JP2005029892A - Copper plating material, and copper plating method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain copper oxide powder having a purity of ≥98.5%, high solubility in a plating liquid comprising an additive consisting of organic matter, and suitable as a copper plating material. <P>SOLUTION: Basic copper carbonate powder is heated and thermally decomposed, e.g., at 400°C for 20 min in an atmosphere which does not become a reducing atmosphere in, e.g., an electric heating furnace to obtain copper oxide powder. As for the copper oxide powder obtained in this way, let the peak intensity of the (-1, 1, 1) plane of an X-ray diffraction spectrum be I, and the peak intensity of the (-1, 1, 1) plane of the X-ray diffraction spectrum of standard copper oxide powder after the completion of recrystallization be Is. Then the peak intensity ratio between the peak intensity I of the copper oxide powder and the peak intensity Is of the standard copper oxide powder, I/Is, is ≤0.36. The copper oxide powder having the above structure has high solubility to a plating liquid containing an additive consisting of organic matter. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a copper plating material composed of basic copper carbonate powder, copper oxide powder obtained by a direct wet method and copper oxide powder made of cupric hydroxide powder, and a copper plating method using the copper oxide powder. .

  As one method of performing copper plating treatment on a body to be plated, a copper plating material is supplied to an electrolytic solution (a plating liquid containing sulfuric acid or copper sulfate as a main component), and between the body to be plated forming an insoluble anode and a cathode. There is an electroplating method to energize. As a copper plating material used in this method, copper oxide powder obtained by thermally decomposing basic copper carbonate powder is known. Since the copper plating material is appropriately replenished in the electrolyte, it must be easily soluble in sulfuric acid, but the copper oxide powder obtained by pyrolyzing the basic copper carbonate powder is Since this condition is satisfied, it is a suitable material.

  As a method for producing such copper oxide powder, for example, a method shown in Patent Document 1 has been proposed. In this document 1, as an example, the basic copper carbonate powder is heated at a temperature of 400 ° C. to 800 ° C. for 60 minutes in an atmosphere that is not a reducing atmosphere, and thermally decomposed, thereby converting the copper oxide powder to a high conversion efficiency. It can be manufactured with. In this temperature range, the higher the processing temperature, the higher the conversion efficiency can be secured in a shorter time. For this reason, since throughput is required industrially, thermal decomposition is performed at a high temperature of, for example, 700 ° C. or more.

Japanese Patent Application No. 2000-267018

  By the way, in the plating solution, an additive is often dissolved in order to ensure the uniformity and gloss of the plating film. Examples of the additive include SPS (sodium salt of bis (3-sulfopropyl) disulfide), thiourea, Janus green and the like, -C = S group having a double bond of carbon (C) and sulfur (S). Or -S-S- group (disulfide compound) having a single bond between S and S, or -N = N- group (diazo compound) having a double bond between nitrogen (N) and N Organic matter is used.

  However, it was recognized that the copper oxide powder produced by the method of the above-mentioned Patent Document 1 has a considerably low solubility in the plating solution containing the additive component made of the above-mentioned organic substance. Further, when the -SS- group is reduced to -SH group (thioalcohols), when an additive having -SS-group is dissolved in the plating solution, -S-S is added to the plating solution. Although it is presumed that -H group exists, it was confirmed that the above copper oxide powder has low solubility even by the presence of this -S-H group. Thus, when the solubility of the copper plating material with respect to a plating solution is bad, the copper (Cu) replenishment in a plating tank will be delayed. In addition, since the copper ion concentration in the plating solution is not constant, the uniformity of the plating film is deteriorated, or there is a copper plating material that does not dissolve in the plating solution, and the filter provided between the plating bath is clogged. In addition, the copper plating material that has passed through the filter may adversely affect the plated product.

  The present invention has been made based on such circumstances, and an object of the present invention is to provide a high-purity copper plating material that is highly soluble in an electrolyte containing an organic additive, and such a copper plating. It is to provide a copper plating method using a material.

The present invention provides a copper plating material provided with an insoluble anode and an object to be plated to form a cathode, and supplied to an electrolytic solution containing an organic additive.
This copper plating material is a copper oxide powder having a purity of 98.5% or more obtained by thermally decomposing basic copper carbonate powder in an atmosphere that is not a reducing atmosphere,
The peak intensity of the (-1,1,1) plane of the X-ray diffraction spectrum of this copper oxide powder is I,
When the peak intensity of the (-1, 1, 1) plane of the X-ray diffraction spectrum of the reference copper oxide powder that has been crystallized is Is,
The copper oxide powder is characterized in that the peak intensity ratio I / Is between the peak intensity I of the copper oxide powder and the peak intensity Is of the reference copper oxide powder is 0.36 or less.

The copper plating material is a copper oxide powder having a purity of 98.5% or more obtained by pyrolyzing basic copper carbonate powder in an atmosphere that is not a reducing atmosphere,
The full width at half maximum of the (-1,1,1) plane of the X-ray diffraction spectrum of this copper oxide powder is F,
When the full width at half maximum of the (−1, 1, 1) plane of the X-ray diffraction spectrum of the reference copper oxide powder that has been crystallized is Fs,
A copper oxide powder having a half-value width ratio F / Fs of 2.9 or more between the half-value width F of the copper oxide powder and the half-value width Fs of the reference copper oxide powder can also be used.

  Further, the copper plating material is a copper oxide powder having a purity of 98.5% or more obtained by thermally decomposing basic copper carbonate powder in an atmosphere that is not a reducing atmosphere, and has a specific surface area of 7. A copper oxide powder of 3 m 2 / g or more can also be used.

Further, the present invention provides a copper plating material provided with an insoluble anode and an object to be plated to form a cathode, and supplied to an electrolytic solution containing an organic additive.
This copper plating material is a copper oxide powder having a purity of 98.5% or more obtained by reacting an aqueous solution of a copper salt with an alkaline solution to obtain copper oxide powder and heating the copper oxide powder. ,
The peak intensity of the (-1,1,1) plane of the X-ray diffraction spectrum of this copper oxide powder is I,
When the peak intensity of the (-1, 1, 1) plane of the X-ray diffraction spectrum of the reference copper oxide powder that has been crystallized is Is,
The copper oxide powder is characterized in that the peak intensity ratio I / Is between the peak intensity I of the copper oxide powder and the peak intensity Is of the reference copper oxide powder is 0.52 or less. Here, examples of the aqueous solution of the copper salt include aqueous solutions of cupric chloride, cupric sulfate, cupric nitrate, and the like.

The copper plating material is a copper oxide powder having a purity of 98.5% or more obtained by reacting an aqueous solution of copper salt with an alkaline solution to obtain copper oxide powder and heating the copper oxide powder. There,
The full width at half maximum of the (-1,1,1) plane of the X-ray diffraction spectrum of this copper oxide powder is F,
When the full width at half maximum of the (−1, 1, 1) plane of the X-ray diffraction spectrum of the reference copper oxide powder that has been crystallized is Fs,
A copper oxide powder having a half-value width ratio F / Fs of 2.9 or more between the half-value width F of the copper oxide powder and the half-value width Fs of the reference copper oxide powder can also be used.

  Further, as the copper plating material, a copper oxide powder having a purity of 98.5% or more obtained by reacting an aqueous solution of a copper salt with an alkaline solution to obtain a copper oxide powder and heating the copper oxide powder is used. In addition, copper oxide powder having a specific surface area of 3.3 m 2 / g or more can be used.

Further, the present invention provides a copper plating material provided with an insoluble anode and an object to be plated to form a cathode, and supplied to an electrolytic solution containing an organic additive.
This copper plating material is a copper oxide powder having a purity of 98.5% or more obtained by thermally decomposing cupric hydroxide powder,
The peak intensity of the (-1,1,1) plane of the X-ray diffraction spectrum of this copper oxide powder is I,
When the peak intensity of the (-1, 1, 1) plane of the X-ray diffraction spectrum of the reference copper oxide powder that has been crystallized is Is,
The peak intensity ratio I / Is between the peak intensity I of the copper oxide powder and the peak intensity Is of the reference copper oxide powder is 0.67 or less.

The copper plating material is a copper oxide powder having a purity of 98.5% or more obtained by pyrolyzing cupric hydroxide powder,
The full width at half maximum of the (-1,1,1) plane of the X-ray diffraction spectrum of this copper oxide powder is F,
When the full width at half maximum of the (−1, 1, 1) plane of the X-ray diffraction spectrum of the reference copper oxide powder that has been crystallized is Fs,
A copper oxide powder having a half-value width ratio F / Fs between the half-value width F of the copper oxide powder and the half-value width Fs of the reference copper oxide powder of 1.6 or more can also be used.

  Further, as the copper plating material, copper oxide powder having a purity of 98.5% or more obtained by pyrolyzing cupric hydroxide powder and having a specific surface area of 3.6 m 2 / g or more is used. Powder can also be used.

  Examples of the additive include organic substances including any one of a double bond of carbon and sulfur, a single bond of sulfur and sulfur, a double bond of nitrogen and nitrogen, and a single bond of sulfur and hydrogen, such as bis (3 -Sulfopropyl) disulfide and salt, thiourea, Janus green, dimethyl disulfide, propyl mercaptan, mercaptopropyl sulfonic acid and salt, or methyl yellow can be used.

