducted in the same manner as Example 1 except that H(CF 2 ) 6 COOCH 2 CH 3 was used as a nonionic compound having a CO 2 -affinitive moiety.
  • Fig. 3 shows scanning electron microscope photographs.
  • Plating was conducted in the same manner as Example 1 except that F(CF 2 ) 6 (CH 2 ) 10 H was used as a nonionic compound having a CO 2 -affinitive moiety.
  • Fig. 4 shows scanning electron microscope photographs.
  • Plating was conducted in the same manner as Example 1 except that F(CF 2 ) 7 COOCH 2 CH 3 was used as a nonionic compound having a CO 2 -affinitive moiety.
  • Fig. 5 shows scanning electron microscope photographs.
  • Plating was conducted in the same manner as Example 1 except that F(CF(CF 3 )CF 2 O) 4 CF(CF 3 )COOCH 3 was used as a nonionic compound having a CO 2 -affinitive moiety.
  • Fig. 6 shows scanning electron microscope photographs.
  • Plating was conducted in the same manner as Example 1 except that F(CF 2 ) 7 COO(CH 2 ) 5 CH 3 was used as a nonionic compound having a CO 2 -affinitive moiety.
  • Fig. 7 shows scanning electron microscope photographs.
  • Plating was conducted in the same manner as Example 1 except that F(CF(CF 3 )CF 2 O) 2 CF(CF 3 )CH 2 OH was used as a nonionic compound having a CO 2 -affinitive moiety.
  • Fig. 8 shows scanning electron microscope photographs.
  • Plating was conducted in the same manner as Example 1 except that F(CF(CF 3 )CF 2 O) 3 CF(CF 3 )COOCH 2 CH 2 OCH 3 was used as a nonionic compound having a CO 2 -affinitive moiety.
  • Fig. 9 shows scanning electron microscope photographs.
  • Plating was conducted in the same manner as Example 1 except that F(CF(CF 3 )CF 2 O) 3 CF(CF 3 )COOC 6 H 13 was used as a nonionic compound having a CO 2 -affinitive moiety.
  • Fig. 10 shows scanning electron microscope photographs.
  • Plating was conducted in the same manner as Example 1 except that F(CF(CF 3 )CF 2 O) 3 CF(CF 3 )CO(OCH 2 CH 2 ) 3 OCOCF(CF 3 )(OCF 2 (CF 3 )CF) 3 F was used as a nonionic compound having a CO 2 -affinitive moiety.
  • Fig. 11 shows scanning electron microscope photographs.
  • Plating was conducted in the same manner as Example 1 except that CH 3 OCH 2 CH 2 OCCF 2 (OCF 2 CF 2 ) 6 OCF 2 COOCH 2 CH 2 OCH 3 was used as a nonionic compound having a CO 2 -affinitive moiety.
  • Fig. 12 shows scanning electron microscope photographs.
  • Fig. 13 shows scanning electron microscope photographs.
  • a 50 cm 3 high-pressure container 8 were placed 20 cm 3 of an acid gold plating bath (comprising 10 g/L potassium gold cyanide and 90 g/L citric acid) and 0.3 wt% of F(CF(CF 3 )CF 2 O) 3 CF(CF 3 )COO(CH 2 CH 2 O) 2 CH 3 relative to the plating bath.
  • an acid gold plating bath comprising 10 g/L potassium gold cyanide and 90 g/L citric acid
  • F(CF(CF 3 )CF 2 O) 3 CF(CF 3 )COO(CH 2 CH 2 O) 2 CH 3 relative to the plating bath After attaching a nickel-plated brass plate to the cathode and platinum-plated titanium plate to the anode (both having a surface area of 4 cm 2 ), the high-pressure container 8 was sealed, and then heated to 40°C in a thermostat 4. CO 2 was filled in the container using a liquid feeding pump 3 and pressure regulator 10 until the pressure reached 10 MPa.
  • Gold plating was conducted by stirring the CO 2 -plating solution by rotating a rotor 6 at 500 rpm using a stirrer 5 and passing an electric current at 2 A/dm 2 for 2 minutes. After completion of electric current passage, the high-pressure container 8 was subjected to decompression, the cathode was removed and sufficiently washed with water, obtaining an excellent gold-plated film.
  • Fig. 14 shows scanning electron microscope photographs (magnification: 500 times).
  • a 50 cm 3 high-pressure container 8 were placed 20 cm 3 of copper sulfate plating bath (comprising 200 g/L copper sulfate pentahydrate, 50 g/L sulfuric acid, and q.s. hydrochloric acid) and 0.3 wt% of F(CF(CF 3 )CF 2 O) 3 CF(CF 3 )COO(CH 2 CH 2 O) 2 CH 3 relative to the plating bath.
  • the high-pressure container 8 was sealed, and then heated to 50°C in a thermostat 4.
  • CO 2 was filled in the bath using a liquid feeding pump 3 and pressure regulator 10 until the pressure reached 10 MPa.
  • Copper plating was conducted by stirring the CO 2- plating solution by rotating a rotor 6 at 500 rpm using a stirrer 5 and passing an electric current at 5 A/dm 2 for 5 minutes. After completion of electric current passage, the high-pressure container 8 was subjected to decompression, the cathode was removed and sufficiently washed with water, obtaining an excellent copper plated film.
