JP2011162875A - Phosphorus-containing copper anode for electrolytic copper plating, method of producing the same and electrolytic copper plating method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a phosphorus-containing copper anode for electrolytic copper plating, a method of producing the phosphorus-containing copper anode for electrolytic copper plating and an electrolytic copper plating method capable of reducing plating defectives due to slime. <P>SOLUTION: Working is performed onto a phosphorus-containing copper for electrolytic copper plating to give a working strain to the phosphorus-containing copper for electrolytic copper plating, thereafter, re-crystallizing heat treatment is performed, thereby, such a crystal grain boundary structure that the special grain boundary length rate Lσ<SB>N</SB>/L<SB>N</SB>of the unit total special grain boundary length Lσ<SB>N</SB>calculated by converting the total special grain boundary length Lσ of a special grain boundary into the value per unit area 1 mm<SP>2</SP>to the unit total grain boundary length L<SB>N</SB>calculated by converting the total grain boundary length L of a crystal grain boundary of a copper crystal grain on the anode surface into the value per unit area 1 mm<SP>2</SP>becomes 0.4 or more is produced, a black film is evenly formed on the initial time of electrolytic copper plating, the black film is prevented from coming off and, thereby, the plating defectives can be reduced. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention, for example, suppresses generation of anode slime generated from a phosphorus-containing copper anode electrode when performing electrolytic copper plating on a semiconductor wafer or the like, and contamination of the cathode surface made of a semiconductor wafer or the like, plating defects such as protrusions TECHNICAL FIELD The present invention relates to a phosphorous copper anode for electrolytic copper plating that prevents the occurrence of copper, a method for producing the phosphorous copper anode, and an electrolytic copper plating method using the phosphorous copper anode electrode.

Conventionally, electrolytic copper plating using electrolytic copper or oxygen-free copper has been performed as an anode electrode for electrolytic copper plating, but a large amount of anode slime is likely to occur, and this causes plating defects in the material to be treated. There was a problem that was likely to occur.
In order to solve this problem, electrolytic copper plating using phosphorous copper as an anode electrode has been performed.
According to electrolytic copper plating using a phosphorous copper anode, a black film mainly composed of cuprous oxide or copper powder is formed on the anode surface during electrolysis, so that the generation of anode slime is reduced. The occurrence of plating defects has also been reduced. For example, when forming precise copper wiring on a semiconductor wafer or the like, the surface of the semiconductor wafer can also be obtained by electrolytic copper plating using phosphorous copper as an anode. It cannot be said that the prevention of plating defects such as contamination and protrusions is sufficiently performed.

  Therefore, recently, the amount of oxygen contained in the anode is specified, and copper electroplating using a pure copper anode in which the crystal grain size of the anode electrode is specified (see Patent Document 1), or the phosphorus content contained in the anode The copper electroplating (see Patent Documents 2 and 3) using a phosphorous copper anode that defines the amount and the crystal grain size of the anode electrode has been developed to reduce the generation of anode slime and prevent plating defects. It has been.

Japanese Patent No. 4011336 Patent No. 4034095 specification Patent No. 4076751

In electrolytic copper plating using a conventional phosphorous copper anode, as the electrolysis progresses, a black film composed mainly of copper powder, cuprous oxide, copper phosphide, copper chloride, etc. is formed on the phosphorous copper anode surface. However, when the electrolysis progresses further and the black film grows thick, it falls off the surface of the phosphorous copper anode and causes the generation of anode slime, or diffuses into the plating bath to cause the surface of the material to be plated (cathode). The surface of the material to be plated such as a semiconductor wafer or the like, causing plating defects such as protrusions.
Therefore, the present invention suppresses the generation of anode slime and prevents contamination and protrusions on the surface of a material to be plated such as a semiconductor wafer, even when forming an accurate copper wiring on a semiconductor wafer or the like by electrolytic copper plating. Another object is to provide a phosphorous copper anode for electrolytic copper plating that can prevent the occurrence of plating defects such as the above.
It is another object of the present invention to provide a new method for producing a phosphorous copper anode for electrolytic copper plating, which can reduce the generation of anode slime and prevent the occurrence of plating defects such as contamination and protrusions on the surface of the material to be plated. For other purposes.
Further, by using the phosphorous copper anode for the electrolytic copper plating, it is possible to reduce the generation of anode slime, and at the same time, prevent the occurrence of plating defects such as contamination and protrusions on the surface of the material to be plated such as a semiconductor wafer. It is still another object to provide an electrolytic copper plating method that can be used.

As a result of intensive studies on the relationship between the grain boundary form of the phosphorous copper anode, the generation of anode slime, and plating defects during electrolytic copper plating, the present inventors have obtained the following knowledge.
In electrolytic copper plating using a conventional phosphorous copper anode, the black film grows thick and falls off as the electrolysis progresses.
2Cu ⁺ → Cu (powder) + Cu ²⁺
This is because metallic copper and cuprous oxide are produced, but the properties of the black film formed in the early stage of electrolysis affect the later, so that uniform and monovalent copper ions (Cu ⁺ ) are produced in the early stage of electrolysis. From the viewpoint that it is important to form a black film with less generation, various conditions for forming a black film that is uniform and low in the generation of monovalent copper ions (Cu ⁺ ) at the beginning of electrolysis were examined. It has been found that the shape of the grain boundary of the anode has a great influence on the properties of the black film formed in the early stage of electrolysis.

That is, the present inventors, in the phosphorous copper anode for electrolytic copper plating, increase the formation rate of so-called special grain boundaries among the grain boundaries of the crystal grains on the phosphorous copper anode surface, Convert the units all special grain boundary length per unit area 1 mm ² per special grain boundary length Lσ Lσ _N is the unit total grain boundary length in terms of unit area 1 mm ² per total grain boundary length L of all crystal grains if it becomes more than a specific value for the _{L N (Lσ N / L N} ≧ 0.4), the entire anode in the electrolytic early stage, it is possible to form a uniform black film, as a result, It has been found that the black film can be prevented from falling off and the plating defects caused by the anode slime can be greatly reduced.
Here, the special grain boundary is a corresponding grain boundary belonging to 3 ≦ Σ ≦ 29 with a Σ value defined based on “Trans.Met.Soc.AIME, 185,501 (1949)”, and “ Acta.Metallurica.Vol.14, p.1479, (1966) ”, the corresponding corresponding portion lattice orientation defect Dq in the corresponding grain boundary is a grain boundary satisfying Dq ≦ 15 ° / Σ1 / ^2. Is defined as being.

In addition, the present inventors gave a predetermined cold working and hot working to produce a processing strain in producing a phosphorous copper anode for electrolytic copper plating, and then given a predetermined temperature range (350 to 900 ° C.). By performing the recrystallization heat treatment in the above, a so-called special grain boundary formation ratio (Lσ _N / L _N ≧ 0.4) among the grain boundaries existing on the surface of the copper anode is high. It has been found that a phosphorous copper anode can be produced.

Furthermore, the present inventors use a phosphorous copper anode having a high special grain boundary formation rate (Lσ _N / L _N ≧ 0.4). For example, when copper plating is performed on a semiconductor wafer or the like, the semiconductor wafer It has been found that a fine copper wiring having no plating defects such as contamination and protrusions can be formed on the surface.

The present invention has been made based on the above findings,
“(1) In the phosphorous copper anode for electroplating,
(A) Using a scanning electron microscope, each crystal grain on the anode surface is irradiated with an electron beam, and the interface between crystal grains having an orientation difference between adjacent crystal grains of 15 ° or more is used as a grain boundary. The total grain boundary length L of the crystal grain boundary in the range was measured, and the unit total grain boundary length L _N was calculated by converting this per unit area 1 mm ² (b). Similarly, using a scanning electron microscope, The individual crystal grains on the anode surface are irradiated with an electron beam to determine the position of the crystal grain boundary where the interface between adjacent crystal grains constitutes the special grain boundary, and the total special grain boundary length Lσ of the special grain boundary. When this is converted per unit area 1 mm ² and the unit total special grain boundary length Lσ _N is obtained,
(C) The special grain boundary length ratio Lσ _N / L _N between the measured unit total grain boundary length L _{N of} the crystal grain boundary and the unit total special grain boundary length Lσ _N of the measured special grain boundary is ,
Lσ _N / L _N ≧ 0.4
A phosphorous copper anode for electroplating, characterized by having a grain boundary structure satisfying the following relationship:
(2) The phosphorus-containing copper anode for electroplating according to (1) above, containing 100 to 800 ppm of phosphorus in mass%.
(3) The phosphorous copper anode for electroplating according to (1) or (2), wherein the average crystal grain size is 3 to 1000 μm.
(4) After processing the phosphor-containing copper for electroplating to give processing strain, a recrystallization heat treatment is performed at 350 to 900 ° C., so that the special grain boundary length ratio Lσ _N / L _N is 0.4 or more. The method for producing a phosphorous copper anode for electroplating according to any one of the above (1) to (3).
(5) The method for producing a phosphorous copper anode for electroplating according to (4), wherein the processing is performed by at least one of cold processing and hot processing.
(6) Repeat cold working and recrystallization heat treatment, or hot working and recrystallization heat treatment, or a combination of these until the special grain boundary length ratio Lσ _N / L _N is 0.4 or more. The manufacturing method of the phosphorous copper anode for electroplating as described in said (4) or (5) performed.
(7) Hot working is performed at a reduction rate of 5 to 80% in a temperature range of 400 to 900 ° C., and then statically held without giving the processing strain for 3 to 300 seconds, and a recrystallization heat treatment is performed. The manufacturing method of the phosphorous copper anode for electroplating as described in said (4).
(8) Cold-working at a rolling reduction of 5 to 80%, and then heating to a temperature range of 350 to 900 ° C. and statically holding without applying the processing strain for 5 minutes to 5 hours, followed by recrystallization The manufacturing method of the phosphorous copper anode for electroplating as described in said (4) which performs crystallization heat processing.
(9) An electrolytic copper plating method using the phosphorous copper anode for electroplating according to any one of (1) to (3). "
It is characterized by.

  Next, the present invention will be described in detail.

First, the present inventors investigated the progress of dissolution of the phosphorous copper anode surface in electrolytic copper plating, and obtained the following knowledge.
As shown in the schematic diagrams of FIGS. 1A to 1D, in the initial state (a) in which electrolysis is started, a large change does not occur on the anode surface, but a certain period of time has elapsed after the start of electrolysis (b ), Selective dissolution of the crystal grains on the anode surface starts from the grain boundaries that are chemically unstable compared to the inside of the grains, and at the time point (c) when electrolysis proceeds, the grain boundaries are selectively dissolved. As a result, the current density becomes non-uniform due to the shape factor. Therefore, the grain boundary is selectively dissolved at an accelerated rate, and the dissolution of the grain boundary proceeds at the point (d) when the electrolysis proceeds. Along with the black film (surface oxide film) formed on the anode surface, undissolved crystal grains are peeled off and peeled off, resulting in generation of anode slime, which also causes plating failure. In addition, a new surface is generated in the anode portion where undissolved crystal grains are peeled off and peeled off, voltage fluctuations are generated, and it becomes increasingly difficult to perform stable electrolytic operation.