  The copper plating method of the present invention is a copper plating method in which an insoluble anode and a cathode to be plated are provided, a copper plating material is supplied to an electrolytic solution containing an organic additive, and the plated body is plated with copper. The copper plating material is a copper oxide powder having a purity of 98.5% or more obtained by thermally decomposing basic copper carbonate powder in an atmosphere that is not a reducing atmosphere. The peak intensity of the (-1,1,1) plane of the X-ray diffraction spectrum of I is defined as I, and the peak intensity of the (-1,1,1) plane of the X-ray diffraction spectrum of the reference copper oxide powder after crystallization is completed. When Is, it is a copper oxide powder having a peak intensity ratio I / Is between the peak intensity I of the copper oxide powder and the peak intensity Is of the reference copper oxide powder of 0.36 or less.

  In the copper plating method of the present invention, the copper plating material is a copper oxide powder having a purity of 98.5% or more obtained by thermally decomposing basic copper carbonate powder in an atmosphere that is not a reducing atmosphere. Then, the half-value width of the (-1,1,1) plane of the X-ray diffraction spectrum of this copper oxide powder is F, and the (-1,1,1) of the X-ray diffraction spectrum of the reference copper oxide powder after crystallization is completed. ) When the half width of the surface is Fs, the copper oxide powder having a half width ratio F / Fs of the half width F of the copper oxide powder and the half width Fs of the reference copper oxide powder of 2.9 or more, or a specific surface area However, you may make it use the copper oxide powder of 7.3 m2 / g or more.

  In such an invention, the copper plating material is a copper oxide powder having a purity of 98.5% or more, and the peak intensity ratio I / Is is 0.36 or less or the half width ratio F / Fs is 2.9. As described above, since the copper oxide powder having a specific surface area of 7.3 m 2 / g or more is used, high solubility can be ensured even in an electrolytic solution containing an organic additive.

  Further, another copper plating method of the present invention is provided with an insoluble anode and a body to be a cathode, and a copper plating material is supplied to an electrolytic solution containing an organic additive to perform copper plating on the body to be plated. A copper plating material is obtained by reacting an aqueous solution of a copper salt with an alkaline solution to obtain a copper oxide powder, and the purity obtained by heating the copper oxide powder is 98.5% or more. It is copper powder, Comprising: The peak intensity of the (-1,1,1) plane of the X-ray diffraction spectrum of this copper oxide powder is set to I, and (-1 , 1, 1) copper oxide powder having a peak intensity ratio I / Is between the peak intensity I of the copper oxide powder and the peak intensity Is of the reference copper oxide powder of 0.52 or less, where Is is the peak intensity of the plane. It is characterized by being.

  Furthermore, in another copper plating method of the present invention, as the copper plating material, an aqueous copper salt solution and an alkali solution are reacted to obtain copper oxide powder, and the purity obtained by heating the copper oxide powder is 98. X-ray of a reference copper oxide powder having a crystallization of 5% or more of copper oxide powder, where the half-value width of the (-1,1,1) plane of the X-ray diffraction spectrum of this copper oxide powder is F When the half-value width of the (-1, 1, 1) plane of the diffraction spectrum is Fs, the half-value width ratio F / Fs between the half-value width F of the copper oxide powder and the half-value width Fs of the reference copper oxide powder is 2. You may make it use the 9 or more copper oxide powder and the copper oxide powder whose specific surface area is 3.3 m <2> / g or more.

  In such an invention, the copper plating material is a copper oxide powder having a purity of 98.5% or more, and the peak intensity ratio I / Is is 0.52 or less or the half width ratio F / Fs is 2.9. As mentioned above, since the copper oxide powder having a specific surface area of 3.3 m 2 / g or more is used, high solubility can be ensured even in an electrolytic solution containing an organic additive.

  Furthermore, in another copper plating method of the present invention, an insoluble anode and a cathode to be plated are provided, a copper plating material is supplied to an electrolytic solution containing an organic additive, and the copper to be plated is plated. A copper plating method, wherein the copper plating material is a copper oxide powder having a purity of 98.5% or more obtained by pyrolyzing cupric hydroxide powder, and X-ray diffraction of the copper oxide powder When the peak intensity on the (-1,1,1) plane of the spectrum is I and the peak intensity on the (-1,1,1) plane of the X-ray diffraction spectrum of the reference copper oxide powder after crystallization is Is Further, the copper oxide powder is characterized in that the peak intensity ratio I / Is between the peak intensity I of the copper oxide powder and the peak intensity Is of the reference copper oxide powder is 0.67 or less.

  Furthermore, in another copper plating method of the present invention, the copper plating material is a copper oxide powder having a purity of 98.5% or more obtained by thermally decomposing cupric hydroxide powder. The half-value width of the (-1, 1, 1) plane of the X-ray diffraction spectrum of the copper powder is F, and the half of the (-1, 1, 1) plane of the X-ray diffraction spectrum of the reference copper oxide powder after crystallization is completed. When the value width is Fs, the copper oxide powder having a full width at half maximum F / Fs of 1.6 or more and the specific surface area of 3.6 m 2 between the half width F of the copper oxide powder and the half width Fs of the reference copper oxide powder. / G or more of copper oxide powder may be used.

  In such an invention, the copper plating material is a copper oxide powder having a purity of 98.5% or more, and the peak intensity ratio I / Is is 0.67 or less or the half width ratio F / Fs is 1.6. As described above, since the copper oxide powder having a specific surface area of 3.6 m 2 / g or more is used, high solubility can be ensured even in an electrolytic solution containing an organic additive.

  According to the present invention, the copper oxide powder obtained by thermally decomposing basic copper carbonate powder in an atmosphere that is not a reducing atmosphere has a high purity of 98.5% and a peak intensity ratio I of X-ray diffraction. Since copper oxide powder having a / Is of 0.36 or less, a half-width ratio F / Fs of 2.9 or more, or a specific surface area of 7.3 m 2 / g or more is used as a copper plating material, electrolysis including an organic additive High solubility is ensured also for the liquid, and a good plating process can be performed.

  According to the present invention, copper oxide powder is obtained by a direct wet method using an aqueous solution of copper salt and an alkaline solution, and the copper oxide powder obtained by heating the copper oxide powder has a purity of 98.5. As a copper plating material, copper oxide powder having a high X-ray diffraction peak intensity ratio I / Is of 0.52 or less, a full width at half maximum F / Fs of 2.9 or more, or a specific surface area of 3.3 m 2 / g or more is used. Even if it uses, high solubility is ensured with respect to the electrolyte solution containing the additive of organic substance, and a favorable plating process can be performed.

  Furthermore, according to the present invention, the copper oxide powder obtained by thermally decomposing cupric hydroxide powder has a high purity of 98.5% and the peak intensity ratio I / Is of X-ray diffraction is 0.00. Even if a copper oxide powder having a ratio of 67 or less or a full width at half maximum F / Fs of 1.6 or more or a specific surface area of 3.6 m 2 / g or more is used as a copper plating material, it is highly soluble in an electrolyte containing an organic additive. Property is secured, and a good plating process can be performed.

[First Embodiment]
In the first embodiment of the present invention, a commercially available product may be purchased as the basic copper carbonate powder that is a raw material of the copper plating material (copper oxide powder). In this embodiment, the basic copper carbonate powder is purchased. It will be manufactured at the factory without purchasing powder. FIG. 1 is an explanatory view showing the production flow in this case. For example, an aqueous solution of cupric chloride (CuCl2) having a copper concentration of 10% by weight and an alkali metal carbonate, for example, a carbonic acid having a carbonic acid concentration of 7% by weight. An aqueous solution of sodium (Na2 CO3) is introduced into the reaction vessel 1 so that the pH of the mixed solution becomes, for example, 7-9, and is stirred by the stirring means 11 while being heated so that the temperature of the mixed solution becomes, for example, 70 ° C. Stir for 30 minutes to react. The mixed liquid is heated by, for example, providing bubbling means (not shown) including a diffuser tube or the like in the reaction tank 1 and supplying steam from the bubbling means to the mixed liquid.

The above reaction proceeds as follows. First, copper carbonate is generated as in equation (1),
Na2 CO3 + CuCl2 → CuCO3 + 2NaCl (1)
Subsequently, copper carbonate is hydrated as shown in formula (2) to produce basic copper carbonate dihydrate,
CuCO3 + 3 / 2H2 O → 1/2 {CuCO3 · Cu (OH) 2 · 2H2 O} + 1 / 2CO2 (2)
Furthermore, as shown in the formula (3), water is released from the dihydrate, and anhydrous basic copper carbonate is generated.

CuCO3 · Cu (OH) 2 · 2H 2 O → CuCO 3 · Cu (OH) 2 + 2H 2 O (3)
In this way, basic copper carbonate is precipitated and formed into a powder. And the valve | bulb 12 is opened, the slurry which is a deposit is extracted, it sends to the centrifuge 2, and solid content is isolate | separated from mother liquor here by centrifugation, the solid content is put into the dryer 3, and it dries, and basic carbonate is obtained. Obtain copper powder.

  As a copper ion source which is a raw material of basic copper carbonate, an aqueous solution of a copper salt such as copper sulfate or copper nitrate can be used in addition to copper chloride. Sources of carbonate ions include sodium carbonate, alkali metal carbonates such as sodium bicarbonate and potassium carbonate, alkaline earth metal carbonates such as calcium carbonate, magnesium carbonate, and barium carbonate, or ammonium carbonate ((NH4) 2 CO3) or the like can be used.

  Next, the basic copper carbonate, which is a powder, is supplied to a heating furnace, for example, the rotary kiln 4, where it is thermally decomposed by heating at a predetermined temperature for a predetermined time. In this example, as a heating furnace, a rotating tube 41 made of, for example, stainless steel that rotates about a tube axis as a rotating shaft is provided with a slight inclination, and the rotating tube 41 is surrounded by a heater 42 and rotated. A rotary kiln for transferring basic copper carbonate powder is used. If the basic copper carbonate powder is heated in this way, the heating atmosphere does not become a reducing atmosphere. The reason why the basic copper carbonate powder is not directly heated by the burner is that when it is in a reducing atmosphere, the copper carbonate itself or copper carbonate is decomposed into copper oxide, and then partially reduced to cuprous oxide (Cu2 O) or metallic copper This is to avoid (Cu).

  When copper oxide powder is used as a copper plating material, metallic copper does not dissolve or hardly dissolves in sulfuric acid, which is an electrolytic solution, and becomes an insoluble residue, requiring new filtration equipment. Further, when metallic copper or cuprous oxide is formed, the amount of copper to be supplied into the plating bath is not constant, and the quality of the plated product varies. Therefore, it is necessary not to use a reducing atmosphere when heating the basic copper carbonate powder.

  Here, the heating temperature and the heating time in the first embodiment will be described. The copper oxide powder used as a copper plating material in the present invention is required to satisfy the following requirements in consideration of solubility in a copper plating solution and plating quality.

  [1] The purity is 98.5% or more.

  [2] The peak intensity of the (-1, 1, 1) plane of the X-ray diffraction spectrum of the copper oxide powder is I, and the (-1, 1, 1) X-ray diffraction spectrum of the reference copper oxide powder after crystallization is completed. When the peak intensity of the surface is Is, the peak intensity ratio I / Is between the peak intensity I of the copper oxide powder and the peak intensity Is of the reference copper oxide powder is 0.36 or less, or the copper oxide powder The half width of the (-1,1,1) plane of the X-ray diffraction spectrum is F, and the half width of the (-1,1,1) plane of the reference copper oxide powder after crystallization is Fs. When the half-value width F / Fs of the half-value width F of the copper oxide powder and the half-value width Fs of the reference copper oxide powder is 2.9 or more, or the specific surface area of the copper oxide powder is 7.3 m 2 / g. That's it. Here, “−1” on the (−1, 1, 1) plane of the X-ray diffraction spectrum means a bar notation above “1”.

  Here, the reference copper oxide powder refers to a copper oxide powder that has been crystallized, that is, a powder that does not change the peak intensity and the half-value width of X-ray diffraction even if the heat treatment is further performed on the copper oxide powder. Specifically, the reference copper oxide powder in the first embodiment is obtained by heat-treating basic copper carbonate powder at a heating temperature of 750 ° C. for 8 hours in a heating furnace to obtain copper oxide powder. The powder is heat-treated at a heating temperature of 850 ° C. for 12 hours.

  The purity of the copper oxide powder in the first embodiment is a value obtained by measuring the Cu concentration in the copper oxide powder and converted to CuO. The low purity of the copper oxide powder means that the conversion rate of copper carbonate is low and oxidation is performed. This means that a large amount of copper carbonate that does not change to copper remains. When the purity of the copper oxide powder is low and a large amount of copper carbonate remains, variation in the copper oxide concentration increases. For this reason, when used as a copper plating material, the copper concentration tends to change each time the treatment is performed, and it becomes difficult to control the copper concentration of the plating solution. Therefore, as in the requirement [1], the purity is low. 98.5% or more of copper oxide powder is preferred.

  The requirement [2] is a requirement for determining the solubility in the plating solution. Due to the trial and error of the present inventors, the solubility in the plating solution containing an organic additive differs depending on the structure of the copper oxide powder. The copper oxide powder having a structure satisfying the requirement [2] is determined as a result of finding that the copper oxide powder has high solubility in the plating solution.

  In order to obtain copper oxide powder satisfying these requirements, there is a problem in the heating temperature and heating time in a heating furnace. Regarding the heating temperature, thermal decomposition does not occur at 200 ° C., and a temperature of 250 ° C. or higher is required. In order to obtain high-purity copper oxide powder at a temperature of about 0 ° C., a heating time of, for example, 2 hours or more is required. On the other hand, if the heating temperature is too high or the heating time is too long, the requirement [1] is ensured, but the requirement [2] is not met, and the solubility in the plating solution deteriorates.

Therefore, the present inventors conducted various experiments described later, and attempted to optimize the heating temperature and the heating time for producing the copper oxide powder having the above-mentioned requirements. An example of the heat treatment conditions for the basic copper carbonate powder is shown below. The copper oxide powder obtained by thermal decomposition under these conditions satisfies the above two requirements.
(Example of heat treatment conditions for basic copper carbonate powder)
When the heating temperature is 300 ° C, the heating time is 240 minutes or more and 480 minutes or less. When the heating temperature is 400 ° C, the heating time is 20 minutes or more and 40 minutes or less. When the heating temperature is 500 ° C, the heating time is 5 minutes. 40 minutes or less When the heating temperature is 550 ° C., the heating time is 5 minutes or more and 40 minutes or less. When the heating temperature is 600 ° C., the heating time is 5 minutes or more and 20 minutes or less. When the heating temperature is 650 ° C., heating is performed. The time is not less than 5 minutes and not more than 20 minutes After obtaining the copper oxide powder in this way, the copper oxide powder is put into a cleaning tank 5 containing pure water as a cleaning liquid, and stirred by the stirring means 51 and washed with water. . And the valve | bulb 52 is opened, the mixed slurry of water and copper oxide powder is extracted from the washing tank 5, and it is made to dry with the drying machine 7 after removing water with the centrifuge 6 or the filter, and the said copper oxide powder is obtained. As the cleaning liquid, pure water such as distilled water or ion-exchanged water can be used, but water having a lower impurity content than that, such as ultrapure water, can also be used.

  An example of an apparatus for carrying out a copper plating method using copper oxide powder as a copper plating material is shown in FIG. In FIG. 2, reference numeral 8 denotes a plating bath, which is filled with a copper oxide powder produced by the above-described method in sulfuric acid as an electrolytic solution and a plating bath (plating solution) in which an organic additive is dissolved. An insoluble anode 81 connected to the positive electrode side of the DC power source E, for example, a titanium plate coded with white metal platinum and iridium at a ratio of 7: 3, and a cathode connected to the negative electrode side of the DC power source E. A material 82 to be plated, such as a metal plate to be plated, is immersed.

  83 is a dissolution tank, and when the copper ions in the plating bath 8 are reduced, a predetermined amount of copper oxide powder as a copper plating material is supplied into the dissolution tank 83 from a hopper 84 as a supply source, and stirring means After being stirred by 85 and dissolved in sulfuric acid, the pumps P1 and P2 are operated to circulate the plating bath, and then the next copper plating treatment is performed. F is a filter.

  Examples of the additive include a -C = S group having a double bond of C and S, a -S-S- group having a single bond of S and S (disulfide compound), and two of N and N. An organic substance having either a -N = N- group having a heavy bond (diazo compound) or a -SH group having a bond of S and H (thioalcohols), for example, several ppm relative to the plating solution It is added at a ratio of about several hundred ppm. Examples of the additive include thiourea containing a —C═S group (see FIG. 3A), dimethyl disulfide containing a —S—S— group, such as SPS ((bis (3-sulfopropyl) disulfide). Sodium salt: (Bis (3-sulfopropyl) disulfide and salt, such as NaO3S (CH2) 3-SS- (CH2) 3SO3Na), Janus Green containing -N = N- group (see FIG. 3 (b)) And methyl yellow, propyl mercaptan, mercaptopropyl sulfonic acid and salts containing -S-H group, and the like are used.

  According to the above-described embodiment, the thermal decomposition is performed by heating the copper carbonate powder under the above-described heat treatment conditions, so that the peak intensity ratio I / Is is ensured while ensuring a high purity of 98.5% or more. Is 0.36 or less, or a copper oxide powder having a full width at half maximum F / Fs of 2.9 or more or a copper oxide powder having a specific surface area of 7.3 m 2 / g or more. Thereby, although it is high purity copper oxide powder, high solubility is securable also with respect to the plating solution containing the said organic additive with low solubility of the said copper oxide powder. Thus, since the solubility with respect to the plating solution containing an additive is favorable, if this copper oxide powder is used as a copper plating material, the concentration of copper ions in the copper plating bath can be easily stabilized, and the uniformity of the plating film can be achieved. improves. At this time, since the plating solution contains an additive, it is possible to further ensure high uniformity and gloss of the plating film. Further, since the solubility in the plating solution is good, the load on the filter can be suppressed, and the adverse effect on the plated product by the insoluble component can be suppressed.

Furthermore, the purity of the present invention is 98.5% or more, and the copper oxide powder having a peak intensity ratio I / Is of 0.36 or less or a half-width ratio F / Fs of 2.9 or more or a specific surface area of 7. A copper oxide powder of 3 m @ 2 / g or more shows good solubility in a plating solution containing, for example, EDTA (ethylenediaminetetraacetate) as a chelating agent, and this makes it possible to use the copper oxide powder as a copper plating material. It is effective to secure a good plating film.
[Second Embodiment]
In the second embodiment of the present invention, copper oxide powder was obtained using an aqueous solution of copper salt and an alkaline solution, and the copper oxide powder was heated to produce high-purity copper oxide powder. Since this manufacturing method can obtain copper oxide powder directly, it is called a direct wet method in contrast to the indirect wet method in which copper oxide powder is obtained via copper carbonate or the like. Here, examples of the aqueous solution of the copper salt include aqueous solutions of cupric chloride, cupric sulfate, cupric nitrate, and the like. The production | generation of the copper oxide powder by this direct wet method is demonstrated concretely using FIG. 4 that are the same as those in FIG. 1 are denoted by the same reference numerals as those in FIG. First, an aqueous solution of copper salt, for example, an aqueous solution of cupric chloride (CuCl2) having a copper concentration of 10% by weight and an alkaline solution, for example, an aqueous solution of sodium hydroxide (NaOH) having a concentration of 20% by weight, for example, the pH of the mixed solution is The mixture is charged into the reaction vessel 1 so as to be 9.8 to 10.2, and is stirred for 60 minutes, for example, by the stirring means 11 while being heated so that the temperature of the mixed solution becomes 73 to 77 ° C. The mixed liquid is heated by, for example, providing bubbling means (not shown) including a diffuser tube or the like in the reaction tank 1 and supplying steam from the bubbling means to the mixed liquid.

  The above reaction proceeds as follows to produce copper oxide.

CuC12 + 2NaOH → CuO + 2NaCl + H2O (4)
Thus, copper oxide is precipitated and formed into a powder. And the valve | bulb 12 is opened, the slurry which is a deposit is extracted, and it sends to the suction filtration means 20, and while separating the copper oxide powder which is solid content from a mother liquid here, it is a washing liquid in the said suction filtration means 20, for example, pure water The copper oxide powder is washed with water to wash away traces of impurities adhering to the copper oxide surface. After washing, the copper oxide powder is supplied to a heating furnace, for example, the rotary kiln 4, where it is heated and dried at a predetermined temperature for a predetermined time. Moreover, when the purity of the obtained copper oxide is low, the purity is increased by heat treatment.

  Here, the heating temperature and the heating time in the second embodiment will be described. The heating here is heating performed for the purpose of drying or increasing the purity. The copper oxide powder used as a copper plating material in the present invention is required to satisfy the following requirements in consideration of solubility in a copper plating solution and plating quality.

  [3] The purity is 98.5% or more.

  [4] The peak intensity of the (-1,1,1) plane of the X-ray diffraction spectrum of the copper oxide powder is I, and the (-1,1,1) X-ray diffraction spectrum of the reference copper oxide powder after crystallization is completed. When the peak intensity of the surface is Is, the peak intensity ratio I / Is between the peak intensity I of the copper oxide powder and the peak intensity Is of the reference copper oxide powder is 0.52 or less, or the copper oxide powder The half width of the (-1,1,1) plane of the X-ray diffraction spectrum is F, and the half width of the (-1,1,1) plane of the reference copper oxide powder after crystallization is Fs. When the half-value width F / Fs of the half-value width F of the copper oxide powder and the half-value width Fs of the reference copper oxide powder is 2.9 or more, or the specific surface area of the copper oxide powder is 3.3 m 2 / g. That's it.

  Further, the reference copper oxide powder in the second embodiment refers to a copper oxide powder obtained by a direct wet method using an aqueous copper salt solution, for example, an aqueous cupric chloride solution and an alkaline solution, and heated at 700 ° C. in a heating furnace. Then, the copper oxide powder was heat-treated at a heating temperature of 850 ° C. for 12 hours.

  Moreover, the purity of the copper oxide powder in the second embodiment is a value obtained by measuring the Cu concentration in the copper oxide powder and converting it to CuO as in the first embodiment. Here, in order to use this copper oxide powder as a copper plating agent, the purity is reduced as described in the above requirement [3] so that the change in the copper concentration in the plating process can be prevented and the copper concentration of the plating solution can be easily controlled. It is preferable that it is 98.5% or more of copper oxide powder.

  The requirement [4] is a requirement for determining the solubility of the copper oxide powder in the plating solution, and the requirement determined by the inventors through trial and error as in the first embodiment. It is.

  In order to obtain copper oxide powder satisfying these requirements, heating temperature and heating time in a dryer or heating furnace become a problem. If the heating temperature is too high or the heating time is too long, the requirement [3] is ensured. However, requirement [4] does not apply, and the solubility in the plating solution deteriorates.

Therefore, the present inventors conducted various experiments described later, and attempted to optimize the heating temperature and the heating time for producing the copper oxide powder having the above-mentioned requirements. An example of the heat treatment conditions of the copper oxide powder obtained by the direct wet method is shown below. The copper oxide powder obtained by thermal decomposition under these conditions satisfies the above two requirements.
(Example of heat treatment condition of copper oxide powder obtained by direct wet method)
When the heating temperature is 300 ° C., the heating time is 60 minutes or more and 360 minutes or less. When the heating temperature is 500 ° C., the heating time is 30 minutes or more and 360 minutes or less. When the heating temperature is 600 ° C., the heating time is 30 minutes. Hereinafter, after obtaining the copper oxide powder in this way, the copper oxide powder is subjected to the process of washing tank 5 → centrifugal separator 6 → dryer 7 as described in the first embodiment. Is obtained. This copper oxide powder can be used as a copper plating material for the apparatus shown in FIG.

According to the above-described embodiment, the copper oxide powder obtained by the direct wet method is heated and pyrolyzed using an aqueous copper salt solution, for example, an aqueous cupric chloride solution and an alkaline solution under the above-described heat treatment conditions. Therefore, while ensuring a high purity of 98.5% or more, the copper oxide powder or the specific surface area of the peak intensity ratio I / Is is 0.52 or less or the half width ratio F / Fs is 2.9 or more. A copper oxide powder of 3.3 m 2 / g or more can be produced. Thereby, the effect similar to 1st Embodiment can be acquired.
[Third Embodiment]
In the third embodiment of the present invention, an aqueous solution of copper salt and an alkali hydroxide are reacted to produce cupric hydroxide powder, and the cupric hydroxide powder is thermally decomposed to achieve purity. A high copper oxide powder was produced. The production of copper oxide powder by such a method has the same configuration as that in FIG. 1 and will be specifically described here with reference to FIG. 1 for convenience. First, an aqueous solution of copper salt, for example, an aqueous solution of cupric sulfate (CuSO4) having a copper concentration of 5% by weight and an alkali hydroxide, for example, an aqueous solution of sodium hydroxide (NaOH) having a concentration of 10% by weight, for example, the pH of the mixed solution. Is put into the reaction tank 1 so as to be 11, and the reaction is performed by stirring, for example, for 60 minutes by the stirring means 11. At this time, the temperature of the liquid mixture is set to 5 ° C., for example.

  The above reaction proceeds as follows to produce cupric hydroxide.

CuSO4 + 2NaOH-> Cu (OH) 2 + Na2 SO4 (5)
Thus, cupric hydroxide is precipitated and formed into a powder. And the valve | bulb 12 is opened, the slurry which is a precipitate is extracted, and it sends to the centrifuge 2, and solid content is isolate | separated from mother liquor here by centrifugation, and the cupric hydroxide powder which is the solid content is heated, for example, Supplying to the rotary kiln 4, it heats at a predetermined temperature for a predetermined time and thermally decomposes to produce copper oxide powder. The above reaction is as follows.

Cu (OH) 2 → CuO + H2O (6)
Here, the heating temperature and the heating time in the third embodiment will be described. The copper oxide powder used as a copper plating material in the present invention is required to satisfy the following requirements in consideration of solubility in a copper plating solution and plating quality.

  [5] Purity is 98.5% or more.

  [6] The peak intensity of the (-1,1,1) plane of the X-ray diffraction spectrum of the copper oxide powder is I, and the (-1,1,1) X-ray diffraction spectrum of the reference copper oxide powder after crystallization is completed. When the peak intensity of the surface is Is, the peak intensity ratio I / Is between the peak intensity I of the copper oxide powder and the peak intensity Is of the reference copper oxide powder is 0.67 or less, or the copper oxide powder The half width of the (-1,1,1) plane of the X-ray diffraction spectrum is F, and the half width of the (-1,1,1) plane of the reference copper oxide powder after crystallization is Fs. When the full width at half maximum F / Fs between the full width at half maximum F of the copper oxide powder and the full width at half maximum Fs of the reference copper oxide powder is 1.6 or more, or the specific surface area of the copper oxide powder is 3.6 m 2 / g. That's it.