  • a 50 cm 3 high-pressure container 8 In a 50 cm 3 high-pressure container 8 were placed 20 cm 3 of acid gold plating bath (comprising 0.10 mol/L palladium chloride, 4.00 mol/L potassium bromide, 0.10 mol/L potassium nitrate, 0.49 mol/L boric acid, 0.10 mol/L glycine, and 90 g/L citric acid) and 0.3 wt% of F(CF(CF 3 )CF 2 O) 3 CF(CF 3 )COO(CH 2 CH 2 O) 2 CH 3 relative to the plating bath.
  • acid gold plating bath comprising 0.10 mol/L palladium chloride, 4.00 mol/L potassium bromide, 0.10 mol/L potassium nitrate, 0.49 mol/L boric acid, 0.10 mol/L glycine, and 90 g/L citric acid
  • the high-pressure container 8 was sealed, and then heated to 40°C in a thermostat 4.
  • CO 2 was filled in the container using a liquid feeding pump 3 and pressure regulator 10 until the pressure reached 12 MPa.
  • the CO 2- plating solution was sufficiently mixed and stirred by rotating a rotor 6 at 650 rpm for one hour using a stirrer 5.
  • Palladium plating was conducted by passing an electric current at 1 A/dm 2 for 15 minutes. After completion of electric current passage, the high-pressure container 8 was subjected to decompression, the cathode was removed and sufficiently washed with water, obtaining an excellent palladium-plated film.
  • Fig. 15 shows scanning electron microscope photographs.
  • Nickel plating was conducted in the same manner as in Example 1 except that an untreated brass plate was attached to the cathode and pure nickel plate to the anode (both having a surface area of 4 cm 2 ). After completion of electric current passage, the high-pressure container 8 was subjected to decompression. The cathode was removed and the surface thereof was observed with the naked eye and using a scanning electron microscope (SEM). It was found that a plated film having almost the same quality as that of Example 1 was obtained. From this result, it became clear that by using the compound of the present invention in supercritical carbon dioxide, the preprocessing and postprocessing conducted before and after plating could be omitted.
  • SEM scanning electron microscope
  • FIG. 16 shows the results as cross-sectional SEM images of magnifications of 10000 times or 30000 times.
  • the crystal diameters were 7 to 12 nm, and the surface of the plated film was very smooth.
  • the variance of the thickness of the surface was about 10 nm. Because the thickness of the film was 1 ⁇ m, this suggests that controlling of the thickness to about 100 nm can be easily conducted.
  • Plating was conducted in the same manner as in Example 1 except that 3 wt% of CH 3 (CH 2 ) 12 (OCH 2 CH 2 ) 8 OH was used instead of the nonionic compound having a CO 2 -affinitive moiety. Clogged pipes were observed during the postprocessing caused by formation of bubbles.
  • Fig. 17 shows scanning electron microscope photographs. From the SEM observations, it was clear that although no pinholes were formed in the plated film, the surface thereof was very rough compared when a nonionic compound having a CO 2 -affinitive moiety was used.
  • plating was conducted without adding CO 2 (i.e., using a prior art plating technique).
  • Fig. 18 shows scanning electron microscope photographs. Large pinholes were observed.
  • Plating was conducted in the same manner as in Example 1 except that F(CF(CF 3 )CF 2 O) 14 CF(CF 3 )COO - NH 4 + was used instead of the nonionic compound having a CO 2 -affinitive moiety. Electric current did not flow, and formation of a plated film was not observed. A gel solution had formed in the apparatus after completion of the reaction.
  • Plating was conducted in the same manner as in Example 1 except that a compound represented by Chemical Formula 1 below was used instead of the nonionic compound having a CO 2 -affinitive moiety.
  • Electric current flowed and plating could be conducted; however, bubbles formed when the plating solution was emulsified during the decompression in the postprocessing overflowed from the apparatus and entered the pipes.
  • Plating was conducted in the same manner as in Example 1 except that F(CF 2 (CF 3 )CF 2 O) 3 (CF 3 )CFCONHCH 2 CH 2 N + (CH 3 ) 3 I - was used instead of the nonionic compound having a CO 2 -affinitive moiety. Electric current did not flow, and adhesion of a brown substance to the surface of the cathode was observed.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Electroplating Methods And Accessories (AREA)
EP05710181A 2004-02-12 2005-02-14 Galvanoplastie en presence de co2 Withdrawn EP1722013A4 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2004035281 2004-02-12
JP2004349651A JP4673612B2 (ja) 2004-02-12 2004-12-02 Ｃｏ２存在下での電気めっき
PCT/JP2005/002179 WO2005078161A1 (fr) 2004-02-12 2005-02-14 Galvanoplastie en présence de co2

Publications (2)

Publication Number Publication Date
EP1722013A1 true EP1722013A1 (fr) 2006-11-15
EP1722013A4 EP1722013A4 (fr) 2007-08-08

Family

ID=34863449

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05710181A Withdrawn EP1722013A4 (fr) 2004-02-12 2005-02-14 Galvanoplastie en presence de co2

Country Status (5)

Country Link
US (1) US20070175763A1 (fr)
EP (1) EP1722013A4 (fr)
JP (1) JP4673612B2 (fr)
KR (1) KR20070001174A (fr)
WO (1) WO2005078161A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007063598A (ja) * 2005-08-30 2007-03-15 Tokyo Univ Of Agriculture & Technology 多孔性金属薄膜およびその製造方法
JP4919262B2 (ja) 2006-06-02 2012-04-18 日立マクセル株式会社 貯蔵容器、樹脂の成形方法及びメッキ膜の形成方法
JP5324191B2 (ja) 2008-11-07 2013-10-23 ルネサスエレクトロニクス株式会社 半導体装置
US20120245019A1 (en) * 2011-03-23 2012-09-27 Brookhaven Science Associates, Llc Method and Electrochemical Cell for Synthesis of Electrocatalysts by Growing Metal Monolayers, or Bilayers and Treatment of Metal, Carbon, Oxide and Core-Shell Nanoparticles
CN106048693B (zh) * 2014-08-20 2018-06-08 江苏理工学院 一种基于移动阳极的超临界复合电镀加工钻头方法
US10011918B2 (en) * 2014-12-23 2018-07-03 Taiwan Semiconductor Manufacturing Co., Ltd. Apparatus and process of electro-chemical plating

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6793793B2 (en) * 2000-08-24 2004-09-21 Hideo Yoshida Electrochemical treating method such as electroplating and electrochemical reaction device therefor

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
No further relevant documents disclosed *
See also references of WO2005078161A1 *

Also Published As

Publication number Publication date
US20070175763A1 (en) 2007-08-02
KR20070001174A (ko) 2007-01-03
WO2005078161A1 (fr) 2005-08-25
JP4673612B2 (ja) 2011-04-20
JP2005256162A (ja) 2005-09-22
EP1722013A4 (fr) 2007-08-08

Similar Documents

Publication Publication Date Title
EP1722013A1 (fr) GALVANOPLASTIE EN PRESENCE DE CO sb 2 /sb
CN102939339B (zh) 包含流平试剂的金属电镀用组合物
JP5722872B2 (ja) サブミクロンの窪みの無ボイド充填用の抑制剤含有金属めっき組成物
EP2231903B1 (fr) Méthode de depôt de revêtements composites pour la réduction de barbes
EP3344800B1 (fr) Bains aqueux de placage de cuivre et procédé de déposition de cuivre ou d'alliage de cuivre sur un substrat
JP2009114548A (ja) スズめっき
US9074292B2 (en) Acid mist mitigation agents for electrolyte solutions
JP2012522900A5 (fr)
CN104105818A (zh) 用于化学镀镍或化学镀镍合金的预处理液、以及镀膜方法
CN101899685B (zh) 电解锡镀覆溶液和电解锡镀覆方法
TW396214B (en) High current density zinc sulfate electrogalvanizing process and composition
WO2017129583A1 (fr) Bain de placage aqueux d'indium ou d'alliage d'indium et procédé de dépôt d'indium ou d'alliage d'indium
Wakabayashi et al. Nano-grain structure of nickel films prepared by emulsion plating using dense carbon dioxide
JP2004315675A (ja) 二酸化炭素溶媒用界面活性剤
EP3272910B1 (fr) Compositions d'électrodéposition d'indium1,10-phénanthroline contenant des composés et des procédés d'électrodéposition de le indium
JP4583811B2 (ja) めっき処理方法
Goh et al. Electrodeposition of lead‐free solder alloys
EP3135709A1 (fr) Polymères d'urée imidazoyle et leur utilisation dans des compositions de bains de placage de métaux ou d'alliages de métaux
US8440857B2 (en) Sulfonate- or sulfate-capped anti-misting agents
CN105917032A (zh) 铜的电沉积
EP3728702B1 (fr) Composition pour électroplacage d'étain ou d'alliage d'étain comprenant un agent suppresseur
WO2007007617A1 (fr) Traitement de surface en présence d’un solvant organique
Hu et al. Interfacial Reactions and Smooth Etching Strategy of n-type Gallium Nitride Photoanodes
JP2006291008A (ja) フッ素系洗浄溶媒
EP3272911B1 (fr) Compositions d'électrodéposition d'indium contenant des composés de 2-imidazolidinethione et procédés d'électrodéposition d'indium

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20060907

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU MC NL PL PT RO SE SI SK TR

RTI1 Title (correction)

Free format text: ELECTROPLATING IN PRESENCE OF CO2

DAX Request for extension of the european patent (deleted)
A4 Supplementary search report drawn up and despatched

Effective date: 20070709

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Effective date: 20080310