US20020053518A1 - Material for copper electroplating, method for manufacturing same and copper electroplating method - Google Patents

Material for copper electroplating, method for manufacturing same and copper electroplating method Download PDF

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US20020053518A1
US20020053518A1 US09/944,344 US94434401A US2002053518A1 US 20020053518 A1 US20020053518 A1 US 20020053518A1 US 94434401 A US94434401 A US 94434401A US 2002053518 A1 US2002053518 A1 US 2002053518A1
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copper
carbonate
basic
aqueous
ion
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Shiroshi Matsuki
Kazunori Akiyama
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Tsurumi Soda Co Ltd
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Tsurumi Soda Co Ltd
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Priority claimed from JP2000267018A external-priority patent/JP4033616B2/ja
Priority claimed from JP2000310547A external-priority patent/JP3839653B2/ja
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Assigned to TSURUMI SODA CO., LTD. reassignment TSURUMI SODA CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: AKIYAMA, KAZUNORI, MATSUKI, SHIROSHI
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/02—Oxides; Hydroxides
    • 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
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties

Definitions

  • This invention relates to a material for copper electroplating (hereinafter also referred to as “copper electroplating material”), a method for manufacturing a copper electroplating material and a copper plating method, and more particularly to a copper electroplating material which is fed as a copper ion supply to a copper plating bath in which an object to be plated is subjected to copper electroplating, a method for producing such a copper electroplating material, and a copper plating method using such a copper electroplating material.
  • copper electroplating material hereinafter also referred to as “copper electroplating material”
  • One of techniques of subjecting an object to be plated (hereinafter also referred to as “plated object”) to copper plating which have been conventionally known in the art is an copper electroplating method wherein a material for copper plating or a copper plating material is introduced into a sulfuric acid solution acting as an electrolyte and a current is flowed between an insoluble anode and a plated object acting as a cathode.
  • a material for copper plating or a copper plating material is introduced into a sulfuric acid solution acting as an electrolyte and a current is flowed between an insoluble anode and a plated object acting as a cathode.
  • copper oxide prepared by subjecting basic copper carbonate to thermal composition is used as the copper plating material (see Japanese Patent No. 2,753,855).
  • Copper oxide is widely used as a material for ferrite. Also, it is used as a copper ion supply for a bath for electroless plating of copper as disclosed in Japanese Patent Application Laid-Open Publication No. 80116/1991. Copper oxide is generally produced by subjecting a mill scale of copper, cuprous oxide or copper hydroxide to a heat treatment. However, a copper mill scale is hard to dissolve in an electrolyte, to thereby fail to be used as a material for copper plating. Also, cuprous oxide contains a chlorine ion (Cl ⁇ (hereinafter merely referred to as “Cl”)) in a large amount, leading to a failure in copper plating.
  • Cl chlorine ion
  • Japanese publication described above Japanese Patent Application Laid-Open Publication No. 800116/1991 discloses that copper oxide may be obtained by heating copper hydroxide to a temperature within a range of between 60° C. and 100° C.
  • use of cupric hydroxide for copper electroplating causes a failure in plating of copper because it contains a chlorine ion and sulfur (S) derived from SO 4 2 ⁇ (hereinafter merely referred to as “SO 4 ”) in a large amount.
  • SO 4 chlorine ion and sulfur
  • copper oxide obtained by subjecting basic copper carbonate to thermal decomposition may be used as a material for copper plating, because a content of Cl and S (derived from SO 4 ) therein is reduced.
  • use of copper oxide obtained by thermal decomposition of basic copper carbonate as a copper plating material causes problems.
  • the copper oxide is usually used as a material for ferrite, so that it is required that copper oxide is reduced in weight reduction in a calcination step in manufacturing of ferrite.
  • a heating temperature employed in thermal decomposition of copper oxide or a heat treatment thereof is generally as high as 900° C. or more.
  • the thus-obtained copper oxide is readily dissolved in an electrolyte as compared with usual copper oxide, it fails to exhibit satisfactory solubility.
  • a furnace for thermal decomposition of the copper oxide is generally constituted by a rotary kiln of the type heated directly by a flame in view of thermal efficiency.
  • it causes the copper oxide to be partially formed into cuprous oxide and metallic copper due to contact of the copper oxide with the flame which is a reducing flame.
  • the thus-formed cuprous oxide and metallic copper lead to an increase in an insoluble residue which is an impurity when it is dissolved in a sulfuric acid solution which is an electrolyte. It is required to keep a concentration of copper in the electrolyte constant. However, this renders a concentration of copper in the electrolyte nonuniform, resulting in quality of an article plated being deteriorated.
  • impurities which are introduced in a small amount into the basic copper carbonate from a material for the basic copper carbonate such as alkaline metals (Na and K), alkaline earth metals (Mg and Ca), a chlorine ion, S derived from SO 4 and the like are increased in concentration by, for example, about 1.4 to 1.5 times in the copper oxide obtained by thermal decomposition. Accumulation of a chlorine ion in the plating bath renders an article plated course or causes formation of nodular or needle-like deposits on the article, resulting in the article being defective.
  • accumulation of S derived from SO 4 therein not only adversely affects the plating, but renders control of a SO 4 concentration in the plating bath difficult, leading to scattering in quality of an article plated.
  • accumulation of alkaline metal and/or alkaline earth metal in the plating bath causes likelihood that sulfates thereof are deposited on an article plated, leading to an increase in frequency at which the plating bath must be renewed or refreshed.
  • Basic copper carbonate is used as a copper plating material in the copper electroplating described above, as disclosed in Japanese Patent No. 2,753,855, of which the disclosure is incorporated herein by reference.