  The reference copper oxide powder in the third embodiment is obtained by heat treating cupric hydroxide powder at 700 ° C. for 6 hours in a heating furnace to obtain copper oxide powder. And this copper oxide powder is heat-treated at a heating temperature of 850 ° C. for 12 hours.

  Moreover, the purity of the copper oxide powder in the third embodiment is a value obtained by measuring the Cu concentration in the copper oxide powder in the same manner as in the first embodiment and converting to CuO, and the purity of the copper oxide powder is low. Means that the conversion rate of cupric hydroxide is low and there are many cupric hydroxides that do not change to copper oxide. If the purity of the copper oxide powder is low and a large amount of cupric hydroxide is present, the variation in the copper oxide concentration increases. For this reason, when used as a copper plating material, the copper concentration easily changes with each treatment, and it becomes difficult to control the copper concentration of the plating solution. 98.5% or more of copper oxide powder is preferred.

  The requirement [6] is a requirement for determining the solubility of the copper oxide powder in the plating solution, and the requirement determined by the inventors through trial and error as in the first embodiment. It is.

  In order to obtain copper oxide powder satisfying these requirements, heating temperature and heating time in the heating furnace become a problem. If the heating temperature is too high or the heating time is too long, the requirement [5] is ensured. The requirement [6] does not apply and the solubility in the plating solution is deteriorated.

Therefore, the present inventors conducted various experiments described later, and attempted to optimize the heating temperature and the heating time for producing the copper oxide powder having the above-mentioned requirements. An example of heat treatment conditions for cupric hydroxide powder is shown below, but the copper oxide powder obtained by thermal decomposition under these conditions satisfies the above two requirements.
(Example of heat treatment conditions for cupric hydroxide powder)
When the heating temperature is 300 ° C., the heating time is 30 minutes or more and 360 minutes or less. When the heating temperature is 500 ° C., the heating time is 30 minutes or more and 360 minutes or less. When the heating temperature is 600 ° C., the heating time is 30 minutes. More than 360 minutes or less When the heating temperature is 650 ° C., the heating time is 30 minutes or more and 60 minutes or less. After obtaining the copper oxide powder in this way, the copper oxide powder is used as described in the first embodiment. The copper oxide powder is obtained through the steps of washing tank 5 → centrifuge 6 → dryer 7. This copper oxide powder can be used as a copper plating material for the apparatus shown in FIG.

  According to the above-described embodiment, since the cupric hydroxide powder is heated and pyrolyzed under the above heat treatment conditions, the peak intensity ratio is ensured while ensuring a high purity of 98.5% or more. A copper oxide powder having an I / Is of 0.67 or less or a half-width ratio F / Fs of 1.6 or more or a copper oxide powder having a specific surface area of 3.6 m @ 2 / g or more can be produced. Thereby, the effect similar to 1st Embodiment can be acquired.

  In the present invention, as a result of trial and error by the present inventors, the solubility of the copper plating material (copper oxide powder) in the plating solution containing the organic additive depends on the structure of the copper oxide powder. In the first embodiment, the structure of the copper powder depends on the heat treatment conditions during the thermal decomposition of the basic copper carbonate powder. In the second embodiment, a direct wet method using an aqueous solution of copper salt and an alkaline solution is used. Since it depends on the heat treatment conditions at the time of heating of the obtained copper oxide powder, in the third embodiment, it is made by finding that it depends on the heat treatment conditions at the time of thermal decomposition of the cupric hydroxide powder. The following is a description of how the inventors have found the present invention.

  First, the inventors pay attention to the fact that the solubility of copper oxide powder deteriorates when an organic additive is added to the plating solution, and in order to investigate which organic substance inhibits the dissolution of copper oxide powder, various additions are made. An agent was added to the plating solution, and a dissolution test of the copper oxide powder was performed. This dissolution test was performed by adding an additive to the plating solution at a predetermined concentration, adding a predetermined amount of copper oxide powder while stirring the plating solution, and visually checking the degree of dissolution. As a result, the solubility of copper oxide powder in plating solutions containing thiourea containing -C = S group, SPS containing -S-S- group, and Janus Green containing -N = N- group as additives. It is recognized that organic substances having any of —C═S group, —S—S— group, —N═N— group, and —S—H group inhibit the dissolution of copper oxide powder. I found it. Here, the copper oxide powder used in this dissolution test was obtained by thermally decomposing a basic copper carbonate powder at a heating temperature of 750 ° C. for 8 hours, an aqueous solution of cupric chloride and an alkaline solution. A copper oxide powder obtained by a direct wet process was heated at 700 ° C. for 6 hours, and a cupric hydroxide powder was heated at 700 ° C. for 6 hours and thermally decomposed. Using.

  Next, basic copper carbonate powder, copper oxide powder obtained by a direct wet method and cupric hydroxide powder are treated under various heat treatment conditions to obtain copper oxide powder, and the purity of each copper oxide powder is measured. Thus, the heat treatment conditions for obtaining a copper oxide powder having a purity of 98.5% or more were determined. Subsequently, a plating solution containing an organic additive that is actually used by a user manufacturer is obtained, and the solubility of the three copper oxide powders obtained by the various heat treatment conditions in the plating solution is obtained. The test was conducted and it was found that the solubility of the copper oxide powder in the plating solution was different depending on the heat treatment conditions. And for this reason, it is presumed that the structure of the copper oxide powder obtained by the heat treatment conditions is different, and the copper oxide powder obtained by various heat treatment conditions is subjected to structural analysis by X-ray diffraction, so that the plating of the user manufacturer The relationship between the solubility in liquid and the structure of copper oxide powder was found.

  In other words, as described above, the copper oxide powder that satisfies the conditions described in [1] to [6] has been determined by performing various experiments to demonstrate that the copper oxide powder has high solubility in the plating solution of the user manufacturer. The present invention can be accomplished by grasping the heat treatment conditions for producing a simple copper oxide powder. As described above, the present invention can be achieved by the trial and error of the present inventors, and subsequently, examples performed by the present inventors will be described. In the copper oxide powders described in the first embodiment, the second embodiment, and the third embodiment, the peak intensity ratio I / Is, the full width at half maximum ratio F / Fs, and the specific surface area values are respectively. One of the reasons for the difference is considered to be that the size and shape of the copper oxide powder particles vary depending on each production method.

(Experimental example 1-1)
In the first embodiment, basic copper carbonate powder was pyrolyzed under various heat treatment conditions to obtain copper oxide powder, and the purity was measured. The result is shown in FIG. As a result, by performing thermal decomposition at a heating temperature of 300 ° C. for 240 minutes or more, at 400 ° C. for 20 minutes or more, and at 500 ° C. to 750 ° C. for 5 minutes or more, a copper oxide powder having a purity of 98.5% or more is obtained. It was recognized that

(Experimental example 1-2)
For several types of copper oxide powders having a purity of 98.5% or more obtained under the above-mentioned predetermined heat treatment conditions, a dissolution test was performed on a plating solution obtained from a user manufacturer. This dissolution test was performed by the following method. That is, 500 ml of the plating solution of the user manufacturer is stirred at a rotation speed of 200 rpm, 5 g of copper oxide powder is added thereto, and after 2 minutes, stirring is stopped and filtration is performed, and the amount of insoluble residue is measured. Thus, the dissolution rate was calculated. Here, the plating solution of the user manufacturer contained CuSO4 · 5H2O, H2SO4, and 200 ppm of SPS as an additive, and the plating solution temperature was 25 ° C.

  The dissolution rate at this time is shown in FIG. As a result, the dissolution rate of copper oxide powder obtained by pyrolysis at 700 ° C. for 20 minutes is 21.6%, whereas copper oxide powder obtained by pyrolysis at 650 ° C. for 20 minutes. Was found to be 96.5%. Thereby, it is inferred that the structure of the copper oxide powder changes depending on the heat treatment conditions, and this change in the structure affects the solubility in the plating solution.

(Experimental Example 1-3)
Subsequently, in order to clarify the relationship between the structure of the copper oxide powder and the solubility in the plating solution, the copper oxide powder subjected to the dissolution test in (Experimental Example 1-2) was analyzed by X-ray diffraction. Structural analysis was performed. At this time, an X-ray diffraction spectrum is measured for the copper oxide powder, the peak intensity of the (−1, 1, 1) plane of the spectrum is I, and the X-ray diffraction spectrum of the reference copper oxide powder after crystallization is completed. The peak intensity ratio I / Is, which is the ratio of the peak intensity I of the copper oxide powder and the peak intensity Is of the reference copper oxide powder, was determined when the peak intensity of the (-1,1,1) plane was Is. .

  At this time, the half-value width of the diffraction peak of the (−1, 1, 1) plane of the X-ray diffraction spectrum of the copper oxide powder is F, and the (−1, 1, 1) of the X-ray diffraction spectrum of the reference copper oxide powder is 1) When the half-value width of the diffraction peak on the surface is Fs, the half-value width ratio F / Fs, which is the ratio between the half-value width F of the copper oxide powder and the half-value width Fs of the reference copper oxide powder, was obtained. These results are shown in FIG. Here, as the standard copper oxide powder, a copper oxide powder obtained by heat-treating basic copper carbonate powder at 750 ° C. for 8 hours and further heat-treating at 850 ° C. for 12 hours was used.

  According to this result, when the heat treatment conditions are different, the value of the peak intensity ratio I / Is is different, and the copper oxide powder having a smaller value of the peak intensity ratio I / Is has a higher dissolution rate in the plating solution of the user manufacturer. confirmed. Thus, it is understood that the requirement that the peak intensity ratio I / Is is 0.36 or less is necessary to ensure high solubility in the plating solution of the user manufacturer.

  Similarly, when the heat treatment conditions are different, the value of the half width ratio F / Fs is different, and the copper oxide powder having a larger half width ratio F / Fs has a higher dissolution rate with respect to the plating solution of the user manufacturer. Thus, it is understood that the requirement that the half width ratio F / Fs is 2.9 or more is necessary to ensure high solubility in the plating solution of the user manufacturer.

  Here, as the peak intensity ratio I / Is is larger (the half-value width ratio F / Fs is smaller), the crystallization of the copper oxide powder progresses, indicating a stable state. Crystallized and stable copper oxide powder is difficult to dissolve in the liquid component. Therefore, in order to ensure high solubility in the plating solution containing the organic additive, the peak intensity ratio I / Is is 0.36. The crystallinity is required to be below (half-value width ratio F / Fs is 2.9 or more).

(Experimental Example 1-4)
The same X-ray diffraction analysis as in (Experimental Example 1-3) by selecting several types of copper oxide powders obtained under the heat treatment conditions with a purity of 98.5% or more by the purity test in (Experimental Example 1-1) Was done. The results are shown in FIG. 8 for the peak intensity ratio I / Is and in FIG. 9 for the half width ratio F / Fs.

  Thus, if the heating temperature is the same, the value of the peak intensity ratio I / Is is larger as the heating time is longer, and if the heating time is the same, the value of the peak intensity ratio I / Is is larger as the heating temperature is higher. It was. In addition, when the heating temperature is the same, the longer the heating time is, the smaller the half width ratio F / Fs is. When the heating time is the same, the higher the heating temperature is, the smaller the half width ratio F / Fs is. It was.

Therefore, the heat treatment conditions for obtaining a copper oxide powder having a purity of 98.5% or more and a peak intensity ratio I / Is of 0.36 or less are:
When the heating temperature is 300 ° C, the heating time is 240 minutes or more and 480 minutes or less. When the heating temperature is 400 ° C, the heating time is 20 minutes or more and 40 minutes or less. When the heating temperature is 500 ° C, the heating time is 5 minutes. 40 minutes or less When the heating temperature is 550 ° C., the heating time is 5 minutes or more and 40 minutes or less. When the heating temperature is 600 ° C., the heating time is 5 minutes or more and 20 minutes or less. When the heating temperature is 650 ° C., heating is performed. It was confirmed that the time was 5 minutes or more and 20 minutes or less. In addition, the copper oxide powder produced under the above heat treatment conditions is
The condition that the purity is 98.5% or more and the half-width ratio F / Fs is 2.9 or more is also satisfied.

(Experimental example 1-5)
According to the purity test of (Experimental Example 1-1), several types were selected from the copper oxide powders obtained under the heat treatment conditions with a purity of 98.5% or more, and the analysis by specific surface area was performed. At this time, the specific surface area was measured by the BET single point method. The result is shown in FIG.

  From this result, it was confirmed that when the heat treatment conditions were different, the value of the specific surface area of the copper oxide powder was different, the copper oxide powder having the larger specific surface area value was more soluble in the plating solution of the user manufacturer. Accordingly, it is understood that the specific surface area needs to be 7.3 m 2 / g or more in order to ensure high solubility in the plating solution of the user. Furthermore, the copper oxide powder produced under the heat treatment conditions obtained in (Experimental Example 1-4) satisfies the condition that the purity is 98.5% or more and the specific surface area is 7.3 m 2 / g or more. It was recognized that

(Experimental example 1-6)
A copper oxide powder having a purity of 98.5% or more obtained under the same heat treatment conditions as in (Experimental Example 1-1) was subjected to a dissolution test with respect to a plating solution (laboratory level plating solution) to which 200 ppm of SPS was added. This dissolution test was performed by the following method. In other words, 500 ml of plating solution is stirred at a rotation speed of 200 rpm, 5 g of copper oxide powder is added thereto, and after 2 minutes, stirring is stopped, filtration is performed, and the amount of insoluble residue is measured to dissolve the plating solution. The rate was calculated. Here, the composition of the plating solution was CuSO4 · 5H2O: 100 g / L, H2SO4: 200 g / L, SPS: 200 ppm, and the plating solution temperature was 25 ° C. The dissolution rate at this time is shown in FIG.

  As a result, the dissolution rate in the plating solution may be higher than the dissolution rate in the plating solution of the user manufacturer, and the dissolution rate tends to decrease as the heating temperature increases and the heating time increases. Admitted. Here, SPS is also included in the plating solution of the user manufacturer, but the decomposition solution of SPS is included in the plating solution of the user manufacturer, and the amount of the decomposition product increases cumulatively. It is presumed that the dissolution rate of the copper oxide powder is lower than the laboratory level plating solution used in this example. Therefore, compared with the plating solution of the user manufacturer, the plating solution at the laboratory level has better solubility even if the specific surface area is small. In actual SPS, it is considered that SPS itself is decomposed by use, and the decomposition product has deteriorated solubility, and the effect of the present invention is evaluated using a plating solution of a user manufacturer. .

(Experimental example 1-7)
A dissolution test for thiourea, Janus green, propyl mercaptan, mercatopropyl sulfonic acid, and methyl yellow was performed on the copper oxide powder produced under the heat treatment conditions obtained in (Experimental Example 1-4). In other words, 500 ml of plating solution added with 20 ppm of thiourea is stirred at a rotation speed of 200 rpm, 5 g of copper oxide powder is added thereto, and after 2 minutes, stirring is stopped and filtration is performed, and the amount of insoluble residue The solubility was confirmed by measuring. The composition of the plating solution was CuSO4 · 5H2O: 100 g / L, H2SO4: 200 g / L, and the plating solution temperature was 25 ° C. As a result, it was confirmed that the copper oxide powder produced under the heat treatment conditions secured a dissolution rate of 99.9 or higher with respect to the plating solution containing thiourea, and high solubility was confirmed. The dissolution rate of copper oxide obtained by thermal decomposition at 750 ° C. for 480 minutes was 39.2%, and the solubility was poor under these treatment conditions.

  Similarly, the solubility was confirmed under the same conditions with respect to 500 ml of plating solution to which 40 ppm of Janus Green was added. The composition temperature of the plating solution was the same as when thiourea was used. As a result, it was confirmed that a dissolution rate of 99.9 or more was secured with respect to the plating solution containing Janus Green, and high solubility was confirmed. The dissolution rate of copper oxide obtained by thermal decomposition at 750 ° C. for 480 minutes was 64.7%, and the solubility was poor under this heat treatment condition.

  Similarly, the solubility was confirmed under the same conditions with respect to 500 ml of plating solution to which 200 ppm of propyl mercaptan was added. The composition and temperature of the plating solution were the same as when thiourea was used. As a result, it was confirmed that the copper oxide powder produced under the heat treatment conditions secured a dissolution rate of 99.8% or more with respect to the plating solution containing propyl mercaptan, and high solubility was confirmed.

  Similarly, the solubility was confirmed under the same conditions for 500 ml of a plating solution to which 200 ppm of mercatopropylsulfonic acid was added. The composition and temperature of the plating solution were the same as when thiourea was used. As a result, it was confirmed that the copper oxide powder produced under the heat treatment conditions ensure a dissolution rate of 99.6% or more with respect to the plating solution containing mercatopropylsulfonic acid, and high solubility can be confirmed. It was.

  Similarly, the solubility was confirmed under the same conditions with respect to 500 ml of plating solution to which 5 ppm of methyl yellow was added. The composition and temperature of the plating solution were the same as when thiourea was used. As a result, it was confirmed that the copper oxide powder produced under the heat treatment conditions secures a dissolution rate of 99.9% or more with respect to the plating solution containing methyl yellow, and high solubility was confirmed.

(Experimental Example 1-8)
Furthermore, in order to clarify the relationship between the structure of copper oxide powder and the solubility in the plating solution, SEM is used for the copper oxide powder having high solubility in the plating solution of the user manufacturer and the copper oxide powder having low solubility. Observation was performed with a scanning electron microscope. As a result, there was no difference in the surface shapes of both at a magnification of 1000 times, but the surface shapes of both were greatly different at a magnification of 100,000 times, and the highly soluble copper oxide powder was an aggregate of fine particles. However, it was confirmed that the low-solubility copper oxide powder was advanced in solid-phase sintering of fine particles. It is inferred that the difference in solubility between the two is caused by the difference in the state of the particles.