Based on the above knowledge, the present inventors have further developed a phosphorous copper anode for electrolytic copper plating that does not cause selective dissolution (non-uniform dissolution) from grain boundaries with the passage of electrolysis time. As a result of the research, the special grain boundary as defined above in the phosphorus-containing copper anode (corresponding grain boundary belonging to 3 ≦ Σ ≦ 29 in Σ value), and the inherent corresponding site lattice orientation defect Dq in the corresponding grain boundary is , Dq ≦ 15 ° / Σ1 / ² ), and the total special grain boundary length Lσ _N converted from the total special grain boundary length Lσ per unit area 1 mm ² , and the crystal in the phosphorous copper anode The special grain boundary length ratio Lσ _N / L _N with respect to the unit total grain boundary length L _{N obtained} by converting the total grain boundary length L of the grain boundary per unit area 1 mm ² is Lσ _N / L _N ≧ 0.4 When having a grain boundary structure that satisfies the relationship of Since the ratio of special grain boundaries that are stable in terms of crystal structure and chemically stable increases, the selective dissolution of the grain boundaries is less likely to occur, and as a result, peeling and peeling of undissolved crystal grains occurs. As a result, the present invention found out that the formation of a uniform black film is suppressed, the generation of anode slime is reduced, and at the same time, the occurrence of plating defects due to slime is also reduced. is there.
Here, the total grain boundary length L is based on crystal orientation data obtained from a backscattered electron diffraction pattern obtained by irradiating individual crystal grains on the anode surface with an electron beam using a scanning electron microscope. By measuring the total grain boundary length L of the crystal grain boundary in the measurement range with the interface between crystal grains having an orientation difference between adjacent crystal grains of 15 ° or more as the crystal grain boundary.
When the special grain boundary length ratio Lσ _N / L _N is Lσ _N / L _N <0.4, selective dissolution of crystal grain boundaries during electrolysis cannot be suppressed, and formation of a uniform black film and generation of anode slime Since the reduction and generation of plating defects due to slime cannot be achieved, the special grain boundary length ratio Lσ _N / L _N was determined to be Lσ _N / L _N ≧ 0.4.

The phosphorus-containing copper anode of the present invention desirably contains 100 to 800 ppm of phosphorus by mass%. If the phosphorus content is out of this range, a stable black film is not formed and anode slime is generated.
The average crystal grain size of the phosphorous-containing copper anode of the present invention (twins are also counted as crystal grains) is desirably 3 to 1000 μm, and when the average crystal grain size is out of this range, more anode slime is generated. To do.

The unit total special grain boundary length Lσ _{N obtained} by converting the total special grain boundary length Lσ of the special grain boundary per unit area 1 mm ² and the total grain boundary length L of the crystal grain boundary are converted per unit area 1 mm ^2. The phosphorous copper anode having a grain boundary structure in which the special grain boundary length ratio Lσ _N / L _N to the unit total grain boundary length L _N satisfies the relationship of Lσ _N / L _N ≧ 0.4 is When producing phosphorous copper for plating, after processing (cold processing and / or hot processing) to give processing strain, it can be manufactured by performing recrystallization heat treatment at 350 to 900 ° C. .
As a specific manufacturing example, for example,
(B) Hot-working with a rolling reduction of 5 to 80% on phosphorous-containing copper for electroplating in a temperature range of 400 to 900 ° C., and then statically holding for 3 to 300 seconds without giving the processing strain And a method for producing a phosphorous copper anode for electroplating having a grain boundary structure satisfying a relationship of Lσ _N / L _N ≧ 0.4 by performing recrystallization heat treatment,
As other production examples,
(B) After cold working at a reduction rate of 5 to 80%, the steel is heated to a temperature range of 350 to 900 ° C., statically held for 5 minutes to 5 hours without giving the above-described distortion, and recrystallized. A method for producing a phosphorous copper anode for electroplating having a grain boundary structure satisfying a relationship of Lσ _N / L _N ≧ 0.4 by performing a crystallization heat treatment,
Can be mentioned.
After straining by hot working or cold working at a specific reduction ratio of (A) and (B) above, recrystallization is performed in a recrystallization temperature range in a statically maintained state without imparting strain. it allows promotes the formation of special grain boundaries, increasing the proportion of the unit total special grain boundary length Erushiguma _N, the value of the special grain boundary length ratio Lσ _{N /} L _N may be 0.4 or more.
It is also possible to obtain a grain boundary structure satisfying Lσ _N / L _N ≧ 0.4 by repeatedly performing the hot working, cold working and recrystallization heat treatment.

The special grain boundary length ratio Lσ _N / L _N between the unit total special grain boundary length Lσ _{N of the} special grain boundary and the unit total grain boundary length L _N of the crystal grain boundary is Lσ _N / L _N ≧ 0.4 The generation of anode slime can be reduced by performing electrolytic copper plating using a phosphorous copper anode having a grain boundary structure satisfying the above relationship as an anode for electroplating. When the surface of the material to be plated is copper-plated, it is possible to form a precise copper wiring free from plating defects such as contamination and protrusions on the surface of the semiconductor wafer.

The grain boundary of the phosphorous copper anode is specified and the total grain boundary length L _N is measured by irradiating the individual crystal grains on the anode surface with an electron beam using a scanning electron microscope, and the obtained backscattered electrons. Based on the crystal orientation data obtained from the diffraction pattern, the interface between adjacent crystal grains having an orientation difference between adjacent crystal grains of 15 ° or more is used as the crystal grain boundary, and the total grain boundary length L of the crystal grain boundary in the measurement range is calculated. Measurement is performed by dividing this by the measurement area and converting it to the unit total grain boundary length per 1 mm ^{2 of} unit area. Also, the special grain boundary is specified and the unit total special grain boundary length Lσ _N is measured by irradiating each crystal grain on the anode surface with an electron beam and using the field emission scanning electron microscope. While determining the position of the grain boundary where the interface of the crystal grains constitutes the special grain boundary, the total special grain boundary length Lσ of the special grain boundary is measured, and this is divided by the measurement area to obtain the total unit per unit area of 1 mm ² This is done by converting to a special grain boundary length.
Specifically, an EBSD measuring apparatus using a field emission scanning electron microscope (S4300-SE manufactured by HITACHI, OIM Data Collection manufactured by EDAX / TSL) and analysis software (OIM Data Analysis ver. 5 manufactured by EDAX / TSL). .2), the crystal grain boundary and the special grain boundary are specified, and the length can be calculated.
In addition, the average grain size of the phosphorous-containing copper anode (twices are counted as crystal grains) is determined by determining the grain boundaries from the results obtained by the EBSD measuring device and analysis software, and the crystals in the observation area. The average crystal grain size (diameter) can be obtained by calculating the number of particles, dividing the area by the number of crystal grains, calculating the crystal grain area, and converting it into a circle.

  According to the phosphorous copper anode for electrolytic copper plating of the present invention, a method for producing the same, and an electrolytic copper plating method, for example, even when fine copper wiring is formed on a semiconductor wafer or the like by electrolytic copper plating, In addition to suppressing the occurrence of plating, it is possible to prevent the occurrence of plating defects such as contamination and protrusions due to slime on the surface of the material to be plated such as a semiconductor wafer.

(A)-(d) is a schematic diagram which shows the dissolution progress state of the anode surface by electrolysis, (a) is the initial state when electrolysis was started, (b) is the time when electrolysis was started and a fixed time elapsed. In the state where the selective dissolution of the grain boundary has started, (c) shows the result of the selective dissolution of the grain boundary, resulting in non-uniform current density due to the shape factor. (D) shows the state in which undissolved crystal grains are peeled off and peeled off together with the black film (surface oxide film) formed on the anode surface by dissolution of the grain boundaries. The EBSD analysis result of this invention 3 is shown, a thick line shows a special grain boundary, and a thin line shows a general grain boundary (the same also about FIGS. 3-9). The EBSD analysis result of this invention 7 is shown. The EBSD analysis result of this invention 11 is shown. The EBSD analysis result of this invention 13 is shown. The EBSD analysis result of this invention 21 is shown. The EBSD analysis result of this invention 27 is shown. The EBSD analysis result of the comparative example 4 is shown. The EBSD analysis result of the comparative example 6 is shown.

  Next, the present invention will be specifically described with reference to examples.

Recycled phosphorus-containing copper containing a predetermined amount of P (phosphorus) shown in Table 1 and having a total content of Pb, Fe, Sn, Zn, Mn, Ni, and Ag as inevitable impurities is 0.002% by mass or less. The crystal material or cast material is subjected to hot processing (temperature, processing method, processing rate), cold processing (processing method, processing rate), and recrystallization heat treatment (temperature, time) under the conditions shown in Table 1. Alternatively, these were repeated, and after the recrystallization heat treatment, water-cooled to produce phosphorous copper anodes (referred to as the present invention anodes) 1 to 28 of the present invention having predetermined sizes shown in Table 3.
As examples in Table 1, only hot processing-recrystallization heat treatment, cold processing-recrystallization heat treatment, or repetition of these under required conditions are listed, It does not necessarily have to be repeated under the same conditions, and it is repeated under different conditions (processing temperature, processing method, processing rate, holding temperature, holding time) as long as they are within the conditions specified in the claims. Of course, it is possible to perform.

About the anode of the present invention manufactured as described above, the EBSD measurement apparatus (HITACHI S4300-SE, EDAX / TSL OIM Data Collection) and analysis software (EDAX / TSL OIM Data Analysis ver. 5.2) are used. The crystal grain boundaries and special grain boundaries were specified, and the unit total grain boundary length L _N and the unit total special grain boundary length Lσ _N were determined.
Table 3 shows L _N , Lσ _N and special grain boundary length ratio Lσ _N / L _N.
Table 3 also shows the average crystal grain size values obtained from the results obtained by the EBSD measuring apparatus and analysis software.
2 to 7 show the EBSD analysis results of the anodes 3, 7, 11, 13, 21, and 27 of the present invention, respectively.

For comparison, hot processing (temperature, processing method, processing rate) was performed on the phosphorous-containing copper anode material prepared above under the conditions shown in Table 2 (at least one condition is outside the scope of the present invention). ), Cold working (working method, working rate), and recrystallization heat treatment (temperature, time) were performed to produce phosphorous copper anodes (referred to as comparative example anodes) 1 to 8 of Comparative Examples shown in Table 4.
For the comparative anode produced as described above, the unit total grain boundary length L _N , the unit total special grain boundary length Lσ _N , the special grain boundary length ratio Lσ _N / L _N and the average were also obtained in the same manner as in the present invention. The crystal grain size was determined.
This value is shown in Table 4.
8 and 9 show the EBSD analysis results of the comparative anodes 4 and 6, respectively.

Using the above-described anodes 1 to 28 of the present invention and comparative anodes 1 to 8 (both having an anode surface area of 530 cm ² ), using a semiconductor wafer as a cathode, electroplating copper on five semiconductor wafers under the following conditions Went.
Plating _{solution: CuSO 4 · 5H 2 O 200g} / L,
H ₂ SO ₄ 50 g / L,
Cl ^- 50 ppm,
Additives Polyethylene glycol: 400 ppm (molecular weight 6000)
Plating conditions: liquid temperature 25 ° C,
Cathode current density 2 A / dm ² ,
Plating time 1 hour / sheet,

For the above-described inventive anodes 1 to 28 and comparative anodes 1 to 8, the amount of anode slime generated from the start of electrolytic copper plating to the completion of electrolytic copper plating (5 hours) on the fifth wafer was measured.
Further, the surface of the semiconductor wafer after plating was observed with an optical microscope, and protrusions with a height of 5 μm or more formed on the wafer surface were regarded as defects, and the number of protrusion defects was counted.
The measurement results are shown in Tables 5 and 6.

From the results shown in Tables 5 and 6, according to the phosphorous copper anode for electrolytic copper plating, the method for producing phosphorous copper anode for electrolytic copper plating and the electrolytic copper plating method of the present invention, for example, a semiconductor wafer or the like In the case of forming a precise copper wiring, it is possible to suppress the generation of anode slime and prevent the occurrence of plating defects such as contamination and protrusions on the surface of a material to be plated such as a semiconductor wafer.
However, it can be seen that in the comparative example anode in which the special grain boundary length ratio Lσ _N / L _N is less than 0.4, not only the amount of anode slime generated is large, but also plating defects due to slime frequently occur.

  As described above, the present invention has an excellent effect that it can suppress the generation of anode slime during electrolytic copper plating and can prevent the occurrence of plating defects on the surface of the material to be plated. When it is applied to the formation of a copper wiring, it is possible to prevent the occurrence of defects such as contamination and protrusions on the semiconductor wafer, so that the industrial utility is extremely high.

Claims (9)

In phosphorous copper anode for electroplating,
(A) Using a scanning electron microscope, each crystal grain on the anode surface is irradiated with an electron beam, and the interface between crystal grains having an orientation difference between adjacent crystal grains of 15 ° or more is used as a grain boundary. The total grain boundary length L of the crystal grain boundary in the range was measured, and the unit total grain boundary length L _N was calculated by converting this per unit area 1 mm ² (b). Similarly, using a scanning electron microscope, The individual crystal grains on the anode surface are irradiated with an electron beam to determine the position of the crystal grain boundary where the interface between adjacent crystal grains constitutes the special grain boundary, and the total special grain boundary length Lσ of the special grain boundary. When this is converted into a unit area of 1 mm ² and the unit total special grain boundary length Lσ _N is obtained,
(C) A special grain boundary length ratio Lσ _N / L _N between the unit grain boundary length L _N of the measured grain boundary and the unit total special grain boundary length Lσ _N of the special grain boundary that is also measured ,
Lσ _N / L _N ≧ 0.4
A phosphorous copper anode for electroplating, characterized by having a grain boundary structure satisfying the following relationship:   The phosphorus-containing copper anode for electroplating according to claim 1, which contains 100 to 800 ppm of phosphorus by mass%.   3. The phosphorous copper anode for electroplating according to claim 1, wherein the average crystal grain size is 3 to 1000 μm. The special grain boundary length ratio Lσ _N / L _{N is set} to 0.4 or more by performing recrystallization heat treatment at 350 to 900 ° C. after processing the phosphor-containing copper for electroplating to give processing strain. The method for producing a phosphorous copper anode for electroplating according to any one of claims 1 to 3.   The method for producing a phosphorous copper anode for electroplating according to claim 4, wherein the processing is performed by at least one of cold processing and hot processing. Claims wherein cold working and recrystallization heat treatment, or hot working and recrystallization heat treatment, or a combination thereof are repeated until the special grain boundary length ratio Lσ _N / L _N becomes 0.4 or more. A method for producing a phosphorous copper anode for electroplating according to 4 or 5.   5. A hot crystallization process is performed at a reduction rate of 5 to 80% in a temperature range of 400 to 900 ° C., and then statically held without applying the processing strain for 3 to 300 seconds, and a recrystallization heat treatment is performed. A method for producing a phosphorous copper anode for electroplating as described in 1.   Cold-working at a reduction rate of 5 to 80%, then heating to a temperature range of 350 to 900 ° C., and statically holding without applying the processing strain for 5 minutes to 5 hours, recrystallization heat treatment The manufacturing method of the phosphorous copper anode for electroplating of Claim 4 to perform.   The electrolytic copper plating method using the phosphorus-containing copper anode for electroplating as described in any one of Claims 1 thru | or 3.

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