  • Basic copper carbonate is suitable for use as a material for copper plating from a viewpoint of the fact that it is increased in solubility.
  • basic copper carbonate is produced by reacting an aqueous cupric chloride solution or an aqueous cupric sulfate solution with an aqueous solution containing a carbonate ion.
  • an aqueous cupric chloride solution causes the basic copper carbonate to contain a chlorine ion and that of an aqueous cupric sulfate solution causes it to contain SO 4 , however, a content of such impurities in the basic copper carbonate is relatively reduced.
  • a plating plant in view of the fact that accumulation of a Cl ion and S derived from SO 4 in the plating bath leads to a deterioration in copper plating, it is carried out to monitor a concentration of such impurities in the plating bath, to thereby renew or refresh the plating bath when the impurities accumulate to an upper limit determined from a viewpoint of control of the plating.
  • renewal or refreshment of the plating bath causes a significant increase in plating cost, leading to an increase in cost of the article plated. Therefore, it would be highly desirable to minimize a content of the impurities in the basic copper carbonate.
  • a method for manufacturing a material for copper electroplating or a copper electroplating material adapted to be fed as a copper ion supply to a copper plating bath in copper electroplating includes the step of heating basic copper carbonate to a temperature of 250° C. to 800° C. in an atmosphere which is not rendered reducing or reductive to carry out thermal decomposition of the basic copper carbonate, to thereby produce easily soluble copper oxide constituting the copper electroplating material.
  • heating of the basic copper carbonate in the atmosphere which is not rendered reducing or reductive” referred to herein is intended to mean heating by means of an electric furnace rather than direct heating by means of, for example, a burner.
  • basic copper carbonate which is a material for easily soluble copper oxide may be commercially available. Alternatively, it may be obtained by mixing an aqueous solution of copper chloride, copper sulfate or copper nitrate with an aqueous carbonate solution of, for example, alkaline metal, alkaline earth metal or ammonia (NH 4 ) and then reacting the aqueous solutions with each other while heating them.
  • aqueous solution of copper chloride, copper sulfate or copper nitrate with an aqueous carbonate solution of, for example, alkaline metal, alkaline earth metal or ammonia (NH 4 )
  • mixing between the aqueous carbonate solution and the aqueous solution of copper chloride, copper sulfate or copper nitrate may be carried out by charging the carbonate in the form of a solid into the aqueous solution of copper chloride, copper sulfate or copper nitrate to dissolve the former in the latter or charging copper chloride, copper sulfate or copper nitrate in the form of a solid into the aqueous carbonate solution to dissolve the former in the latter.
  • a copper plating method includes the steps of feeding the copper electroplating material described above to an electrolyte in which an insoluble anode and a plated object acting as a cathode are arranged and subjecting the plated object to copper plating.
  • a method for manufacturing a copper electroplating material fed as a copper ion supply to a copper plating bath in copper electroplating includes the steps of mixing an aqueous cupric chloride solution and an aqueous solution containing a carbonate ion with each other to prepare a mixed solution, keeping the mixed solution at a pH within a range of between 8.0 and 9.0 and a temperature within a range of between 75° C. and 90° C. to form basic copper carbonate, and subjecting the basic copper carbonate to solid-liquid separation and washing, so that the basic copper carbonate may have a chlorine concentration of 80 ppm or less.
  • a method for manufacturing a copper electroplating material fed as a copper ion supply to a copper plating bath in copper electroplating includes the steps of mixing an aqueous cupric sulfate solution and an aqueous solution containing a carbonate ion with each other to prepare a mixed solution, keeping the mixed solution at a pH within a range of between 8.0 and 9.0 and a temperature within a range of between 75° C. and 90° C. to form basic copper carbonate, and subjecting the basic copper carbonate to solid-liquid separation and washing, so that the basic copper carbonate may have a SO 4 concentration of 200 ppm or less.
  • mixing between the aqueous cupric chloride solution or aqueous cupric sulfate solution and the aqueous carbonate ion-containing solution is carried out while controlling a pH of the mixed solution.
  • the inventors found that the mixing at a temperature of 95° C. or more causes a substantial difference between the apparent pH and the actual pH, thus, feed of the aqueous solutions based on pH control causes the basic copper carbonate to contain a large amount of impurities.
  • a method for manufacturing a copper electroplating material fed as a copper ion supply to a copper plating bath in copper electroplating includes the steps of feeding an aqueous cupric chloride solution and an aqueous solution containing a carbonate ion to a reaction tank while adjusting a feed ratio between both aqueous solutions so that a molar ratio of a copper ion to a carbonate ion in a mixed solution of both aqueous solutions may be within a range of between 1:1.3 to 2.6, keeping a temperature of the mixed solution at a level of 95° C. or more without pH control of the mixed solution to produce basic copper carbonate, and subjecting the basic copper carbonate to solid-liquid separation and washing, to thereby provide the copper electroplating material constituted by the basic copper carbonate.
  • the feed rate is so adjusted that a molar ratio between the copper ion and the carbonate ion is 1:2.3 to 4.6.
  • Mixing between the aqueous cupric chloride or cupric sulfate solution and the aqueous carbonate ion-containing solution may be also carried out by charging cupric chloride or cupric sulfate in the form of a solid into the aqueous carbonate solution, charging the carbonate in the form of a solid into the aqueous cupric chloride or cupric sulfate solution, or introducing carbon dioxide into the aqueous cupric chloride or cupric sulfate solution.
  • a method for manufacturing basic copper carbonate fed as a copper ion supply to a copper plating bath in copper electroplating includes the steps of feeding an aqueous cupric sulfate solution and an aqueous solution containing a carbonate ion to a reaction tank while adjusting a feed ratio between both aqueous solutions so that a molar ratio of a copper ion to carbonate ion in a mixed solution of both aqueous solutions may be within a range of between 1:2.3 to 4.6, keeping a temperature of the mixed solution at a level of 95° C. or more without pH control of the mixed solution to produce basic copper carbonate, and subjecting the basic copper carbonate to solid-liquid separation and washing, to thereby provide the copper electroplating material constituted by the basic copper carbonate.
  • FIG. 1 is a flow diagram showing an embodiment of a method for manufacturing a material for copper electroplating or a copper electroplating material according to the present invention
  • FIG. 2 is a schematic block diagram showing a plating apparatus used in copper electroplating of the present invention by way of example;
  • FIG. 3 is a graphical representation showing a variation in conductivity shown in Table 1 with time;
  • FIG. 4 is a graphical representation showing a variation in conductivity shown in Table 1 with time;
  • FIG. 5 is a flow diagram showing another embodiment of a method for manufacturing a copper electroplating material according to the present invention.
  • FIG. 6 is a flow diagram showing a further embodiment of a method for manufacturing a copper electroplating material according to the present invention.
  • basic copper carbonate which is a material for significantly soluble copper oxide may be commercially available.
  • it may be obtained by mixing an aqueous solution of copper chloride, copper sulfate or copper nitrate with an aqueous carbonate solution of, for example, alkaline metal, alkaline earth metal or ammonia(NH 4 ), reacting both aqueous solutions with each other while heating them, depositing a reaction product, and then separating the reaction product by filtration.
  • mixing between the aqueous carbonate solution and the aqueous solution of copper chloride, copper sulfate or copper nitrate may be carried out by charging the carbonate in the form of a solid into the aqueous solution of copper chloride, copper sulfate or copper nitrate to dissolve the former in the latter or charging copper chloride, copper sulfate or copper nitrate in the form of a solid into the aqueous carbonate solution to dissolve the former in the latter.
  • FIG. 1 an embodiment of a method for manufacturing a material for copper electroplating or a copper electroplating material which is basic copper carbonate is illustrated in the form of a flow diagram.
  • an aqueous solution of cupric chloride (CuCl 2 ) which has a copper concentration of 10% by weight and an aqueous solution of alkaline metal carbonate such as, for example, an aqueous sodium carbonate (Na 2 CO 3 ) solution having a carbonate concentration of 7% by weight are charged in a reaction tank 1 so that a mixed solution of both aqueous solutions has a pH of 7.0 to 9.0.
  • CuCl 2 cupric chloride
  • Na 2 CO 3 aqueous sodium carbonate
  • the solutions thus mixed are stirred for, for example, 30 minutes using a stirring means 11 while being heated so that the mixed solution has a temperature of, for example, 70° C.
  • a stirring means 11 Such heating of the mixed solution may be carried out by providing any suitable bubbling means constituted by an air diffusing pipe (not shown) or the like the reaction tank 1 and introducing bubbled steam into the mixed solution using the bubbling means.
  • the basic copper carbonate thus formed is then deposited or precipitated in the form of a powder.
  • a valve 2 is rendered open to draw out the thus-precipitated slurry therethrough to a centrifugal separator 2 , in which the slurry is subjected to centrifuging to separate a solid matter of the slurry from a mother liquor thereof.
  • the solid matter is placed in a drier 3 , to thereby be dried therein, resulting in basic copper carbonate being obtained in the form of a powder.
  • Copper ion sources for the basic copper carbonate may include aqueous solutions of copper chloride, as well as copper salts such as, for example, copper sulfate, copper nitrate and the like.
  • Carbonate ion sources may include carbonates of alkaline metals such as sodium carbonate, sodium bicarbonate, potassium carbonate and the like, as well as carbonates of alkaline earth metals such as calcium carbonate, magnesium carbonate and barium carbonate, ammonium carbonate ((NH 4 ) 2 CO 3 ), and the like.
  • the above-described basic copper carbonate which is in the form of a powder is introduced into a heating furnace such as, for example, a rotary kiln 4 , in which it is heated to a temperature between, for example, 250° C. and 800° C. for thermal decomposition thereof.
  • the heating furnace may be constituted by a rotary kiln which is so constructed that a rotary pipe 41 made of, for example, stainless steel and adapted to revolve about an axis thereof is arranged in a manner to be slightly inclined and a heater 42 is arranged so as to surround the rotary pipe 41 , resulting in the basic copper carbonate powder being carried by rotation of the rotary pipe 41 , as shown in FIG. 1.
  • Heating of the basic copper carbonate in such a manner prevents an atmosphere in which the carbonate powder is heated from being reducing or reductive.
  • the basic copper carbonate is not heated directly in a burner. This is for the reason that such direct heating of copper carbonate leads to formation of a reducing atmosphere, which causes reduction or deoxidation of a part of copper carbonate and/or copper oxide formed by decomposition of copper carbonate, to produce cuprous oxide (Cu 2 O) and/or metallic copper (Cu).
  • Metallic copper is insoluble or hard to dissolve in an aqueous sulfuric acid solution used as an electrolyte when copper oxide is used as a material for copper plating or a copper plating material, to thereby form an insoluble residue, resulting in a new filter being required for removing the residue. Also, formation of metallic copper and cuprous oxide renders feed of copper to a plating bath nonuniform, resulting in quality of an article plated being considerably scattered. Thus, it is essential to prevent the heating atmosphere in which the basic copper carbonate is heated from being rendered reducing or reductive.
  • the above-described impurities are contained in a large amount in the material for copper plating or copper plating material, an article plated is deteriorated in quality.
  • the basic copper carbonate contains a large amount of impurities such alkaline metals (Na, and K), alkaline earth metals (Mg, and Ca), anions (a chlorine ion Cl ⁇ , and a sulfate ion SO 4 2 ⁇ ), and the like
  • the highly soluble copper oxide obtained by thermal decomposition is preferably washed with water.
  • the copper oxide after formation of the copper oxide, it is charged in a washing tank 5 which is filled therein with pure water acting as wash liquid and washed while stirring the wash liquid using a stirring means 51 . Then, a valve 52 is opened to draw a mixed slurry of water and copper oxide out of the washing tank 5 , resulting in the slurry being fed to a centrifugal separator 6 or a filter, in which the slurry is dewatered. Subsequently, the dewatered slurry is dried in a drier 7 , so that copper oxide may be obtained in the form of a powder. Pure water such as distilled water, ion-exchanged water or the like may be used as the wash liquid. Alternatively, water further reduced in impurity such as superpure water may be used for this purpose.
  • reference numeral 8 designates a plating bath, which is filled therein with plating liquid including sulfuric acid acting as an electrolyte and copper oxide dissolved therein.
  • the plating liquid has an insoluble anode 81 and a cathode 82 immersed therein.
  • the insoluble anode 81 is constituted, for example, by a titanium plate having platinum or platinum-iridium coated thereon at a ratio of 7:3 and connected to a positive electrode of a DC power supply E.
  • the cathode 82 which is constituted by an object to be plated or a plated object and may be in the form of, for example, a metal plate is connected to a negative electrode of the DC power supply E.
  • Reference numeral 83 designates a dissolution tank for dissolving copper oxide therein.
  • the dissolution tank 83 is fed with a predetermined amount of copper oxide in the form of a powder from a hopper 84 acting as a copper oxide feed source. Then, the copper oxide is dissolved in an aqueous sulfuric acid solution in the dissolving tank 83 while being stirred with a stirring means 85 .
  • the copper oxide thus dissolved is fed to the plating bath 8 by means of pumps P 1 and P 2 for the next copper plating, when the amount of copper ion in the plating bath 8 is reduced.
  • Reference character F is a filter.
  • copper oxide is prepared by subjecting basic copper carbonate to thermal decomposition at a temperature within a range of between 250° C. and 800° C. This permits the copper oxide to be easily dissolved in an aqueous sulfuric acid solution as described hereinafter. Also, the thermal decomposition does not take place in a reducing atmosphere, to thereby minimize or substantially prevent production of an insoluble residue such as cuprous oxide, metallic copper and the like. This almost prevents application of load to the filter and renders a copper ion concentration in the copper plating bath stabilized, when copper oxide is used as a material for copper plating or a copper plating material.
  • Basic copper carbonate inherently contains an anion and a cation depending on a material therefor.
  • basic copper carbonate is made of an aqueous solution of cupric chloride (CuCl 2 ) and an aqueous solution of sodium carbonate (Na 2 CO 3 ), it contains a chlorine ion and a sodium ion.
  • cupric sulfate (CuSO 4 ) is substituted for cupric chloride, basic copper carbonate prepared contains a sodium ion and S derived from a SO 4 ion.
  • washing of the basic copper carbonate fails to permit the impurities such as a chlorine ion, S of a SO 4 ion, a sodium ion, a potassium ion and the like to be substantially removed therefrom, leading to a failure in purification of the carbonate.
  • the impurities such as a chlorine ion, S of a SO 4 ion, a sodium ion, a potassium ion and the like
  • the impurities may be reduced.
  • use of copper oxide as a material for copper plating or a copper plating material permits a period of time in which a concentration of the impurities reaches an upper limit determined from a viewpoint of control of the plating bath to be increased, to thereby reduce the number of times of renewal or refreshment of the plating bath, leading to a reduction in plating cost.
  • Copper oxide was obtained by subjecting basic copper carbonate to thermal decomposition at a temperature of 400° C. for about 60 minutes according to the embodiment described above.
  • Copper oxide was obtained by subjecting basic copper carbonate to thermal decomposition at a temperature of 600° C. for about 60 minutes according to the embodiment described above.
  • Copper oxide was obtained by subjecting basic copper carbonate to thermal decomposition at a temperature of 700° C. for about 60 minutes according to the embodiment described above.
  • Copper oxide was obtained by subjecting basic copper carbonate to thermal decomposition at a temperature of 750° C. for about 60 minutes according to the embodiment described above.
  • Copper oxide was obtained by subjecting basic copper carbonate to thermal decomposition at a temperature of 800° C. for about 60 minutes according to the embodiment described above.
  • Copper oxide was obtained by subjecting basic copper carbonate to thermal decomposition at a temperature of 900° C. for about 60 minutes according to the embodiment described above.
  • a temperature of thermal decomposition of the basic copper carbonate up to 800° C. ensures that the copper oxide is easily dissolved in the aqueous sulfuric acid solution, however, an increase in the temperature to a level of 900° C. causes the copper oxide to fail to be easily dissolved therein.
  • a reduction in thermal decomposition temperature from 800° C. to 600° C. permits a reduction in dissolution time or permits the copper oxide to be easily dissolved in the solution.
  • the thermal decomposition temperature is preferably below 800° C., and, for example, more preferably 600° C. or below. A reduction in solubility of the copper oxide due to an increase in temperature would be due to the reason that an increase in temperature promotes solid phase sintering of the copper oxide obtained by thermal decomposition.
  • Copper oxide was obtained by subjecting basic copper carbonate to thermal decomposition at a temperature of 400° C. for about 60 minutes according to the embodiment described above.
  • Example 2 The procedure described in Example 2 was substantially repeated except that a rotary kiln which has a reducing atmosphere formed therein due to direct heating by a burner was used.
  • Example 2 The procedure described in Example 2 was substantially repeated except that a temperature at which the basic copper carbonate is thermally decomposed was set to be 900° C.
  • Example 2 A powder of copper oxide obtained in each of Example 2, and Comparative Examples 2-1 and 2-2 was charged in an amount of 550 g into 10 l of an aqueous sulfuric acid solution having a H 2 SO 4 concentration of 245 g/l and dissolved therein, to thereby obtain each of sample solutions. Then, the sample solutions each were subjected to filtration by means of a filter paper and then the amount of an insoluble residue left on the filter paper was measured. Results thereof were as shown in Table 3. TABLE 3 Comparative Comparative Example 2 Example 2-1 Example 2-2 Amount of 22 1100 280 Residue (mg) Ratio of 0.01 or less (0.004) 0.20 0.05 Residue * (%)
  • Copper oxide was obtained by subjecting basic copper carbonate to thermal decomposition at a temperature of 400° C. for about 60 minutes according to the embodiment described above. Then, the copper oxide was washed with water under conditions described below. Then, concentration of Na and Cl contained in copper oxide before the washing and those thereafter were measured by inductively coupled plasma-analysis of emission spectrum (ICP-AES) or titration. Results of the measurement were as shown in Table 4. TABLE 4 Copper Oxide Before Water Washing After Water Washing Na Concentration (ppm) 1440 84 Cl Concentration (ppm) 58 10
  • Washing Conditions 500 g of the copper oxide powder was charged in 4500g of water, stirred for 10 minutes, and filtered followed by water washing. The water washing was carried out using 5000 g of water with respect to 500 g of copper oxide powder.
  • Copper electroplating was executed under the following conditions while using copper oxide having a chlorine concentration (Cl concentration) of about 20 ppm as a copper supply.
  • Electrode area 10 cm ⁇ 10 cm
  • a chlorine concentration in the plating bath at the time of starting of the copper plating was adjusted to be about 20 ppm.
  • a chlorine concentration in the plating bath was not increased but reduced.
  • chlorine was added at a rate of 5 to 20 ppm/day thereto.
  • the cathode ultimately obtained had a highly flat and smooth surface.
  • Copper electroplating was executed under substantially the same conditions as in Example 4 described above while using copper oxide having a chlorine concentration of about 140 ppm as a copper supply.
  • a chlorine concentration in the plating bath at the time of starting of the copper plating was adjusted to be about 20 ppm.
  • a chlorine concentration in the plating bath was increased at a rate of 2 to 4 ppm/day. This would be due to the fact that the amount of chlorine contained in the copper oxide fed was increased as compared with the amount of chlorine generated from the anode.
  • a chlorine concentration in the plating bath was increased to a level of about 150 ppm.
  • the cathode ultimately obtained had a rough surface as compared with that obtained in Example 4 described above.
  • FIG. 5 generally shows an apparatus of the batch type for executing such a method.
  • an aqueous cupric chloride (CuCl 2 ) solution having a copper concentration, for example, of 10% by weight and an aqueous solution containing a carbonate ion are fed through feed lines 100 and 200 to a reaction tank 9 in which, for example, pure water is previously filled so that a mixed solution of both aqueous solutions has a predetermined pH value within a range of between 8.0 and 9.0.
  • CuCl 2 aqueous cupric chloride
  • aqueous solution containing a carbonate ion may be an aqueous solution of sodium carbonate having a carbonate concentration of 7% by weight. Then, the mixed solution is stirred for a predetermined period of time by stirring means 91 , to thereby lead to a reaction between cupric chloride and sodium carbonate.
  • reference numeral 301 designates a pH detection section for detecting a pH (hydrogen ion concentration) of the solution in the reaction tank 9 .
  • Reference numeral 302 is a temperature detection section for detecting a temperature of the solution in the reaction tank 9 . Detection signals detected by the pH detection section 301 and temperature detection section 302 are fed to a control section 400 .
  • the feed lines 100 and 200 are provided with flow control sections 101 and 201 , respectively.
  • the flow control sections 101 and 201 each may be constituted by a valve.
  • the flow control sections 101 and 201 each are operated to control a feed rate of each of the aqueous cupric chloride solution and aqueous sodium carbonate solution so that a pH detected by the pH detection section 301 may have a predetermined value.
  • heated water vapor steam
  • a bubbling means 303 such as an air diffusing pipe or the like arranged in the reaction tank 9 , to thereby heat the mixed solution so as to permit it to have a predetermined temperature within a range of between 75° C. and 90° C., resulting in a reaction of the mixed solution being carried out.
  • the reaction may take place for, for example, two hours.
  • the above-described heating of the mixed solution may be controlled by adjusting the degree of opening of a valve 305 provided on a steam line 304 through the control section 400 depending on a signal detected by the temperature detection section 302 .
  • a pH of the mixed solution in the reaction tank 9 below 8.0 causes a chlorine concentration of the thus-obtained basic copper carbonate to be increased, whereas the pH above 9.0 causes the basic copper carbonate to be partially changed into copper oxide and leads to an increase in the amount of alkali used.
  • the pH is preferably set within a range of between 8.0 and 9.0.
  • a reaction temperature of the mixed solution (temperature of the mixed solution) in the reaction tank 9 which is 70° C. or below would permit a chlorine concentration of the basic copper carbonate to be reduced when the reaction time is increased.
  • a reduction in chlorine concentration to a level below a reference level predetermined by the present invention is not attained even by the reaction extending over 8 hours, as will be noted from examples described below; thus, the reaction temperature at 70° C. or below is not commercially accepted.
  • the reaction temperature at 75° C. leads to a satisfactory reduction in chlorine concentration by the reaction for, for example, 1.5 hours or more.
  • the chlorine concentration tends to be decreased with an increase in reaction temperature when the reaction time is rendered the same.
  • the reaction temperature is set at a target value, it is unavoidable that the temperature is actually somewhat varied.
  • the target value is necessarily set to be within a range of between 75° C. and 90° C.
  • the illustrated embodiment is directed to the method of the batch type.
  • the method of the illustrated embodiment may be continuously practiced, for example, in a manner to discharge the mixed solution from an upper peripheral edge of the reaction tank while upwardly feeding an aqueous cupric chloride solution and an aqueous cupric sulfate solution to the reaction tank from a bottom thereof.
  • the reaction time is defined to be a period of time for which the solution resides or is retained in the reaction tank.
  • the copper ion source which is a material for the basic copper carbonate may be constituted by an aqueous cupric sulfate solution in place of an aqueous cupric chloride solution. This causes SO 4 to be introduced from the cupric sulfate into the basic copper carbonate.
  • reaction conditions for permitting a reduction in SO 4 concentration which include a pH of the mixed solution, a reaction temperature thereof and a reaction time thereof are the same as those for reducing introduction of Cl from cupric chloride into the basic copper carbonate.
  • a concentration of copper in the aqueous cupric chloride solution is preferably within a range of, for example, between 5% by weight and 24% by weight.
  • a concentration of copper in the aqueous cupric sulfate solution is preferably within a range of, for example, between 5% by weight and 16% by weight.
  • a carbonate concentration of the aqueous sodium carbonate solution is preferably, within a range of, for example, between 2% by weight and 15% by weight.
  • the carbonate ion sources may include carbonates of alkaline metals such as sodium carbonate, sodium bicarbonate, potassium carbonate and the like, carbonates of alkaline earth metals such as calcium carbonate, magnesium carbonate, barium carbonate and the like, ammonium carbonate ((NH 4 ) 2 CO 3 ), and the like.
  • carbon dioxide gas may be introduced or blown into the aqueous solution without using the carbonates.
  • cupric chloride permits the amount of Cl contained in the basic copper carbonate to be reduced and use of cupric sulfate reduces a content of S (derived from SO 4 ) in the copper carbonate.
  • use of the basic copper carbonate as a material for copper plating or a copper plating material permits an increase in a period of time in which a concentration of impurities in the plating bath reaches an upper limit predetermined from a viewpoint of control of the plating bath, resulting in the number of times of renewal or refreshment of the plating bath being reduced, leading to a decrease in plating cost.
  • the reaction temperature is set to be within a range of between 75° C. and 90° C.
  • a reaction temperature is set to be 95° C. or more.
  • an increase in reaction temperature leads to a reduction in a content of Cl and S (derived from SO 4 ) in the basic copper carbonate.
  • Cl and S derived from SO 4
  • the reaction temperature is set to be 95° C. or more
  • the feed ratio rather than pH is controlled.
  • a range in which the feed ratio is set is varied depending on a concentration of the mixed solution.
  • a molar ratio between a copper ion and a carbonate ion in the mixed solution is defined for the feed ratio.
  • the aqueous cupric sulfate solution and the aqueous solution containing the carbonate ion are fed to the reaction tank 9 while adjusting the feed ratio so as to ensure that a molar ratio between the copper ion and the carbonate ion in the mixed solution is 1:2.3 to 4.6.
  • the method of the illustrated embodiment may be executed by means of a continuous processing apparatus shown in FIG. 6 by way of example.
  • the continuous processing apparatus of FIG. 6 is constructed in such a manner that a reaction tank 9 has feed lines 100 and 200 connected to, for example, a bottom thereof and is configured so as to discharge the solution through an overflow portion 93 formed on an upper peripheral edge thereof.
  • a control section 400 controls flow control sections 101 and 201 depending on a feed ratio (set value of feed ratio) between the aqueous cupric chloride solution and the aqueous sodium carbonate solution which permits a molar ratio between the copper ion and the carbonate ion to be 1:1.3 to 2.6, to thereby control the feed ratio.
  • a pH detection section 301 may be arranged so as to monitor a pH of the mixed solution, to thereby output any alarm and provide a warning to an operator when a value detected is out of a predetermined range. Such construction ensures stabilization of the processing.
  • the illustrated embodiment not only permits a reduction in concentration of each of Cl and SO 4 contained in the basic copper carbonate, but reduces alkaline metal such as sodium and/or alkaline earth metal incorporated from the carbonate into the plating bath. Accumulation of alkaline metal and/or alkaline earth metal in the plating bath causes sulfate thereof to be possibly deposited on an surface of an article plated. In order to avoid such a problem, it is required to increase the number of times of refreshment of the plating bath.
  • the illustrated embodiment constructed as described above effectively eliminates the disadvantage.
  • the thus-obtained basic copper carbonate may be fed as a copper supply for copper plating to such an apparatus as described above with reference to FIG. 2.
  • a laboratory-scale apparatus constructed in correspondence to the apparatus shown in FIG. 5 was used.
  • a reaction tank of the apparatus was previously filled therein with a suitable amount of pure water, which was kept at a temperature of 75° C. while being stirred.
  • the reaction tank was fed therein with the aqueous cupric chloride solution and aqueous sodium carbonate solution so as to render a pH target value (controlled pH) constant and was heated by a heater so as to maintain a reaction temperature therein constant.
  • the mixed solution was stirred to deposit or precipitate basic copper carbonate in the reaction tank, which was then subjected to solid-liquid separation, to thereby obtain a powder of basic copper carbonate.
  • the reaction conditions were as follows:
  • Aqueous cupric chloride solution Copper concentration of 10% by weight
  • Aqueous sodium carbonate solution Carbonate ion concentration of 7% by weight
  • Basic copper carbonate was obtained by substantially repeating the procedure of Example 5-1 except that the pH target value was set to be 8.5, 8.75 and 9.0, respectively.
  • Basic copper carbonate was obtained by substantially repeating the procedure of Example 5-1 except that the reaction temperature was set to be 80° C. and 90° C., respectively.
  • Basic copper carbonate was obtained by substantially repeating the procedure of Example 5-1 except that the reaction time was set to be 4 hours and 8 hours, respectively.
  • Basic copper carbonate was obtained by substantially repeating the procedure of Example 5-1 except that a carbonate ion concentration of the aqueous sodium carbonate solution was set to be 2.0% by weight and 3.5% by weight, respectively.
  • Basic copper carbonate was obtained by substantially repeating the procedure of Example 5-1 except that the reaction time was set to be 4 hours and the pH target value was set to be 8.5.
  • Basic copper carbonate was obtained by substantially repeating the procedure of Example 5-1 except that the reaction temperature was set to be 70° C., the pH target value was set to be 8.0, and the reaction time was set to be 2 hours.
  • Basic copper carbonate was obtained by substantially repeating the procedure of Example 5-1 except that the reaction temperature was set to be 70° C., the pH target value was set to be 8.0 and the reaction time was set to be 8 hours.
  • Basic copper carbonate was obtained by substantially repeating the procedure of Example 5-1 except that an aqueous cupric sulfate solution having a copper concentration of 5% by weight was substituted for the aqueous cupric chloride solution.
  • Basic copper carbonate was obtained by substantially repeating the procedure of Example 6-1 except that the reaction temperature was set to be 80° C. and 90° C., respectively.
  • Basic copper carbonate was obtained by substantially repeating the procedure of Example 6-1 except that the pH target value was set to be 7.3.
  • Example 6-1 to Comparative Example 6-1 substitution of the aqueous cupric sulfate solution for the aqueous cupric chloride solution causes an anion introduced into the basic copper carbonate to be SO 4 rather than Cl.
  • SO 4 an anion introduced into the basic copper carbonate
  • a variation in SO 4 concentration depending on a variation in pH was measured. As a result, the concentration was increased to a level as high as 510 ppm when pH is below 8.0; whereas it was reduced to a level as low as 200 ppm or less when pH is at 8.0.
  • Basic copper carbonate was obtained by substantially repeating the procedure of Example 5-1 except that the reaction temperature was set to be each of 75° C., 80° C., 90° C., 95° C. and 100° C. Then, a concentration of Cl in each of the basic copper carbonates thus obtained was measured. Results of the measurement were as shown in Table 7. (Results in connection with 75° C., 80° C. and 90° C. were described above.) Also, a feed ratio of the aqueous sodium carbonate which constitutes an alkali side to the aqueous cupric chloride solution which constitutes an acid side(fed amount of an aqueous sodium carbonate solution divided by fed amount of an aqueous cupric chloride solution) was as shown in Table 7. TABLE 7 Reaction Temperature (° C.) 75 80 90 95 100 Cl Concentration (ppm) 75 70 40 110 50000 Feed Ratio 2.0 1.9 1.8 1.5 1.2
  • Basic copper carbonate was obtained by substantially repeating the procedure of Example 6-1 except that the aqueous cupric sulfate solution was substituted for the aqueous cupric chloride and the reaction temperature was set to be each of 75° C., 80° C., 90° C., 95° C. and 100° C. Then, a concentration of SO 4 in each of the basic copper carbonates thus obtained was measured. Results of the measurement were as shown in Table 8. (Results in connection with 75° C., 80° C. and 90° C. were described above.) Also, a feed ratio of the aqueous sodium carbonate which constitutes an alkali side to the aqueous cupric sulfate solution which constitutes an acid side was as shown in Table 8. TABLE 8 Reaction Temperature (° C.) 75 80 90 95 100 SO 4 Concentration (ppm) 190 180 130 360 15000 Feed Ratio 1.8 1.7 1.6 1.3 1.0
  • Electrode area 10 cm ⁇ 10 cm
  • a chlorine concentration in the plating bath at the time of starting of the plating was adjusted to be about 20 ppm.
  • a chlorine concentration in the plating bath was increased to a level of 1 to 2 ppm/day.
  • the Cl concentration was rendered constant at the time when the Cl concentration in the plating bath reached a level of about 40 ppm. An increase in Cl concentration was not observed even after lapse of 40 days.
  • the cathode ultimately obtained had a highly flat and smooth surface.
  • Copper electroplating was executed by substantially repeating the procedure of Example 8-1 except that basic copper carbonate having a SO 4 concentration of about 150 ppm was used as a copper supply.
  • the copper electroplating was started while keeping an initial sulfuric acid concentration in the plating bath at 180 g/l.
  • a SO 4 concentration in the plating bath was increased to a level of 9 mg/day. Volatilization of SO 4 from the plating bath or the like was not observed. Accumulation of SO 4 in the plating bath was very slow, therefore, it would be considered that dilution of the plating bath or the like is not required for control of the SO 4 concentration in the plating bath.
  • Copper electroplating was executed by substantially repeating the procedure of Example 8-1 except that basic copper carbonate having a Cl concentration of about 200 ppm was used as a copper supply.
  • a chlorine concentration in the plating bath at the time of starting of the plating was adjusted to be about 20 ppm.
  • a Cl concentration in the plating bath was increased to a level of 3 to 4 ppm/day. This would be due to the fact that the amount of chlorine generated from the anode is reduced as compared with the amount of chlorine contained in basic copper carbonate oxide fed.
  • the Cl concentration in the plating bath was increased to about 160 ppm. The cathode ultimately obtained had a coarse surface as compared with that obtained in Example 8-1.
  • Copper electroplating was executed by substantially repeating the procedure of Example 8-2 described above except that basic copper carbonate having a SO 4 concentration of about 500 ppm was used as a copper supply.
  • the copper electroplating was started while keeping an initial sulfuric acid concentration in the plating bath at 180 g/l.
  • a SO 4 concentration in the plating bath was increased to a level of 30 mg/day. Volatilization of SO 4 from the plating bath or the like was not observed. This caused SO 4 to be accumulated in the plating bath, so that it was required to carry out dilution or the like in order to control of the SO 4 concentration in the plating bath.
  • a Cl concentration of the basic copper carbonate is 80 ppm or less, no increase of the Cl concentration in the plating bath is observed, resulting in satisfactory copper electroplating.
  • a Cl concentration of the basic copper carbonate is preferably 80 ppm or less.
  • SO 4 concentration of the basic copper carbonate is 200 ppm or less, accumulation of SO 4 is delayed. It is further expected to take a long period until dilution or the like is required to control of the SO 4 concentration in the plating bath, even if necessary.
  • SO 4 concentration of the basic copper carbonate is preferably 200 ppm or less.
  • the present invention provides a copper electroplating material which is easily dissolved, minimizes formation of an insoluble residue and ensures satisfactory copper plating. Also, copper electroplating by means of the copper electroplating material of the present invention minimizes the number of times of refreshment of the plating bath, to thereby restrain an increase in plating cost.

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  • Electrochemistry (AREA)
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  • Automation & Control Theory (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Electrolytic Production Of Metals (AREA)
US09/944,344 2000-09-04 2001-09-04 Material for copper electroplating, method for manufacturing same and copper electroplating method Abandoned US20020053518A1 (en)

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Cited By (4)

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US6723219B2 (en) * 2001-08-27 2004-04-20 Micron Technology, Inc. Method of direct electroplating on a low conductivity material, and electroplated metal deposited therewith
US20070225328A1 (en) * 2006-03-17 2007-09-27 Monika Fritz Synthetic nacre
CN103303960A (zh) * 2013-05-23 2013-09-18 东又悦（苏州）电子科技新材料有限公司 一种球状碱式碳酸铜粉的制备方法
CN103303961A (zh) * 2013-05-23 2013-09-18 东又悦（苏州）电子科技新材料有限公司 一种球状电镀级氧化铜粉的制备方法

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TWI267494B (en) * 2004-06-18 2006-12-01 Tsurumisoda Co Ltd Copper plating material, and copper plating method
US8262894B2 (en) 2009-04-30 2012-09-11 Moses Lake Industries, Inc. High speed copper plating bath
KR101313844B1 (ko) 2012-04-02 2013-10-01 (주)에이치에스켐텍 동폐액으로부터 동 도금 재료용 및 고품위 산화동을 제조하는 방법
JP6619718B2 (ja) * 2016-10-14 2019-12-11 株式会社荏原製作所 基板のめっきに使用される酸化銅粉体、該酸化銅粉体を用いて基板をめっきする方法、該酸化銅粉体を用いてめっき液を管理する方法

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JPH0380116A (ja) * 1989-08-23 1991-04-04 Sumitomo Metal Mining Co Ltd 酸化第二銅粉末の製造方法
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US4659555A (en) * 1984-05-12 1987-04-21 Th. Goldschmidt Ag 03 Process for the preparation of basic copper carbonate
US4677234A (en) * 1985-02-04 1987-06-30 Union Carbide Corporation Process for the preparation of ethylene glycol
US5449845A (en) * 1988-11-22 1995-09-12 E. I. Du Pont De Nemours And Company Purification of saturated halocarbons
US5492681A (en) * 1993-03-22 1996-02-20 Hickson Corporation Method for producing copper oxide
US6218335B1 (en) * 1998-07-24 2001-04-17 Chiyoda Corporation Spinel type compound oxide and method of manufacturing the same

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6723219B2 (en) * 2001-08-27 2004-04-20 Micron Technology, Inc. Method of direct electroplating on a low conductivity material, and electroplated metal deposited therewith
US20070225328A1 (en) * 2006-03-17 2007-09-27 Monika Fritz Synthetic nacre
CN103303960A (zh) * 2013-05-23 2013-09-18 东又悦（苏州）电子科技新材料有限公司 一种球状碱式碳酸铜粉的制备方法
CN103303961A (zh) * 2013-05-23 2013-09-18 东又悦（苏州）电子科技新材料有限公司 一种球状电镀级氧化铜粉的制备方法

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CN1170010C (zh) 2004-10-06
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TW539652B (en) 2003-07-01

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