(Experimental example 2-1)
In the second embodiment, copper oxide powder obtained by reacting cupric chloride with an alkaline solution was heated under various heat treatment conditions to obtain copper oxide powder, and the purity was measured. The result is shown in FIG. From this result, it was confirmed that a copper oxide powder having a purity of 98.5% or more can be obtained by heating at a heating temperature of 300 ° C. for 60 minutes or more, and at 500 ° C. to 700 ° C. for 30 minutes or more.

(Experimental example 2-2)
The copper oxide powder having a purity of 98.5% or more obtained under the above-described predetermined heat treatment conditions was subjected to a dissolution test for a plating solution obtained from a user manufacturer. This dissolution test was conducted in the same manner as in (Experimental Example 1-2).

  FIG. 13 shows a comparison between the heat treatment conditions and the dissolution rate of the copper oxide powder. As a result, the dissolution rate of copper oxide powder obtained by pyrolysis at 700 ° C. for 60 minutes is 19.8%, whereas copper oxide powder obtained by pyrolysis at 600 ° C. for 30 minutes. Was found to be 95.5%. Thereby, it is inferred that the structure of the copper oxide powder changes depending on the heat treatment conditions, and this change in the structure affects the solubility in the plating solution.

(Experimental Example 2-3)
Subsequently, in order to clarify the relationship between the structure of the copper oxide powder and the solubility in the plating solution, X was compared with several types of copper oxide powder subjected to the dissolution test in (Experimental Example 2-2). Structural analysis by line diffraction was performed. At this time, an X-ray diffraction spectrum is measured for the copper oxide powder, the peak intensity of the (−1, 1, 1) plane of the spectrum is I, and the X-ray diffraction spectrum of the reference copper oxide powder after crystallization is completed. The peak intensity ratio I / Is, which is the ratio of the peak intensity I of the copper oxide powder and the peak intensity Is of the reference copper oxide powder, was determined when the peak intensity of the (-1,1,1) plane was Is. .

  At this time, the half-value width of the diffraction peak of the (−1, 1, 1) plane of the X-ray diffraction spectrum of the copper oxide powder is F, and the (−1, 1, 1) of the X-ray diffraction spectrum of the reference copper oxide powder is 1) When the half-value width of the diffraction peak on the surface is Fs, the half-value width ratio F / Fs, which is the ratio between the half-value width F of the copper oxide powder and the half-value width Fs of the reference copper oxide powder, was obtained. These results are shown in FIGS. Here, as the reference copper oxide powder, a copper oxide powder obtained by a direct wet method using an aqueous solution of cupric chloride and an alkaline solution is heat-treated at 700 ° C. for 6 hours, and then the copper oxide powder is treated again. Heat treatment was performed at a heating temperature of 850 ° C. for 12 hours.

  As a result, in order to ensure high solubility in the plating solution containing the organic additive, the peak intensity ratio I / Is is 0.52 or less (half-width ratio F / Fs is 2.9 or more). The crystallinity is required.

The heat treatment conditions for obtaining a copper oxide powder having a purity of 98.5% or more and a peak intensity ratio I / Is of 0.52 or less are as follows:
When the heating temperature is 300 ° C., the heating time is 60 minutes or more and 360 minutes or less. When the heating temperature is 500 ° C., the heating time is 30 minutes or more and 360 minutes or less. When the heating temperature is 600 ° C., the heating time is 30 minutes. It was confirmed that: Moreover, the copper oxide powder manufactured on the above-mentioned heat processing conditions is 98.5% or more of purity, and also satisfy | fills the conditions that half value width ratio F / Fs is 2.9 or more.

(Experimental example 2-4)
According to the purity test of (Experimental example 2-1), several types of copper oxide powders obtained under heat treatment conditions with a purity of 98.5% or more were selected and analyzed by specific surface area. At this time, the specific surface area was measured by the BET single point method. The result is shown in FIG.

  From this result, it is understood that the specific surface area must be 3.3 m @ 2 / g or more in order to ensure high solubility in the plating solution of the user. Furthermore, the copper oxide powder manufactured under the heat treatment conditions obtained in (Experimental Example 2-3) has a condition that the purity is 98.5% or more and the specific surface area is 3.3 m 2 / g or more. It was approved to meet.

(Experimental Example 2-5)
Tests for dissolution of copper oxide powder produced under the heat treatment conditions determined in (Experimental Example 2-3) in additives such as thiourea, Janus Green, propyl mercaptan, mercatopropyl sulfonic acid, and methyl yellow Went. Test conditions for each plating solution using this additive are as shown in (Experimental Example 1-7).

  The copper oxide powder produced under the heat treatment conditions is confirmed to secure a dissolution rate of 99.9 or more with respect to each plating solution using the above additives, and high solubility can be confirmed. It was.

(Experimental example 3-1)
In the third embodiment, cupric hydroxide powder was pyrolyzed under various heat treatment conditions to obtain copper oxide powder, and its purity was measured. The result is shown in FIG. From this result, it was recognized that a copper oxide powder having a purity of 98.5% or more can be obtained by performing thermal decomposition for 30 minutes or more at a heating temperature of 300 ° C. to 700 ° C.

(Experimental example 3-2)
For several types of copper oxide powders having a purity of 98.5% or more obtained under the above-mentioned predetermined heat treatment conditions, a dissolution test was performed on a plating solution obtained from a user manufacturer. This dissolution test was conducted in the same manner as in (Experimental Example 1-2).

  FIG. 18 shows a comparison between the heat treatment conditions and the dissolution rate of the copper oxide powder. As a result, the dissolution rate of copper oxide powder obtained by pyrolysis at 700 ° C. for 30 minutes is 20.2%, whereas copper oxide powder obtained by pyrolysis at 650 ° C. for 60 minutes. Was found to be 95.6%. Thereby, it is inferred that the structure of the copper oxide powder changes depending on the heat treatment conditions, and this change in the structure affects the solubility in the plating solution.

(Experimental Example 3-3)
Subsequently, in order to clarify the relationship between the structure of the copper oxide powder and the solubility in the plating solution, X was measured for several types of copper oxide powder subjected to the dissolution test in (Experimental Example 3-2). Structural analysis by line diffraction was performed. At this time, an X-ray diffraction spectrum is measured for the copper oxide powder, the peak intensity of the (−1, 1, 1) plane of the spectrum is I, and the X-ray diffraction spectrum of the reference copper oxide powder after crystallization is completed. The peak intensity ratio I / Is, which is the ratio of the peak intensity I of the copper oxide powder and the peak intensity Is of the reference copper oxide powder, was determined when the peak intensity of the (-1,1,1) plane was Is. .

  At this time, the half-value width of the diffraction peak of the (−1, 1, 1) plane of the X-ray diffraction spectrum of the copper oxide powder is F, and the (−1, 1, 1) of the X-ray diffraction spectrum of the reference copper oxide powder is 1) When the half-value width of the diffraction peak on the surface is Fs, the half-value width ratio F / Fs, which is the ratio between the half-value width F of the copper oxide powder and the half-value width Fs of the reference copper oxide powder, was obtained. These results are shown in FIG. 19 and FIG. Here, as the reference copper oxide powder, cupric hydroxide powder was heat-treated at 700 ° C. for 6 hours, and then this copper oxide powder was heat-treated at a heating temperature of 850 ° C. for 12 hours.

  As a result, in order to ensure high solubility in the plating solution containing the organic additive, the peak intensity ratio I / Is is 0.67 or less (half-width ratio F / Fs is 1.6 or more). The crystallinity is required.

The heat treatment conditions for obtaining a copper oxide powder having a purity of 98.5% or more and a peak intensity ratio I / Is of 0.67 or less are as follows:
When the heating temperature is 300 ° C., the heating time is 30 minutes or more and 360 minutes or less. When the heating temperature is 500 ° C., the heating time is 30 minutes or more and 360 minutes or less. When the heating temperature is 600 ° C., the heating time is 30 minutes. For 360 minutes or less When the heating temperature is 650 ° C., it was confirmed that the heating time was 30 minutes or more and 60 minutes or less. Moreover, the copper oxide powder manufactured on the above-mentioned heat processing conditions is 98.5% or more of purity, and also satisfy | fills the conditions that half value width ratio F / Fs is 1.6 or more.

(Experimental example 3-4)
According to the purity test of (Experimental example 3-1), several types were selected from the copper oxide powder obtained under the heat treatment conditions with a purity of 98.5% or more, and the analysis was performed based on the specific surface area. At this time, the specific surface area was measured by the BET single point method. The result is shown in FIG.

  From this result, it is understood that the specific surface area needs to be 3.6 m 2 / g or more in order to ensure high solubility in the plating solution of the user. Furthermore, the copper oxide powder produced under the heat treatment conditions obtained in (Experimental Example 3-3) has a purity of 98.5% or more and a specific surface area of 3.6 m 2 / g or more. It was approved to meet.

(Experimental Example 3-5)
A dissolution test for thiourea, Janus Green, propyl mercaptan, mercatopropyl sulfonic acid, and methyl yellow as additives for the copper oxide powder produced under the heat treatment conditions determined in (Experimental Example 3-3) Went. Test conditions for each plating solution using this additive are as shown in (Experimental Example 1-7).

  The copper oxide powder produced under the heat treatment conditions is confirmed to secure a dissolution rate of 99.9 or more with respect to each plating solution using the above additives, and high solubility can be confirmed. It was.

