Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/31—Coating with metals
  • C23C18/38—Coating with copper
  • C23C18/40—Coating with copper using reducing agents

Definitions

• This application relates to an electroless copper plating solution.
• the present invention relates to a reduced electroless copper plating solution used in the neutral region.
• Patent Document 1 describes "a electrolytic copper plating bath having a pH of 4 to 9 containing a water-soluble copper salt and aminoborane or a substituted derivative thereof as a reducing agent and containing no formaldehyde, and polyaminopoly as a complexing agent.
• a electrolyzed copper plating bath characterized by containing a phosphonic acid, an anionic surfactant, an antimony compound, and a nitrogen-containing aromatic compound.
• the electroless copper plating bath disclosed in Patent Document 1 has the following problems.
• the first problem is that the electroless copper plating bath disclosed in Patent Document 1 tends to deposit copper on the bottom of the tank, a stirring jig, etc. when left in the plating tank for a long time after use, and is used as a plating solution. It tends to lack solution stability.
• the second problem is that the electroless copper plating film formed by using the electroless copper plating bath disclosed in Patent Document 1 tends to have a non-uniform appearance.
• the third problem is that when plating is performed on an aluminum material using the electroless copper plating bath disclosed in Patent Document 1, even if the aluminum itself is not damaged, the copper plating film swells and pits are generated. Also tends to occur easily.
• the electroless copper plating solution according to the present application is a reduction type electroless copper plating solution used in the neutral region, and is a copper salt as a copper ion supply source, a complexing agent for chelating copper ions, and reduction. It contains an aromatic compound containing an agent, a surfactant and nitrogen, and also contains a tellurium compound as a precipitation stabilizer, and has a solution pH of 6 to 9.
• the tellurium compound as a precipitation stabilizer is preferably used as tellurium in a concentration range of 0.1 mg / L to 100 mg / L.
• the complexing agent for chelating copper ions is a phosphonic acid-based chelating agent, which is 0.1 to 0.1 to the number of moles of copper in the electroless copper plating solution. It is preferable to use it in a concentration range of 10 times.
• the reducing agent is preferably amine borane or a derivative thereof.
• an anionic surfactant in a concentration range of 0.01 mg / L to 1500 mg / L as the surfactant.
• the nitrogen-containing aromatic compound is preferably used in a concentration range of 0.01 mg / L to 1000 mg / L.
• the electroless copper plating solution according to the present application contains a tellurium compound as a precipitation stabilizer of the electroless copper plating solution, so that it is used in a neutral region without containing formaldehyde, but is a solution as a plating solution. Stability is dramatically improved. As a result, there is little fluctuation in the composition of the plating solution during the plating operation, and even if there is some fluctuation in the composition, a stable copper plating film can be formed, and the film thickness uniformity and uniform appearance quality of the copper plating film can be obtained. You can now do it.
• the electroless copper plating solution in the neutral region according to the present application, when the aluminum material is plated, the aluminum itself is not damaged, and plating defects such as swelling and pits in the plating film are efficiently removed. It can be resolved.
• the electroless copper plating solution according to the present application is a reduction type electroless copper plating solution used in the neutral region.
• the electroless copper plating solution is characterized by containing a tellurium compound as a constituent component as a precipitation stabilizer and having a solution pH of 6 to 9.
• the solution pH of this electroless copper plating solution will be described, and then each component will be described.
• the solution pH is preferably 6.0 to 9.0.
• the pH of the solution is less than 6.0, it is in an acidic region, so that the effects of the constituent components such as the reducing agent described below are likely to decrease, and it becomes difficult to extend the life of the electroless copper plating solution, which is not preferable.
• the pH of the solution is higher than 9.0, it becomes an alkaline region, and there is a high possibility that the surface of the aluminum material, the ceramic material, etc., which is the object to be plated, is damaged, which is not preferable.
• the pH is 6.5 to 8.5, which is closer to neutral, damage to the object to be plated can be prevented more reliably.
• the pH adjuster may be hydrochloric acid or sulfuric acid to adjust to the acid side, sodium hydroxide to adjust to the alkaline side, or the like. Potassium hydroxide or the like may be used.
• Tellurium compound as a precipitation stabilizer is used in the electroless copper plating solution according to the present application.
• the tellurium compound include any one or more of telluric acid and its salt, tellurous acid and its salt, tellurium dioxide, tellurium trioxide, tellurium chloride, and dimethyl tellurium.
• the tellurium compound as the precipitation stabilizer is preferably contained in the electroless copper plating solution as tellurium in a concentration range of 0.1 mg / L to 100 mg / L.
• the content of the tellurium compound is less than 0.1 mg / L as the tellurium concentration, the solution stability of the electroless copper plating solution cannot be improved, the life of the plating solution cannot be extended, and the composition. Since the characteristics of the plating solution fluctuate due to fluctuations, it is difficult to use it as a non-electrolytic copper plating solution for a long time, which is not preferable.
• the content of the tellurium compound exceeds 100 mg / L in terms of the tellurium concentration, a phenomenon is observed in which the precipitation of copper is remarkably reduced, which makes it difficult to form a rapid copper plating film, which is not preferable. Therefore, from the viewpoint of ensuring the stability of the copper precipitation rate, the content of the tellurium compound is more preferably in the concentration range of 0.3 mg / L to 70 mg / L as the tellurium. In order to minimize the effect of adding the tellurium compound and the variation in the formation rate of the copper plating film, it is best to include the tellurium compound in a concentration range of 0.5 mg / L to 50 mg / L as tellurium. preferable.
• Copper ion supply source In the electroless copper plating solution according to the present application, a copper salt as a copper ion supply source is used.
• the copper salt may be, for example, one or more of water-soluble copper salts represented by copper sulfate, copper nitrate, copper chloride, copper acetate, copper citrate, copper tartrate, copper gluconate and the like, and hydrates thereof. Can be mentioned.
• the copper salt of the present application can be used in combination of two or more kinds at the same time, and as long as the amount of copper ions is within the following range, there is no particular limitation on the mixing ratio of the two or more kinds of copper salts. .. Considering conditions such as raw material cost and wastewater load, copper sulfate (copper sulfate / pentahydrate) or a combination of copper sulfate and copper hydrochloride is preferably used in the widest range.
• the copper salt content is preferably in the concentration range of 0.01 mol / L to 1 mol / L as copper.
• the copper salt content of the electroless copper plating solution according to the present application is less than 0.01 mol / L in terms of copper concentration, the copper precipitation rate is significantly reduced, the time required for operation becomes long, and the industry It is not preferable because the required productivity cannot be obtained.
• the content of this copper salt exceeds 1 mol / L in terms of the concentration of copper, the precipitation rate of copper does not improve, but rather the appearance of the formed copper plating film tends to be poor, which is not preferable. Therefore, from the viewpoint of ensuring the appearance quality of the copper plating film to be formed, the content of the copper salt is preferably in the concentration range of 0.02 mol / L to 0.5 mol / L in terms of the concentration of copper. ..
• the electroless copper plating solution according to the present application is used in the neutral region, and it is preferable to use a phosphonic acid-based chelating agent as the complexing agent. This is because this phosphonic acid-based chelating agent easily forms a complex of copper ions in the neutral region.
• these phosphonic acid-based chelating agents are 1-hydroxyethane-1,1-diphosphonic acid, N, N, N', N'-ethylenediaminetetrakis (methylenephosphonic acid), nitrilotris (methylenephosphonic acid), and diphosphoric acid.
• ethylenediaminepenta methylenephosphonic acid
• diethylenetriaminepenta methylenephosphonic acid
• glycine-N glycine-N, N-bis (methylenephosphonic acid) and salts thereof. It is also possible to use one or more of the above at the same time.
• the amount added is determined by the copper content in the electroless copper plating solution.
• the phosphonic acid-based chelating agent as the complexing agent is used in a concentration range of 0.1 to 10 times the number of moles of copper in the electroless copper plating solution. Is preferable. If the concentration of the phosphonic acid-based chelating agent is less than 0.1 times the number of moles of the copper, the copper ions cannot be sufficiently complexed, and the solution stability as an electrolytically-free copper plating solution cannot be ensured. Therefore, it is not preferable.
• the concentration of the phosphonic acid-based chelating agent exceeds 10 times the number of moles of the copper, the amount exceeds the amount required for complexing the copper ions, which wastes resources and at the same time improves the appearance quality of the copper plating film. It is not preferable because it causes a decrease.
• Reducing agent Various kinds of reducing agents for copper ions can be used. However, in the case of the electroless copper plating solution according to the present application, since it is used in the neutral region, the solution stability is ensured by using amineboran or a derivative thereof as a reducing agent that can be used in the neutral region. It is preferable for this. More specifically, any one or more of dimethylamine borane, diethylamine borane, tert-butylamine borane, triethylamine borane, trimethylamine borane and the like can be used. The concentration of this reducing agent is not particularly limited, but it is appropriate to set it in the range of 0.01 mol / L to 0.5 mol / L.
• the concentration of the reducing agent is less than 0.01 mol / L, the precipitation rate of copper becomes slow, which is not preferable.
• the concentration of the reducing agent exceeds 0.5 mol / L, the precipitation rate of copper does not increase, which is not preferable because it is a mere waste of resources.
• Surfactant In the electroless copper plating solution according to the present application, it is preferable to use a surfactant for the purpose of improving the solution stability, the film thickness uniformity of the plating film to be formed, and the appearance quality. In particular, in the case of an electroless copper plating solution used in the neutral region, it is preferable to use an anionic surfactant.
• anionic surfactant all those referred to as “anionic surfactant” and “anionic surfactant” in the market can be used.
• alkylcarboxylic acid-based surfactants such as sodium salt of ⁇ -naphthalenesulfonic acid formarin condensate, polyoxyethylene lauryl ether sodium sulfate, polyoxyethylene alkyl ether sulfate triethanolamine and the like.
• Any one or more of polyoxyalkylene ether sulfate, sodium dodecyl sulfate and the like can be mentioned, and no particular limitation is required.
• the concentration of this surfactant is not particularly limited, but it is appropriate to set it in the range of 0.01 mg / L to 1500 mg / L.
• concentration of the surfactant is less than 0.01 mg / L, the solution stability of the electroless copper plating solution does not improve, it becomes difficult to extend the life of the plating solution, and the appearance quality of the obtained copper plating film deteriorates. It tends to be unfavorable.
• concentration of the surfactant exceeds 1500 mg / L, there is no particular problem, but the solution stability is not further improved and the appearance quality is not improved. Rather, the bath management during the plating operation is performed. It is not preferable because it is complicated.
• the nitrogen-containing aromatic compound (so-called nitrogen-containing heterocyclic aromatic compound) is the copper in the electroless copper plating. Used to stabilize precipitation.
• the nitrogen-containing aromatic compound include imidazole or a substituted derivative thereof, pyrazole or a substituted derivative thereof, oxazole or a substituted derivative thereof, thiazole or a substituted derivative thereof, pyrazine or a substituted derivative thereof, pyridazine or a substituted derivative thereof, triazine or a substituted derivative thereof.
• Substituted derivative benzothiazole or its substituted derivative, pyridine, 2,2'-dipyridyl, 4,4'-dipyridyl, nicotinic acid, nicotine amide, picolins, lutidines and other pyridines or their substituted derivatives, quinoline, hydroxyquinoline.
• Kinolins or substituted derivatives thereof aclysine, 3,6-dimethylaminoaclydin, proflavin, aclydic acid, quinoline-1,2-dicarboxylic acid and other quinolins or substituted derivatives thereof, pyrimidine, uracil, uridine, timine, etc.
• Pyrimidins or their substituted derivatives such as 2-thiouracil, 6-methyl-2-thiouracil, 6-propyl-2-thiouracil, phenanthrolins such as 1,10-phenanthroline, neocuproin, vasofenantroline or their substituted derivatives, purines, amino Any one or more of purines such as purines, adenin, adenosine, guanine, hydrantin, xanthin, hypoxanthin, caffeine, theophylline, theobromine, aminophyllin and the like or substitution derivatives thereof can be mentioned.
• the concentration of the nitrogen-containing aromatic compound contained in the electroless copper plating solution according to the present application is preferably 0.01 mg / L to 1000 mg / L.
• concentration of the aromatic compound containing nitrogen is less than 0.01 mg / L, the effect as a copper precipitation stabilizer cannot be exhibited and the appearance of the formed copper plating film is impaired, which is not preferable.
• concentration of the nitrogen-containing aromatic compound exceeds 1000 mg / L, the solution stability of the electroless copper plating solution becomes excessive, the copper precipitation rate decreases, and plating is not deposited, which is not preferable. ..
• Electroless copper plating method As for the electroless copper plating method, the electroless plating method and conditions known conventionally may be applied by using the above-mentioned electroless copper plating solution. Therefore, it is not necessary to explain the electroless copper plating method in detail here, and the electroless plating method and conditions are described in the examples.
• Example 1 a copper salt as a copper ion supply source, a complexing agent for chelating copper ions, a reducing agent, a surfactant, and an aromatic compound containing nitrogen are contained, and as a precipitation stabilizer. Confirmed the quality of the solution stability as a plating solution after performing electroless copper plating with an electroless copper plating solution containing the tellurium compound of No. 7 and having a solution pH of 7.7 and a liquid temperature of 60 ° C. bottom. Here, the evaluation of the solution stability as a plating solution is performed after the electroless copper plating solution is heated and the plating treatment is performed while keeping the liquid temperature constant, and then the electroless copper plating solution is left for 12 hours.
• