Plating solution, method for producing plating film, and metal member

Abstract

[Problem] To provide a metal member in which the occurrence of cracks can be suppressed even when subjected to a heat treatment. [Solution] According to the present invention, a metal member which contains a metal as a main component, and in which 50 vol% or more of a nitrogen-containing metal region that contains 0.025 at% or more of nitrogen in the member is formed, especially a metal member in which a part or all of the nitrogen-containing metal region is formed inside the metal member is applied to an electric product or the like. The present invention also provides a plating solution which is capable of industrially advantageously forming a plating film that forms the nitrogen-containing metal region.

Description

Plating solution, method for producing plating film, and metal member

[0001] The present invention relates to a plating film useful for electronic components and the like, and a plating solution useful for producing the plating film.

[0002] Porous metal bodies are highly useful as functional materials due to their large specific surface area and excellent material retention properties, and many reports have been published on their manufacturing methods.

[0003] For example, common methods for producing a metal porous body include a method of sintering fine metal particles and a method of making a porous resin conductive and then electroplating it.

[0004] However, all of these methods require special equipment, and the shape of the resulting porous metal body is also limited.

[0005] Other methods of forming porous metal films that have been reported include a method of electrodepositing metal using an electrolytic solution containing an additive made of an electrolyte that combines cations and anions with high ionic mobility (see Patent Document 1), and a method of forming a metallic copper film by electroless plating using an electroless plating solution that contains an acetylene group-containing compound (see Patent Document 2).

[0006] Furthermore, Patent Document 3 discloses a method for easily forming a uniform and excellent porous plating film by adding a water-soluble quaternary ammonium compound having a hydrophobic group to a plating bath when forming a plating film on a conductive substrate by electroplating.

[0007] However, conventional plating films have the problem of cracking when heat treated, and a solution to this problem has been eagerly awaited.

[0008] JP-A-6-65779 JP-A-10-237664 Patent No. 5366076

[0009] An object of the present invention is to provide a plating film that can suppress the occurrence of cracks even when heat treated, and a plating solution that can industrially advantageously form the plating film.

[0010] As a result of intensive research to achieve the above object, the present inventors have succeeded in creating a plating film including anti-crack void generation portions for generating anti-crack voids by using nitrogen to form a plating film having an average crystallite size of 200 Å or less, and have found that such a plating film can suppress crack generation even when heat treated, thereby finding that the above-mentioned conventional problems can be solved in one fell swoop.Furthermore, after obtaining the above findings, the present inventors have conducted further research and have completed the present invention.

[0011] That is, the present invention relates to the following inventions. [1] A plating solution comprising at least a metal compound and an inorganic solvent, wherein the nitrogen content in the plating solution is 0.2 mol / L or more. [2] The plating solution according to [1], wherein the metal compound contains a metal having a potential nobler than −1.0 V vs. a standard hydrogen electrode. [3] The plating solution according to [1], wherein the inorganic solvent is water. [4] A method for producing a plating film using a plating solution, wherein the plating solution is the plating solution according to [1]. [5] A plating film containing crystal grains, wherein the plating film has a crack prevention void generation portion in which a crack prevention void is generated by heat treatment. [6] The plating film according to [5], wherein the crack prevention void generation portion comprises nitrogen and crystal grains. [7] The plating film according to [5], wherein the heat treatment temperature is 150°C or more and the heat treatment time is 5 minutes or more. [8] A plating film containing crystal grains, wherein the average crystallite size of the crystal grains calculated by the Halder-Wagner method is 200 Å or less. [9] The plating film according to [8], wherein the crystal grains are made of metal.

[10] The plating film according to [8], wherein the crystal grains have a crystal lattice distortion of 0.1% or less.

[11] The plating film according to [8], wherein the film thickness is 30 μm or more.

[12] A product containing a plating film, wherein the plating film is the plating film according to [5] or [8].

[13] A plating film containing crystal grains, wherein the plating film contains 0.025 at% to 0.100 at% nitrogen.

[14] The plating film according to

[13] , wherein the average crystallite size of the crystal grains calculated by the Halder-Wagner method is 200 Å or less.

[15] The plating film according to

[13] , wherein the crystal grains are made of metal.

[16] The plating film according to

[13] , further comprising sulfur, wherein the content of sulfur in the plating film is 0.01 to 100 in terms of atomic ratio of sulfur to nitrogen 1.

[17] The plating film according to

[13] , wherein the crystal lattice distortion of the crystal grains is 0.1% or less.

[18] The plating film according to

[13] , wherein the film thickness is 10 μm or more.

[19] A product comprising a plating film, wherein the plating film is the plating film according to

[13] .

[20] A plating solution comprising at least a metal compound and an inorganic solvent, the plating solution containing nitrogen and divalent sulfur, and further characterized in that the nitrogen content in the plating solution is 0.2 mol / L or more.

[21] The plating solution according to

[20] , wherein the metal compound contains a metal having a potential nobler than −1.0 V vs. a standard hydrogen electrode.

[22] The plating solution according to

[20] , wherein the inorganic solvent is water.

[23] A method for producing a plating film using a plating solution, the method comprising producing a plating film using the plating solution according to

[20] .

[24] A plating film containing crystal grains, the plating film containing 0.020 at% to 0.100 at% sulfur.

[25] The plating film according to

[24] , wherein the average crystallite size of the crystal grains calculated by the Halder-Wagner method is 200 Å or less.

[26] The plating film according to

[24] , wherein the crystal grains are made of metal.

[27] The plating film according to

[24] , further comprising carbon, wherein the carbon content in the plating film is 0.01 to 100 carbon to sulfur atomic ratio.

[28] The plating film according to

[24] , wherein the crystal lattice distortion of the crystal grains is 0.1% or less.

[29] The plating film according to

[24] , wherein the film thickness is 10 μm or more.

[30] A product comprising a plating film, wherein the plating film is the plating film according to

[24] .

[31] A plating solution comprising at least a metal compound and an inorganic solvent, the plating solution containing nitrogen and carbon, wherein the nitrogen content in the plating solution is 0.2 mol / L or more.

[32] The plating solution according to

[31] , wherein the metal compound contains a metal having a potential nobler than −1.0 V vs. a standard hydrogen electrode.

[33] The plating solution according to

[31] , wherein the inorganic solvent is water.

[34] A method for producing a plating film using a plating solution, wherein the plating solution is the plating solution according to

[31] .

[35] A plating film containing crystal grains, characterized in that the plating film contains 0.15 at% to 1.00 at% carbon.

[36] The plating film according to

[35] , wherein the average crystallite size of the crystal grains calculated by the Halder-Wagner method is 200 Å or less.

[37] The plating film according to

[35] , wherein the crystal grains are made of metal.

[38] The plating film according to

[35] , further comprising sulfur, wherein the content of sulfur in the plating film is 0.001 to 10 in terms of atomic ratio of sulfur to carbon.

[39] The plating film according to

[35] , wherein the crystal grains have a crystal lattice distortion of 0.1% or less.

[40] The plating film according to

[35] , wherein the film thickness is 10 μm or more.

[41] A product comprising a plating film, wherein the plating film is the plating film according to

[35] .

[42] A plating solution comprising at least a metal compound and an inorganic solvent, the plating solution containing nitrogen and hydrogen, wherein the nitrogen content in the plating solution is 0.2 mol / L or more.

[43] The plating solution according to

[42] , wherein the metal compound contains a metal having a potential nobler than −1.0 V vs. a standard hydrogen electrode.

[44] The plating solution according to

[42] , wherein the inorganic solvent is water.

[45] A method for producing a plating film using a plating solution, wherein the plating solution is the plating solution according to

[42] .

[46] A plating film containing crystal grains, characterized in that the plating film contains 1.0 at% to 5.0 at% hydrogen.

[47] The plating film according to

[46] , wherein the average crystallite size of the crystal grains calculated by the Halder-Wagner method is 200 Å or less.

[48] The plating film according to

[46] , wherein the crystal grains are made of metal.

[49] The plating film according to

[46] , further containing nitrogen, wherein the content of nitrogen in the plating film is 0.001 to 10 in terms of atomic ratio of nitrogen to hydrogen (100).

[50] The plating film according to

[46] , wherein the crystal lattice distortion of the crystal grains is 0.1% or less.

[51] The plating film according to

[46] , wherein the film thickness is 10 μm or more.

[52] A product including a plating film, wherein the plating film is the plating film according to

[46] .

[53] A metal member containing a metal as a main component, characterized in that a nitrogen-containing metal region containing 0.025 at% or more of nitrogen is formed in 50 volume% or more of the member.

[54] The metal member according to

[53] , wherein the nitrogen-containing metal region contains 0.1 at% or less of nitrogen.

[55] The metal member according to

[53] , wherein the nitrogen-containing metal region further contains 0.02 to 0.1 at% of sulfur.

[56] The metallic component according to

[53] , wherein the nitrogen-containing metal region further contains 0.15 to 1.0 at% carbon.

[57] The metallic component according to

[53] , wherein the nitrogen-containing metal region further contains 1 to 5 at% hydrogen.

[58] The metallic component according to

[53] , wherein the metal comprises a metal having a potential more noble than -1.0 V vs. a standard hydrogen electrode.

[59] The metallic component according to

[53] , wherein the nitrogen-containing metal region contains crystal grains, and the average crystallite size of the crystal grains calculated by the Halder-Wagner method is 200 Å or less.

[60] The metallic component according to

[59] , wherein the crystal grains have a crystal lattice distortion of 0.1% or less.

[61] The metallic component according to

[53] , wherein the nitrogen-containing metal region is formed in the form of a film.

[62] The metallic component according to

[61] , wherein the film thickness of the nitrogen-containing metal region is 10 μm or more.

[63] The metal member according to

[53] , wherein a part or all of the nitrogen-containing metal region is formed inside the metal member.

[64] A product including a metal member, wherein the metal member is the metal member according to

[53] .

[0012] The plating film of the present invention can suppress the occurrence of cracks even when heat treated. Furthermore, the plating solution of the present invention can form the plating film in an industrially advantageous manner.

[0013] FIG. 1 is a diagram for explaining the presence or absence of cracks after heat treatment in Example 1. FIG. 2 is a diagram for explaining the presence or absence of cracks after heat treatment in Comparative Example 1. FIG. 3 is a diagram for explaining the presence or absence of cracks after heat treatment in Example 2. FIG. 4 is a diagram for explaining the presence or absence of cracks after heat treatment in Comparative Example 2. FIG. 5 is a diagram for explaining a cross section after heat treatment in Example 1. FIG. 6 is a diagram for explaining a cross section after heat treatment in Example 2. FIG. 7 is a diagram for explaining the relationship of thermal expansion (follow-up ability) in test examples. FIG. 8 is a diagram for explaining the presence or absence of swelling after heat treatment in Example 3. FIG. 9 is a diagram for explaining the presence or absence of swelling after heat treatment in Comparative Example 3. FIG. 10 is a diagram for explaining the presence or absence of cracks after heat treatment in Example 5. FIG. 11 is a diagram for explaining the presence or absence of cracks after heat treatment in Example 6. FIG. 12 is a diagram for explaining the presence or absence of cracks after heat treatment in Example 7. FIG. 13 is a diagram for explaining the presence or absence of cracks after heat treatment in Comparative Example 5. FIG. 14 is a diagram for explaining a cross section after heat treatment in Example 5. FIG. 15 is a diagram for explaining a cross section after heat treatment in Example 6. FIG. 16 is a diagram for explaining a cross section after heat treatment in Example 7.

[0014] Specific embodiments of the inventions described above in [1] to

[12] are described below, but the present invention is not limited to these descriptions. The plating film of the present invention is a plating film containing crystal grains, characterized in that it has a crack prevention void generation portion where crack prevention voids are generated by heat treatment. The plating film of the present invention is also a plating film containing crystal grains, characterized in that the average crystallite size of the crystal grains calculated by the Halder-Wagner method is 200 Å or less.

[0015] In the present invention, the heat treatment temperature is preferably 150° C. or higher and the heat treatment time is preferably 5 minutes or longer. Such a preferred range makes it more suitable for use in manufacturing processes involving heat treatment.

[0016] In the present invention, the crystal grains are preferably made of a metal, and more preferably made of a metal having a potential higher than −1.0 V versus a standard hydrogen electrode. Within this preferred range, cracks due to heat treatment can be more efficiently suppressed.

[0017] In the present invention, the crystal lattice distortion of the crystal grains is preferably 0.1% or less, since this range makes it possible to suppress cracks over a wider range.

[0018] Although there are no particular limitations on the thickness of the plating film, in the present invention, the thickness is preferably 30 μm or more. Within this preferred range, cracks can be more stably suppressed.

[0019] The plating film can be produced using known plating methods. In the present invention, a plating solution containing at least a metal compound and an inorganic solvent is preferably used, and the nitrogen content in the plating solution is preferably 0.2 mol / L or more, and more preferably 0.25 mol / L or more. The means for incorporating nitrogen into the plating solution is not particularly limited as long as it does not impair the objectives of the present invention, and any known means may be used. Examples include bubbling the plating solution with nitrogen or adding a nitrogen compound to the plating solution. By using such a plating solution to produce the plating film, the plating film can be formed more industrially advantageously. Such plating solutions are also encompassed by the present invention.

[0020] In the present invention, the metal compound preferably contains a metal having a potential higher than −1.0 V vs. a standard hydrogen electrode. This preferred range allows for the formation of a higher quality plating film. Examples of the metal include zinc, chromium, iron, tin, copper, silver, nickel, gold, platinum, palladium, rhodium, ruthenium, cobalt, gallium, germanium, cadmium, indium, antimony, osmium, iridium, bismuth, and lead, as well as alloys thereof.

[0021] In the present invention, the inorganic solvent preferably contains water. In accordance with this preferred range, known plating methods can be more suitably applied.

[0022] The plating film formed as described above can be used in various products, for example, electrical and electronic components.

[0023] (Example 1A) An aqueous copper plating solution containing 0.25 mol / L of nitrogen was prepared, and a 200 μm thick film was formed by electroplating. The resulting plated film had an average crystallite size of 102 Å and 0% crystal lattice distortion. The resulting plated film was heat-treated at 250°C for 1 hour, and the presence or absence of cracks after heat treatment was evaluated. The evaluation results are shown in Figure 1. Figure 1 shows that no cracks occurred even after heat treatment. The cross section of the plated film after heat treatment was also observed. A cross-sectional SEM image is shown in Figure 5. As is clear from Figure 5, no cracks occurred, and crack prevention voids were found to have occurred. The respective measurement methods are as follows. (XRD Measurement) The average crystallite size and crystal lattice distortion were calculated from the measured data using the Halder-Wagner method. The average crystallite size was specifically determined by the following method. A Rigaku Corporation SmartLab equipped with a Cu-Kα X-ray source and a D / teX Ultra 250 detector was used. The voltage was set to 40 kV, the current to 150 mA, and measurements were made by the θ-2θ method with a 2θ range of 20-100 degrees, a scanning step of 0.02 degrees, and a scanning speed of 4 degrees / min. (Measurement of the average diameter of crack prevention voids) The generated crack prevention voids were observed using an FE-SEM (JSM-7900F manufactured by JEOL Ltd.) at a magnification of 5000 times and an acceleration voltage of 5 kV, using backscattered electron images. The images were binarized using ImageJ, and the average diameter of the crack prevention voids was calculated by calculating the porosity. The calculated results were as follows. Heat treatment at 300° C. for 10 minutes: 3.07 nm Heat treatment at 300° C. for 60 minutes: 4.71 nm Heat treatment at 400° C. for 60 minutes: 12.49 nm Heat treatment at 500° C. for 60 minutes: 17.73 nm No cracks were generated in any of the heat treatments.

[0024] (Comparative Example 1A) A copper plating solution containing 0.1 mol / L of nitrogen was prepared, and a 200 μm thick film was formed by electroplating. The resulting plating film had an average crystallite size of 230 Å and a crystal lattice distortion of 0.27%. The resulting plating film was heat-treated at 250°C for 1 hour, and the presence or absence of cracks after the heat treatment was evaluated. The evaluation results are shown in Figure 2. As is clear from Figure 2, cracks were generated after the heat treatment.

[0025] (Example 2A) A copper plating solution containing 0.2 mol / L of nitrogen was prepared, and a 200 μm thick film was formed by electroplating. The resulting plated film was heat-treated at 250°C for 1 hour, and the presence or absence of cracks after the heat treatment was evaluated. The evaluation results are shown in Figure 3. Figure 3 shows that no cracks were generated even after the heat treatment. The cross section of the plated film after the heat treatment was also observed. A cross-sectional SEM image is shown in Figure 6. As is clear from Figure 6, no cracks were generated, and it was found that crack-preventing voids were generated.

[0026] (Comparative Example 2A) A copper plating solution containing 0.16 mol / L of nitrogen was prepared, and a 200 μm thick film was formed by electroplating. The resulting plating film was heat-treated at 250° C. for 1 hour, and the presence or absence of cracks after the heat treatment was evaluated. The evaluation results are shown in FIG. 4. As is clear from FIG. 4, cracks were generated after the heat treatment.

[0027] Specific embodiments of the inventions

[13] to

[19] above will be described below, but the invention is not limited to these descriptions. The plating film of the present invention is a plating film containing crystal grains, and is characterized by containing 0.025 at % to 0.100 at % nitrogen in the plating film.

[0028] The plating film of the present invention is a plating film containing crystal grains, characterized in that it has a crack prevention void generation portion where crack prevention voids are generated by heat treatment.The plating film of the present invention is also characterized in that the plating film contains crystal grains, and the average crystallite size of the crystal grains calculated by the Halder-Wagner method is 200 Å or less.

[0029] In the present invention, it is preferable that the plating film further contains sulfur, and the content of sulfur in the plating film is, in atomic ratio, sulfur to nitrogen of 1, from 0.01 to 100. Within such a preferred range, cracks can be more efficiently suppressed.

[0030] In the present invention, the crystal grains are preferably made of a metal, and more preferably made of a metal having a potential higher than −1.0 V versus a standard hydrogen electrode. Within this preferred range, cracks due to heat treatment can be more efficiently suppressed.

[0031] In the present invention, the crystal lattice distortion of the crystal grains is preferably 0.1% or less, since this range makes it possible to suppress cracks over a wider range.

[0032] Although there are no particular limitations on the thickness of the plating film, it is preferable in the present invention that the thickness be 10 μm or more. Within this preferred range, cracks can be more stably suppressed.

[0033] The plating film can be produced using known plating methods. In the present invention, a plating solution containing at least a metal compound and an inorganic solvent is preferably used, and the nitrogen content in the plating solution is preferably 0.2 mol / L or more, and more preferably 0.25 mol / L or more. The means for incorporating nitrogen into the plating solution is not particularly limited as long as it does not impair the objectives of the present invention, and any known means may be used. Examples include bubbling the plating solution with nitrogen or adding a nitrogen compound to the plating solution. By using such a plating solution to produce the plating film, the plating film can be formed more industrially advantageously. Such plating solutions are also encompassed by the present invention.

[0034] In the present invention, the metal compound preferably contains a metal having a potential higher than −1.0 V vs. a standard hydrogen electrode. This preferred range allows for the formation of a higher quality plating film. Examples of the metal include zinc, chromium, iron, tin, copper, silver, nickel, gold, platinum, palladium, rhodium, ruthenium, cobalt, gallium, germanium, cadmium, indium, antimony, osmium, iridium, bismuth, and lead, as well as alloys thereof.

[0035] In the present invention, the inorganic solvent preferably contains water. In accordance with this preferred range, known plating methods can be more suitably applied.

[0036] The plating film formed as described above can be used in various products, for example, electrical and electronic components.

[0037] (Example 1B) A copper plating solution containing 0.25 mol / L of nitrogen was prepared, and a 200 μm thick film was formed by electroplating. The resulting plating film had a nitrogen content of 0.045 at%. The resulting plating film also contained 0.029 at% sulfur. The resulting plating film had an average crystallite size of 102 Å and a crystal lattice distortion of 0%. The resulting plating film was heat-treated at 250°C for 1 hour, and the presence or absence of cracks after the heat treatment was evaluated. The evaluation results are shown in Figure 1. Figure 1 indicates that no cracks occurred even after the heat treatment. The cross-section of the plating film after the heat treatment was also observed. A cross-sectional SEM image is shown in Figure 5. As is clear from Figure 5, no cracks occurred, and crack-preventing voids were observed. The respective measurement methods were as follows. (XRD Measurement) The average crystallite size and crystal lattice distortion were calculated from the measured data using the Halder-Wagner method. The average crystallite size was determined specifically by the following method. A Rigaku Corporation SmartLab equipped with a Cu-Kα X-ray source and a D / teX Ultra 250 detector was used. The voltage was set to 40 kV, the current to 150 mA, and the θ-2θ method was used with a 2θ range of 20-100 degrees, a scanning step of 0.02 degrees, and a scanning rate of 4 degrees / min. (Measurement of the average diameter of crack prevention voids) The generated crack prevention voids were observed as backscattered electron images using an FE-SEM (JSM-7900F manufactured by JEOL Ltd.) at a magnification of 5000x and an acceleration voltage of 5 kV. The images were binarized using ImageJ, and the average diameter of the crack prevention voids was calculated by calculating the porosity. The calculated results were as follows. Heat treatment at 300° C. for 10 minutes: 3.07 nm Heat treatment at 300° C. for 60 minutes: 4.71 nm Heat treatment at 400° C. for 60 minutes: 12.49 nm Heat treatment at 500° C. for 60 minutes: 17.73 nm No cracks were generated in any of the heat treatments.

[0038] (Comparative Example 1B) A copper plating solution containing 0.1 mol / L of nitrogen was prepared, and a film having a thickness of 200 μm was formed by electroplating. The resulting plating film had a nitrogen content of 0.018 at%. The resulting plating film also had an average crystallite size of 230 Å and a crystal lattice distortion of 0.27%. The resulting plating film was heat-treated at 250°C for 1 hour, and the presence or absence of cracks after the heat treatment was evaluated. The evaluation results are shown in Figure 2. As is clear from Figure 2, cracks were generated after the heat treatment.

[0039] (Example 2B) A copper plating solution containing 0.2 mol / L of nitrogen was prepared, and a 200 μm thick film was formed by electroplating. The resulting plating film had a nitrogen content of 0.030 at%. The resulting plating film also contained 0.023 at% sulfur. The resulting plating film was heat-treated at 250°C for 1 hour, and the presence or absence of cracks after the heat treatment was evaluated. The evaluation results are shown in Figure 3. Figure 3 shows that no cracks were generated even after the heat treatment. The cross section of the plating film after the heat treatment was also observed. A cross-sectional SEM image is shown in Figure 6. As is clear from Figure 6, no cracks were generated, and crack-preventing voids were found to have been generated.

[0040] (Comparative Example 2B) A copper plating solution containing 0.16 mol / L of nitrogen was prepared, and a 200 μm thick film was formed by electroplating. The resulting plating film had a nitrogen content of 0.022 at%. The resulting plating film was also heat-treated at 250°C for 1 hour, and the presence or absence of cracks after the heat treatment was evaluated. The evaluation results are shown in Figure 4. As is clear from Figure 4, cracks were generated after the heat treatment.

[0041] Specific embodiments of the inventions

[20] to

[30] above will be described below, but the present invention is not limited to these descriptions. The plating film of the present invention is a plating film containing crystal grains, and is characterized by containing 0.020 at% to 0.100 at% sulfur in the plating film. With such a plating film, even if the nitrogen content is less than 0.02 at% or more, cracking can be suppressed even when heat treated.

[0042] The plating film of the present invention further contains carbon, and the content of carbon in the plating film is preferably in an atomic ratio of carbon to sulfur of 1 to 0.01 to 100. This preferred range makes it more suitable for use in manufacturing processes involving heat treatment.

[0043] In the present invention, the average crystallite size of the crystal grains calculated by the Halder-Wagner method is preferably 200 Å or less. Within this preferred range, cracks due to heat treatment can be more efficiently suppressed.

[0044] In the present invention, the crystal grains are preferably made of a metal, and more preferably made of a metal having a potential higher than −1.0 V versus a standard hydrogen electrode. Within this preferred range, cracks due to heat treatment can be more efficiently suppressed.

[0045] In the present invention, the crystal lattice distortion of the crystal grains is preferably 0.1% or less, since this range makes it possible to suppress cracks over a wider range.

[0046] Although there are no particular limitations on the thickness of the plating film, it is preferable in the present invention that the thickness be 10 μm or more. Within this preferred range, cracks can be more stably suppressed.

[0047] The plating film can be produced using known plating methods. In the present invention, a plating solution containing at least a metal compound and an inorganic solvent, nitrogen, and divalent sulfur is preferably used, and the nitrogen content in the plating solution is 0.2 mol / L or more, and more preferably 0.25 mol / L or more. The means for incorporating nitrogen into the plating solution is not particularly limited as long as it does not impair the objectives of the present invention, and any known means may be used. Examples include bubbling the plating solution with nitrogen or adding a nitrogen compound to the plating solution. The means for incorporating divalent sulfur into the plating solution is not particularly limited as long as it does not impair the objectives of the present invention, and any known means may be used. By using such a plating solution to produce the plating film, the plating film can be formed more industrially advantageously. Such plating solutions are also encompassed by the present invention.

[0048] In the present invention, the metal compound preferably contains a metal having a potential higher than −1.0 V vs. a standard hydrogen electrode. This preferred range allows for the formation of a higher quality plating film. Examples of the metal include zinc, chromium, iron, tin, copper, silver, nickel, gold, platinum, palladium, rhodium, ruthenium, cobalt, gallium, germanium, cadmium, indium, antimony, osmium, iridium, bismuth, and lead, as well as alloys thereof.

[0049] In the present invention, the inorganic solvent preferably contains water. In accordance with this preferred range, known plating methods can be more suitably applied.

[0050] The plating film formed as described above can be used in various products, for example, electrical and electronic components.

[0051] (Example 1C) A copper plating solution containing 0.25 mol / L of nitrogen and divalent sulfur was prepared, and a 200 μm-thick film was formed by electroplating. The resulting plating film contained 0.029 at% divalent sulfur and 0.32 at% carbon. The resulting plating film had an average crystallite size of 102 Å and 0% crystal lattice distortion. The resulting plating film was heat-treated at 250°C for 1 hour and evaluated for the presence or absence of cracks after heat treatment. The evaluation results are shown in Figure 1. Figure 1 indicates that no cracks occurred even after heat treatment. The cross-section of the plating film after heat treatment was also observed. A cross-sectional SEM image is shown in Figure 5. As is clear from Figure 5, no cracks occurred, and crack-preventing voids were observed. The respective measurement methods were as follows. (XRD Measurement) The average crystallite size and crystal lattice distortion were calculated from the measured data using the Halder-Wagner method. The average crystallite size was determined specifically by the following method. A Rigaku Corporation SmartLab equipped with a Cu-Kα X-ray source and a D / teX Ultra 250 detector was used. The voltage was set to 40 kV, the current to 150 mA, and the θ-2θ method was used with a 2θ range of 20-100 degrees, a scanning step of 0.02 degrees, and a scanning rate of 4 degrees / min. (Measurement of the average diameter of crack prevention voids) The generated crack prevention voids were observed as backscattered electron images using an FE-SEM (JSM-7900F manufactured by JEOL Ltd.) at a magnification of 5000x and an acceleration voltage of 5 kV. The images were binarized using ImageJ, and the average diameter of the crack prevention voids was calculated by calculating the porosity. The calculated results were as follows. Heat treatment at 300° C. for 10 minutes: 3.07 nm Heat treatment at 300° C. for 60 minutes: 4.71 nm Heat treatment at 400° C. for 60 minutes: 12.49 nm Heat treatment at 500° C. for 60 minutes: 17.73 nm No cracks were generated in any of the heat treatments.

[0052] (Comparative Example 1C) A copper plating solution containing 0.1 mol / L of nitrogen was prepared, and a 200 μm thick film was formed by electroplating. The resulting plating film contained 0.016 at% divalent sulfur and 0.12 at% carbon. The resulting plating film also had an average crystallite size of 230 Å and a crystal lattice distortion of 0.27%. The resulting plating film was heat-treated at 250°C for 1 hour, and the presence or absence of cracks after the heat treatment was evaluated. The evaluation results are shown in Figure 2. As is clear from Figure 2, cracks were generated upon heat treatment.

[0053] Example 2C A 200 μm thick film was formed by electroplating in the same manner as in Example 1, except that a copper plating aqueous solution containing 0.2 mol / L of nitrogen was prepared. The resulting plated film contained 0.023 at% divalent sulfur. The resulting plated film was also heat-treated at 250°C for 1 hour, and the presence or absence of cracks after the heat treatment was evaluated. The evaluation results are shown in FIG. 3. From FIG. 3, it was found that no cracks were generated even after the heat treatment. The cross section of the plated film after the heat treatment was also observed. A cross-sectional SEM image is shown in FIG. 6. As is clear from FIG. 6, no cracks were generated, and crack-preventing voids were found to have been generated.

[0054] (Comparative Example 2C) A copper plating solution containing 0.16 mol / L of nitrogen was prepared, and a 200 μm thick film was formed by electroplating. The resulting plating film was heat-treated at 250° C. for 1 hour, and the presence or absence of cracks after the heat treatment was evaluated. The evaluation results are shown in FIG. 4. As is clear from FIG. 4, cracks were generated after the heat treatment.

[0055] (Example 3) Plating films were formed in the same manner as in Example 1C, except that the sulfur content in the plating film was changed from 0.020 at% to 0.100 at%, and the presence or absence of cracks after heat treatment was evaluated. As a result, no cracks were generated in any of the plating films, and crack prevention voids were generally generated.

[0056] Comparative Example 3 A plating film was formed in the same manner as in Example 1C, except that the sulfur content in the plating film was set to 0.018 at %, and the presence or absence of cracks after heat treatment was evaluated. As a result, cracks were found to have occurred.

[0057] (Test Example) The stress of the plating films obtained in the Examples and Comparative Examples was evaluated, including its relationship to cracks. The stress was measured using a strip-type electrodeposition stress tester manufactured by Fuji Kasei Co., Ltd. As a result, the Example products (divalent sulfur content 0.023 at% to 0.034 at%) had reduced stress and no cracks. On the other hand, the Comparative Example products had high stress and cracks occurred.

[0058] Specific embodiments of the inventions described above in

[31] to

[41] are explained below, but the invention is not limited to these explanations. The plating film of the present invention is a plating film containing crystal grains, and is characterized by containing 0.15 at% to 1.00 at% carbon in the plating film. Such a plating film has excellent conformability.

[0059] In the present invention, the crystal grains are preferably made of a metal, and more preferably made of a metal having a potential higher than −1.0 V versus a standard hydrogen electrode. Within this preferred range, cracks due to heat treatment can be more efficiently suppressed.

[0060] In the present invention, the crystal lattice distortion of the crystal grains is preferably 0.1% or less, since this range makes it possible to suppress cracks over a wider range.

[0061] The plating film of the present invention further contains sulfur, and the content of sulfur in the plating film is preferably in an atomic ratio of sulfur to carbon of 1 to 0.001 to 10. This preferred range can provide even better conformability.

[0062] In the present invention, the average crystallite size of the crystal grains calculated by the Halder-Wagner method is preferably 200 Å or less.Within this preferred range, better conformability can be achieved.

[0063] Although there are no particular limitations on the thickness of the plating film, it is preferable in the present invention that the thickness be 10 μm or more. Within this preferred range, cracks can be more stably suppressed.

[0064] The plating film can be produced using known plating methods. In the present invention, a plating solution containing at least a metal compound and an inorganic solvent, nitrogen, and carbon is preferably used, and the nitrogen content in the plating solution is 0.2 mol / L or more, and more preferably 0.25 mol / L or more. The means for incorporating nitrogen into the plating solution is not particularly limited as long as it does not impair the objectives of the present invention, and any known means may be used. Examples include bubbling the plating solution with nitrogen or adding a nitrogen compound to the plating solution. The means for incorporating carbon into the plating solution is not particularly limited as long as it does not impair the objectives of the present invention, and any known means may be used. By using such a plating solution to produce the plating film, the plating film can be formed more industrially advantageously. Such plating solutions are also encompassed by the present invention.

[0065] In the present invention, the metal compound preferably contains a metal having a potential higher than −1.0 V vs. a standard hydrogen electrode. This preferred range allows for the formation of a higher quality plating film. Examples of the metal include zinc, chromium, iron, tin, copper, silver, nickel, gold, platinum, palladium, rhodium, ruthenium, cobalt, gallium, germanium, cadmium, indium, antimony, osmium, iridium, bismuth, and lead, as well as alloys thereof.

[0066] In the present invention, the inorganic solvent preferably contains water. In accordance with this preferred range, known plating methods can be more suitably applied.

[0067] The plating film formed as described above can be used for various products, for example, industrial parts.

[0068] (Example 1D) A carbon-containing copper plating solution containing 0.25 mol / L of nitrogen was prepared, and a 200 μm-thick film was formed by electroplating. The resulting plating film contained 0.32 at% carbon and 0.029 at% sulfur. The resulting plating film had an average crystallite size of 102 Å and 0% crystal lattice distortion. The resulting plating film was heat-treated at 250°C for 1 hour, and the presence or absence of cracks after heat treatment was evaluated. The evaluation results are shown in Figure 1. Figure 1 indicates that no cracks occurred even after heat treatment. The cross-section of the plating film after heat treatment was also observed. A cross-sectional SEM image is shown in Figure 5. As is clear from Figure 5, no cracks occurred, and crack-preventing voids were observed. The respective measurement methods are as follows. (XRD Measurement) The average crystallite size and crystal lattice distortion were calculated from the measured data using the Halder-Wagner method. The average crystallite size was specifically determined by the following method. A Rigaku Corporation SmartLab equipped with a Cu-Kα X-ray source and a D / teX Ultra 250 detector was used. The voltage was set to 40 kV, the current to 150 mA, and measurements were made by the θ-2θ method with a 2θ range of 20-100 degrees, a scanning step of 0.02 degrees, and a scanning speed of 4 degrees / min. (Measurement of the average diameter of crack prevention voids) The generated crack prevention voids were observed using an FE-SEM (JSM-7900F manufactured by JEOL Ltd.) at a magnification of 5000 times and an acceleration voltage of 5 kV, using backscattered electron images. The images were binarized using ImageJ, and the average diameter of the crack prevention voids was calculated by calculating the porosity. The calculated results were as follows. Heat treatment at 300° C. for 10 minutes: 3.07 nm Heat treatment at 300° C. for 60 minutes: 4.71 nm Heat treatment at 400° C. for 60 minutes: 12.49 nm Heat treatment at 500° C. for 60 minutes: 17.73 nm No cracks were generated in any of the heat treatments.

[0069] (Comparative Example 1D) A copper plating solution containing 0.1 mol / L of nitrogen was prepared, and a 200 μm thick film was formed by electroplating. The resulting plating film had an average crystallite size of 230 Å and a crystal lattice distortion of 0.27%. The resulting plating film was heat-treated at 250°C for 1 hour, and the presence or absence of cracks after the heat treatment was evaluated. The evaluation results are shown in Figure 2. As is clear from Figure 2, cracks were generated after the heat treatment.

[0070] (Example 2D) A carbon-containing copper plating solution containing 0.2 mol / L of nitrogen was prepared, and a 200 μm thick film was formed by electroplating. The resulting plated film was heat-treated at 250°C for 1 hour, and the presence or absence of cracks after the heat treatment was evaluated. The evaluation results are shown in Figure 3. Figure 3 shows that no cracks were generated even after the heat treatment. The cross section of the plated film after the heat treatment was also observed. A cross-sectional SEM image is shown in Figure 6. As is clear from Figure 6, no cracks were generated, and it was found that crack-preventing voids were generated.

[0071] (Comparative Example 2D) A copper plating solution containing 0.16 mol / L of nitrogen was prepared, and a 200 μm thick film was formed by electroplating. The resulting plating film was heat-treated at 250° C. for 1 hour, and the presence or absence of cracks after the heat treatment was evaluated. The evaluation results are shown in FIG. 4. As is clear from FIG. 4, cracks were generated after the heat treatment.

[0072] (Example 2'D, Example 4D) Plating films were obtained in the same manner as in Example 1 except that the carbon content was changed.

[0073] Test Example The carbon contents of the example and comparative examples are shown in Table 2. These samples were evaluated for thermal expansion (follow-up ability) at 300°C. A good thermal expansion (follow-up ability) was marked "Good," while a poor thermal expansion (follow-up ability) was marked "Poor." The results are also shown in Table 2. The relationship between thermal expansion and temperature (follow-up ability) was evaluated using the plating films of Comparative Example 1, Example 1, Example 2, and Example 4, based on whether the amount of thermal expansion increased exponentially with temperature. The amount of thermal expansion was measured using a thermomechanical analyzer (TMA-60) manufactured by Rigaku Corporation. The plating film was cut into 5 × 20 mm pieces and used as measurement samples. The amount of thermal expansion was measured in tension mode (load 98 mN) in air at a heating rate of 10°C / min from room temperature to 310°C. The change in length along the long side of the measurement sample was recorded as the amount of thermal expansion. The results are shown in Figure 7. As can be seen from FIG. 7, the amount of thermal expansion of the comparative product increases linearly as the temperature increases, whereas the amount of thermal expansion of the product of the present invention increases exponentially as the temperature increases, demonstrating superior followability.

[0074] Specific embodiments of the inventions described above in

[42] to

[52] are described below, but the present invention is not limited to these descriptions. The plating film of the present invention is a plating film containing crystal grains, characterized in that the plating film contains 1.0 at% to 5.0 at% hydrogen. Such a plating film has excellent heat-resistant adhesion. Furthermore, the plating film of the present invention is a plating film containing crystal grains, and it is preferable that the average crystallite size of the crystal grains calculated by the Halder-Wagner method is 200 Å or less. Within this preferred range, better conformability can be obtained.

[0075] In the present invention, the crystal grains are preferably made of a metal, and more preferably made of a metal having a potential higher than −1.0 V versus a standard hydrogen electrode. Within this preferred range, cracks due to heat treatment can be more efficiently suppressed.

[0076] In the present invention, the crystal lattice distortion of the crystal grains is preferably 0.1% or less, since this range makes it possible to suppress cracks over a wider range.

[0077] Although there are no particular limitations on the thickness of the plating film, it is preferable in the present invention that the thickness be 10 μm or more. Within this preferred range, cracks can be more stably suppressed.

[0078] The plating film can be produced using known plating methods. In the present invention, a plating solution containing at least a metal compound and an inorganic solvent, nitrogen, and hydrogen is preferably used, with a nitrogen content of 0.2 mol / L or more, and more preferably 0.25 mol / L or more. The means for incorporating nitrogen into the plating solution is not particularly limited as long as it does not impair the objectives of the present invention, and any known means may be used. Examples include bubbling the plating solution with nitrogen or adding a nitrogen compound to the plating solution. The means for incorporating hydrogen into the plating solution is not particularly limited as long as it does not impair the objectives of the present invention, and any known means may be used. By using such a plating solution to produce the plating film, the plating film can be formed more industrially advantageously. Such plating solutions are also encompassed by the present invention.

[0079] In the present invention, the metal compound preferably contains a metal having a potential higher than −1.0 V vs. a standard hydrogen electrode. This preferred range allows for the formation of a higher quality plating film. Examples of the metal include zinc, chromium, iron, tin, copper, silver, nickel, gold, platinum, palladium, rhodium, ruthenium, cobalt, gallium, germanium, cadmium, indium, antimony, osmium, iridium, bismuth, and lead, as well as alloys thereof.

[0080] In the present invention, the inorganic solvent preferably contains water. In accordance with this preferred range, known plating methods can be more suitably applied.

[0081] The plating film formed as described above can be used in various products, for example, electrical and electronic components.

[0082] Example 1E: A hydrogen-containing copper plating solution containing 0.25 mol / L of nitrogen was prepared, and a 200 μm-thick film was formed by electroplating. The resulting plating film had a hydrogen content of 1.58 at % and a nitrogen content of 0.045 at %. The resulting plating film had an average crystallite size of 102 Å and a crystal lattice distortion of 0%. The resulting plating film was heat-treated and evaluated for heat-resistant adhesion, which showed good adhesion. The resulting plating film was also heat-treated at 250°C for 1 hour and evaluated for the presence or absence of cracks after heat treatment. The evaluation results are shown in Figure 1. It can be seen from Figure 1 that no cracks occurred even after heat treatment. The cross-section of the plating film after heat treatment was also observed. A cross-sectional SEM image is shown in Figure 5. As can be seen from Figure 5, no cracks occurred, and crack-preventing voids were generated. The respective measurement methods are as follows. (XRD Measurement) The average crystallite size and crystal lattice distortion were calculated from the measured data using the Halder-Wagner method. The average crystallite size was specifically determined by the following method. A Rigaku Corporation SmartLab equipped with a Cu-Kα X-ray source and a D / teX Ultra 250 detector was used. The voltage was set to 40 kV, the current to 150 mA, and measurements were performed using the θ-2θ method with a 2θ range of 20-100 degrees, a scan step of 0.02 degrees, and a scan rate of 4 degrees / min. (Measurement of the Average Diameter of Crack Prevention Voids) The generated crack prevention voids were observed as backscattered electron images using an FE-SEM (JSM-7900F manufactured by JEOL Ltd.) at a magnification of 5000x and an acceleration voltage of 5 kV. The images were binarized using ImageJ, and the average diameter of the crack prevention voids was calculated by calculating the porosity. The calculated results were as follows: Heat treatment at 300° C. for 10 minutes: 3.07 nm Heat treatment at 300° C. for 60 minutes: 4.71 nm Heat treatment at 400° C. for 60 minutes: 12.49 nm Heat treatment at 500° C. for 60 minutes: 17.73 nm No cracks were generated in any of the heat treatments.

[0083] (Comparative Example 1E) A copper plating solution containing 0.1 mol / L of nitrogen was prepared, and a 200 μm thick film was formed by electroplating. The resulting plating film had a hydrogen content of 0.72 at% and a nitrogen content of 0.018 at%. The resulting plating film also had an average crystallite size of 230 Å and a crystal lattice distortion of 0.27%. The resulting plating film was heat-treated and evaluated for heat-resistant adhesion. Blisters and other defects were observed, resulting in poor adhesion. The resulting plating film was heat-treated at 250°C for 1 hour, and the presence or absence of cracks after heat treatment was evaluated. The evaluation results are shown in Figure 2. As is clear from Figure 2, cracks were generated upon heat treatment.

[0084] Example 2E: A hydrogen-containing copper plating solution containing 0.2 mol / L of nitrogen was prepared, and a 200 μm-thick film was formed by electroplating. The resulting plating film had a hydrogen content of 1.22 at % and a nitrogen content of 0.030 at %. The resulting plating film was heat-treated and evaluated for heat-resistant adhesion, revealing good adhesion. The resulting plating film was also heat-treated at 250°C for 1 hour, and the presence or absence of cracks after the heat treatment was evaluated. The evaluation results are shown in FIG. 3. It can be seen from FIG. 3 that no cracks were generated even after the heat treatment. The cross-section of the plating film after the heat treatment was also observed. A cross-sectional SEM image is shown in FIG. 6. As is clear from FIG. 6, no cracks were generated, and crack-preventing voids were generated.

[0085] (Comparative Example 2E) A copper plating solution containing 0.16 mol / L of nitrogen was prepared, and a 200 μm thick film was formed by electroplating. The resulting plated film had a hydrogen content of 0.81 at% and a nitrogen content of 0.022 at%. Furthermore, when the resulting plated film was heat-treated and its heat-resistant adhesion was evaluated, blistering and other defects were observed, resulting in poor adhesion. The resulting plated film was heat-treated at 250°C for 1 hour, and the presence or absence of cracks after the heat treatment was evaluated. The evaluation results are shown in Figure 4. As is clear from Figure 4, cracks were generated after the heat treatment.

[0086] (Test Example) The plating films of Example 1E and Comparative Example 1E were subjected to heat treatment at 250°C for 1 hour, and the presence or absence of blistering after the heat treatment was evaluated. The evaluation results of Example 1 are shown in Figure 8, and the evaluation results of Comparative Example 1 are shown in Figure 9. The example product in Figure 8 showed no blistering, while the comparative example product in Figure 9 showed blistering, indicating that the product of the present invention has excellent heat-resistant adhesion.

[0087] Specific embodiments of the inventions described above in

[53] to

[64] are described below, but the present invention is not limited to these descriptions. The plating film of the present invention is a plating film containing crystal grains, characterized by having a crack prevention void generation portion where crack prevention voids are generated by heat treatment. Such a plating film exhibits the effect of suppressing crack generation even when heat treated. The plating film of the present invention is also a plating film containing crystal grains, characterized in that the average crystallite size of the crystal grains calculated by the Halder-Wagner method is 200 Å or less.

[0088] In the present invention, the heat treatment temperature is preferably 150° C. or higher and the heat treatment time is preferably 5 minutes or longer. Such a preferred range makes it more suitable for use in manufacturing processes involving heat treatment.

[0089] In the present invention, the crystal grains are preferably made of a metal, and more preferably made of a metal having a potential higher than −1.0 V versus a standard hydrogen electrode. Within this preferred range, cracks due to heat treatment can be more efficiently suppressed.

[0090] In the present invention, the crystal lattice distortion of the crystal grains is preferably 0.1% or less, since this range makes it possible to suppress cracks over a wider range.

[0091] Although there are no particular limitations on the thickness of the plating film, in the present invention, the thickness is preferably 30 μm or more. Within this preferred range, cracks can be more stably suppressed.

[0092] The plating film can be produced using known plating methods. In the present invention, a plating solution containing at least a metal compound and an inorganic solvent is preferably used, and the nitrogen content in the plating solution is preferably 0.2 mol / L or more, and more preferably 0.25 mol / L or more. The means for incorporating nitrogen into the plating solution is not particularly limited as long as it does not impair the objectives of the present invention, and any known means may be used. Examples include bubbling the plating solution with nitrogen or adding a nitrogen compound to the plating solution. By using such a plating solution to produce the plating film, the plating film can be formed more industrially advantageously. Such plating solutions are also encompassed by the present invention.

[0093] In the present invention, the metal compound preferably contains a metal having a potential higher than −1.0 V vs. a standard hydrogen electrode. This preferred range allows for the formation of a higher quality plating film. Examples of the metal include zinc, chromium, iron, tin, copper, silver, nickel, gold, platinum, palladium, rhodium, ruthenium, cobalt, gallium, germanium, cadmium, indium, antimony, osmium, iridium, bismuth, and lead, as well as alloys thereof.

[0094] In the present invention, the inorganic solvent preferably contains water. In accordance with this preferred range, known plating methods can be more suitably applied.

[0095] The plating film formed as described above can be used in various products, for example, electrical and electronic components.

[0096] (Example 1F) 1. Formation of Nitrogen-Containing Metal Region A copper plating solution containing 0.25 mol / L of nitrogen was prepared, and a 200 μm-thick film was formed as a nitrogen-containing metal region by electroplating. The resulting plating film contained 0.045 at% nitrogen. The nitrogen-containing metal region (film-like) of the resulting plating film had an average crystallite size of 102 Å and a crystal lattice distortion of 0%. The resulting plating film was heat-treated at 250°C for 1 hour, and the presence or absence of cracks after the heat treatment was evaluated. The evaluation results are shown in Figure 1. Figure 1 indicates that no cracks occurred even after the heat treatment. The cross-section of the plating film after the heat treatment was also observed. A cross-sectional SEM image is shown in Figure 5. As is clear from Figure 5, no cracks occurred, and crack-preventing voids were observed. The respective measurement methods were as follows. (XRD Measurement) The average crystallite size and crystal lattice distortion were calculated from the measured data using the Halder-Wagner method. The average crystallite size was determined specifically by the following method. A Rigaku Corporation SmartLab equipped with a Cu-Kα X-ray source and a D / teX Ultra 250 detector was used. The voltage was set to 40 kV, the current to 150 mA, and the θ-2θ method was used with a 2θ range of 20-100 degrees, a scanning step of 0.02 degrees, and a scanning rate of 4 degrees / min. (Measurement of the average diameter of crack prevention voids) The generated crack prevention voids were observed as backscattered electron images using an FE-SEM (JSM-7900F manufactured by JEOL Ltd.) at a magnification of 5000x and an acceleration voltage of 5 kV. The images were binarized using ImageJ, and the average diameter of the crack prevention voids was calculated by calculating the porosity. The calculated results were as follows. Heat treatment at 300° C. for 10 minutes: 3.07 nm Heat treatment at 300° C. for 60 minutes: 4.71 nm Heat treatment at 400° C. for 60 minutes: 12.49 nm Heat treatment at 500° C. for 60 minutes: 17.73 nm No cracks were generated in any of the heat treatments.

[0097] (Comparative Example 1F) A copper plating solution containing 0.1 mol / L of nitrogen was prepared, and a 200 μm thick film was formed by electroplating. The resulting plating film contained 0.018 at% nitrogen. The resulting plating film had an average crystallite size of 230 Å and a crystal lattice distortion of 0.27%. The resulting plating film was heat-treated at 250°C for 1 hour, and the presence or absence of cracks after the heat treatment was evaluated. The evaluation results are shown in Figure 2. As is clear from Figure 2, cracks were generated after the heat treatment.

[0098] (Example 2F) A copper plating solution containing 0.2 mol / L of nitrogen was prepared, and a nitrogen-containing metal region having a thickness of 200 μm was formed by electroplating. The resulting plating film contained 0.030 at% nitrogen. The resulting plating film was heat-treated at 250°C for 1 hour, and the presence or absence of cracks after the heat treatment was evaluated. The evaluation results are shown in Figure 3. Figure 3 shows that no cracks were generated even after the heat treatment. The cross section of the plating film after the heat treatment was also observed. A cross-sectional SEM image is shown in Figure 6. As is clear from Figure 6, no cracks were generated, and crack-preventing voids were generated.

[0099] (Comparative Example 2F) A copper plating solution containing 0.16 mol / L of nitrogen was prepared, and a 200 μm thick film was formed by electroplating. The resulting plating film contained 0.022 at% nitrogen. The resulting plating film was heat-treated at 250°C for 1 hour, and the presence or absence of cracks after the heat treatment was evaluated. The evaluation results are shown in Figure 4. As is clear from Figure 4, cracks were generated after the heat treatment.

[0100] (Examples 5 to 7F and Comparative Example 5F) As shown in Table 3, a nitrogen-containing metal region was laminated on a substrate in the same manner as in Example 1, and a low-nitrogen region was laminated in the same manner as in Comparative Example 1. Each of the resulting laminates was heat-treated and evaluated for the presence or absence of cracks after the heat treatment. The evaluation results of Examples 5 to 7 and Comparative Example 5 are shown in Figures 10 to 13, respectively. As is clear from the figures, no cracks occurred in the laminates of Examples 4 to 6, but cracks occurred in the laminate of Comparative Example 5. For reference, cross-sectional SEM images of Examples 5 to 7 are shown in Figures 14 to 16, respectively.

[0101]

[0102] The plating solution, method for producing a plating film, and metal member of the present invention are useful for products such as electric and electronic parts, and industrial parts that require conformability.

Claims

1. A plating solution comprising at least a metal compound and an inorganic solvent, characterized in that the nitrogen content in the plating solution is 0.2 mol / L or more.

2. The plating solution according to claim 1, wherein said metal compound contains a metal having a potential higher than -1.0 V versus a standard hydrogen electrode.

3. The plating solution according to claim 1, wherein the inorganic solvent is water.

4. A method for producing a plating film by using a plating solution, wherein the plating solution is the plating solution described in claim 1.

5. A plating film containing crystal grains, characterized in that it has a crack prevention void generation portion in which crack prevention voids are generated by heat treatment.

6. The plating film according to claim 5, wherein the crack prevention void generation portion comprises nitrogen and crystal grains.

7. The plating film according to claim 5, wherein the heat treatment temperature is 150° C. or higher and the heat treatment time is 5 minutes or longer.

8. A plating film containing crystal grains, characterized in that the average crystallite size of the crystal grains calculated by the Halder-Wagner method is 200 Å or less.

9. The plating film according to claim 8, wherein the crystal grains are made of metal.

10. The plating film according to claim 8, wherein the crystal lattice distortion of the crystal grains is 0.1% or less.

11. The plating film according to claim 8, having a film thickness of 30 μm or more.

12. A product comprising a plating film, wherein the plating film is the plating film described in claim 5 or 8.

13. A plating film containing crystal grains, characterized in that the plating film contains 0.025 at% to 0.100 at% nitrogen.

14. The plating film according to claim 13, wherein the average crystallite size of the crystal grains calculated by the Halder-Wagner method is 200 Å or less.

15. The plating film according to claim 13, wherein the crystal grains are made of metal.

16. The plating film according to claim 13, further comprising sulfur, the content of sulfur in the plating film being in the range of 0.01 to 100 in atomic ratio to nitrogen.

17. The plating film according to claim 13, wherein the crystal lattice distortion of the crystal grains is 0.1% or less.

18. The plating film according to claim 13, having a film thickness of 10 μm or more.

19. A product comprising a plating film, wherein the plating film is the plating film according to claim 13.

20. A plating solution comprising at least a metal compound and an inorganic solvent, containing nitrogen and divalent sulfur, and further characterized in that the nitrogen content in the plating solution is 0.2 mol / L or more.

21. The plating solution according to claim 20, wherein the metal compound contains a metal having a potential higher than -1.0 V versus a standard hydrogen electrode.

22. The plating solution according to claim 20, wherein the inorganic solvent is water.

23. A method for producing a plating film by using a plating solution, wherein the plating solution is the plating solution described in claim 20.

24. A plating film containing crystal grains, characterized in that the plating film contains 0.020 at% to 0.100 at% sulfur.

25. The plating film according to claim 24, wherein the average crystallite size of the crystal grains calculated by the Halder-Wagner method is 200 Å or less.

26. The plating film according to claim 24, wherein the crystal grains are made of metal.

27. The plating film according to claim 24, further comprising carbon, the carbon content in the plating film being in the range of 0.01 to 100 carbon to sulfur atomic ratio.

28. The plating film according to claim 24, wherein the crystal lattice distortion of the crystal grains is 0.1% or less.

29. The plating film according to claim 24, having a film thickness of 10 μm or more.

30. A product comprising a plating film, said plating film being the plating film of claim 24.

31. A plating solution comprising at least a metal compound and an inorganic solvent, containing nitrogen and carbon, wherein the nitrogen content in the plating solution is 0.2 mol / L or more.

32. The plating solution according to claim 31, wherein the metal compound contains a metal having a potential nobler than -1.0 V versus a standard hydrogen electrode.

33. The plating solution according to claim 31, wherein the inorganic solvent is water.

34. A method for producing a plating film by using a plating solution, wherein the plating solution is the plating solution described in claim 31.

35. A plating film containing crystal grains, characterized in that the plating film contains 0.15 at% to 1.00 at% carbon.

36. The plating film according to claim 35, wherein the average crystallite size of the crystal grains calculated by the Halder-Wagner method is 200 Å or less.

37. The plating film according to claim 35, wherein the crystal grains are made of metal.

38. The plating film according to claim 35, further comprising sulfur, the content of sulfur in the plating film being in an atomic ratio of 0.001 to 10 parts sulfur to 1 part carbon.

39. The plating film according to claim 35, wherein the crystal lattice distortion of the crystal grains is 0.1% or less.

40. The plating film according to claim 35, having a film thickness of 10 μm or more.

41. A product comprising a plating film, said plating film being the plating film of claim 35.

42. A plating solution comprising at least a metal compound and an inorganic solvent, containing nitrogen and hydrogen, wherein the nitrogen content in the plating solution is 0.2 mol / L or more.

43. The plating solution according to claim 42, wherein the metal compound contains a metal having a potential nobler than -1.0 V versus a standard hydrogen electrode.

44. The plating solution according to claim 42, wherein the inorganic solvent is water.

45. A method for producing a plating film by using a plating solution, wherein the plating solution is the plating solution described in claim 42.

46. ​​A plating film containing crystal grains, characterized in that the plating film contains 1.0 at% to 5.0 at% hydrogen.

47. The plating film according to claim 46, wherein the average crystallite size of the crystal grains calculated by the Halder-Wagner method is 200 Å or less.

48. The plating film according to claim 46, wherein the crystal grains are made of metal.

49. The plating film according to claim 46, further comprising nitrogen, the content of nitrogen in the plating film being in the range of 0.001 to 10 parts nitrogen to 100 parts hydrogen in atomic ratio.

50. The plating film according to claim 46, wherein the crystal lattice distortion of the crystal grains is 0.1% or less.

51. The plating film according to claim 46, having a film thickness of 10 μm or more.

52. A product comprising a plating film, said plating film being the plating film of claim 46.

53. A metal component containing a metal as a main component, characterized in that a nitrogen-containing metal region containing 0.025 at% or more of nitrogen is formed in 50% or more by volume of the component.

54. The metallic component according to claim 53, wherein the nitrogen-containing metallic region contains 0.1 at% or less nitrogen.

55. The metallic component according to claim 53, wherein the nitrogen-containing metallic region further contains 0.02 to 0.1 at % sulfur.

56. The metallic component according to claim 53, wherein the nitrogen-containing metallic region further contains 0.15 to 1.0 at % carbon.

57. The metallic component according to claim 53, wherein the nitrogen-containing metallic region further contains 1 to 5 at % hydrogen.

58. The metallic member according to claim 53, wherein the metal includes a metal having a potential nobler than -1.0 V versus a standard hydrogen electrode.

59. The metallic member according to claim 53, wherein the nitrogen-containing metal region contains crystal grains, and the average crystallite size of the crystal grains calculated by the Halder-Wagner method is 200 Å or less.

60. A metal member according to claim 59, wherein the crystal lattice distortion of said crystal grains is 0.1% or less.

61. The metal component according to claim 53, wherein the nitrogen-containing metal region is formed in the form of a film.

62. The metal component according to claim 61, wherein the nitrogen-containing metal region has a film thickness of 10 μm or more.

63. The metallic component of claim 53, wherein part or all of the nitrogen-containing metallic region is formed inside the metallic component.

64. An article of manufacture comprising a metal member, said metal member being the metal member of claim 53.

Images