It is process drawing which shows 1st Embodiment of the manufacturing method of the copper oxide powder which is the copper plating material of this invention. It is a block diagram which shows an example of the plating processing apparatus used for the plating method of this invention. It is a structural formula of thiourea and Janus green. It is process drawing which shows 2nd Embodiment of the manufacturing method of the copper oxide powder which is the copper plating material of this invention. It is a characteristic view which shows the relationship between the heat processing conditions of basic copper carbonate powder, and the purity of copper oxide powder. It is a characteristic view which shows the solubility with respect to the plating solution of the copper oxide powder obtained by various heat processing conditions. It is a characteristic view which shows the result of the structural analysis by X-ray diffraction of the copper oxide powder obtained by various heat processing conditions. It is a characteristic view which shows peak intensity ratio I / Is of the X-ray diffraction of the copper oxide powder obtained by various heat processing conditions. It is a characteristic view which shows the half width ratio F / Fs of the X-ray diffraction of the copper oxide powder obtained by various heat processing conditions. It is a characteristic view which shows the specific surface area of the copper oxide powder obtained by various heat processing conditions. It is a characteristic view which shows the solubility with respect to the plating solution containing SPS as an additive of the copper oxide powder obtained by various heat processing conditions. It is a characteristic view which shows the relationship between the heat processing conditions of the copper oxide powder obtained by the direct wet method, and the purity of the copper oxide powder. It is a characteristic view which shows the solubility with respect to the plating solution of the user maker of the copper oxide powder obtained by various heat processing conditions. It is a characteristic view which shows peak intensity ratio I / Is of the X-ray diffraction of the copper oxide powder obtained by various heat processing conditions. It is a characteristic view which shows the half width ratio F / Fs of the X-ray diffraction of the copper oxide powder obtained by various heat processing conditions. It is a characteristic view which shows the specific surface area of the copper oxide powder obtained by various heat processing conditions. It is a characteristic view which shows the relationship between the heat processing conditions of cupric hydroxide powder, and the purity of copper oxide powder. It is a characteristic view which shows the solubility with respect to the plating solution of the user maker of the copper oxide powder obtained by various heat processing conditions. It is a characteristic view which shows peak intensity ratio I / Is of the X-ray diffraction of the copper oxide powder obtained by various heat processing conditions. It is a characteristic view which shows the half width ratio F / Fs of the X-ray diffraction of the copper oxide powder obtained by various heat processing conditions. It is a characteristic view which shows the specific surface area of the copper oxide powder obtained by various heat processing conditions.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Reaction tank 2 Centrifugal machine 20 Suction filtration means 3 Dryer 4 Heating furnace 5 Washing tank 6 Centrifugal machine 7 Dryer 8 Electrolytic tank 81 Insoluble anode 82 To-be-plated body 83 Dissolution tank 84 Hopper

Claims (12)

In a copper plating material provided with an insoluble anode and an object to be plated to form a cathode, and supplied to an electrolyte containing an organic additive,
This copper plating material is a copper oxide powder having a purity of 98.5% or more obtained by thermally decomposing basic copper carbonate powder in an atmosphere that is not a reducing atmosphere,
The peak intensity of the (-1,1,1) plane of the X-ray diffraction spectrum of this copper oxide powder is I,
When the peak intensity of the (-1, 1, 1) plane of the X-ray diffraction spectrum of the reference copper oxide powder that has been crystallized is Is,
A copper plating material, wherein the peak intensity ratio I / Is between the peak intensity I of the copper oxide powder and the peak intensity Is of the reference copper oxide powder is 0.36 or less. In a copper plating material provided with an insoluble anode and an object to be plated to form a cathode, and supplied to an electrolyte containing an organic additive,
This copper plating material is a copper oxide powder having a purity of 98.5% or more obtained by thermally decomposing basic copper carbonate powder in an atmosphere that is not a reducing atmosphere,
The full width at half maximum of the (-1,1,1) plane of the X-ray diffraction spectrum of this copper oxide powder is F,
When the full width at half maximum of the (−1, 1, 1) plane of the X-ray diffraction spectrum of the reference copper oxide powder that has been crystallized is Fs,
A copper plating material, wherein the half-value width ratio F / Fs between the half-value width F of the copper oxide powder and the half-value width Fs of the reference copper oxide powder is 2.9 or more. In a copper plating material provided with an insoluble anode and an object to be plated to form a cathode, and supplied to an electrolyte containing an organic additive,
This copper plating material is a copper oxide powder having a purity of 98.5% or more obtained by thermally decomposing basic copper carbonate powder in an atmosphere that is not a reducing atmosphere, and has a specific surface area of 7.3 m @ 2/7. A copper plating material characterized by being a copper oxide powder of g or more. In a copper plating material provided with an insoluble anode and an object to be plated to form a cathode, and supplied to an electrolytic solution containing an organic additive,
This copper plating material is a copper oxide powder having a purity of 98.5% or more obtained by reacting an aqueous solution of a copper salt with an alkaline solution to obtain copper oxide powder and heating the copper oxide powder. ,
The peak intensity of the (-1,1,1) plane of the X-ray diffraction spectrum of this copper oxide powder is I,
When the peak intensity of the (-1, 1, 1) plane of the X-ray diffraction spectrum of the reference copper oxide powder that has been crystallized is Is,
A copper plating material, wherein the peak intensity ratio I / Is between the peak intensity I of the copper oxide powder and the peak intensity Is of the reference copper oxide powder is 0.52 or less. In a copper plating material provided with an insoluble anode and an object to be plated to form a cathode, and supplied to an electrolyte containing an organic additive,
This copper plating material is a copper oxide powder having a purity of 98.5% or more obtained by reacting an aqueous solution of a copper salt with an alkaline solution to obtain copper oxide powder and heating the copper oxide powder. ,
The full width at half maximum of the (-1,1,1) plane of the X-ray diffraction spectrum of this copper oxide powder is F,
When the full width at half maximum of the (−1, 1, 1) plane of the X-ray diffraction spectrum of the reference copper oxide powder that has been crystallized is Fs,
A copper plating material, wherein the half-value width ratio F / Fs between the half-value width F of the copper oxide powder and the half-value width Fs of the reference copper oxide powder is 2.9 or more. In a copper plating material provided with an insoluble anode and an object to be plated to form a cathode, and supplied to an electrolyte containing an organic additive,
This copper plating material is a copper oxide powder having a purity of 98.5% or more obtained by reacting an aqueous solution of a copper salt with an alkaline solution to obtain copper oxide powder and heating the copper oxide powder. A copper plating material characterized by being a copper oxide powder having a specific surface area of 3.3 m 2 / g or more. In a copper plating material provided with an insoluble anode and an object to be plated to form a cathode, and supplied to an electrolytic solution containing an organic additive,
This copper plating material is a copper oxide powder having a purity of 98.5% or more obtained by thermally decomposing cupric hydroxide powder,
The peak intensity of the (-1,1,1) plane of the X-ray diffraction spectrum of this copper oxide powder is I,
When the peak intensity of the (-1, 1, 1) plane of the X-ray diffraction spectrum of the reference copper oxide powder that has been crystallized is Is,
A copper plating material, wherein the peak intensity ratio I / Is between the peak intensity I of the copper oxide powder and the peak intensity Is of the reference copper oxide powder is 0.67 or less. In a copper plating material provided with an insoluble anode and an object to be plated to form a cathode, and supplied to an electrolyte containing an organic additive,
This copper plating material is a copper oxide powder having a purity of 98.5% or more obtained by thermally decomposing cupric hydroxide powder,
The full width at half maximum of the (-1,1,1) plane of the X-ray diffraction spectrum of this copper oxide powder is F,
When the full width at half maximum of the (−1, 1, 1) plane of the X-ray diffraction spectrum of the reference copper oxide powder that has been crystallized is Fs,
A copper plating material, wherein the half-value width ratio F / Fs between the half-value width F of the copper oxide powder and the half-value width Fs of the reference copper oxide powder is 1.6 or more. In a copper plating material provided with an insoluble anode and an object to be plated to form a cathode, and supplied to an electrolytic solution containing an organic additive,
This copper plating material is a copper oxide powder having a purity of 98.5% or more obtained by pyrolyzing cupric hydroxide powder and having a specific surface area of 3.6 m 2 / g or more. A copper plating material characterized by being. The additive is an organic substance containing any one of a double bond of carbon and sulfur, a single bond of sulfur and sulfur, a double bond of nitrogen and nitrogen, and a single bond of sulfur and hydrogen. The copper plating material according to any one of claims 1 to 9. The additive is any one of bis (3-sulfopropyl) disulfide and salt, thiourea, Janus green, dimethyl disulfide, propyl mercaptan, mercaptopropyl sulfonic acid and salt, and methyl yellow. The copper plating material as described in any one of thru | or 10. In a copper plating method in which an insoluble anode and a body to be plated are provided, a copper plating material is supplied to an electrolytic solution containing an organic additive, and copper is plated on the body to be plated.
The copper plating method according to claim 1, wherein the copper plating material is a copper plating material according to claim 1.

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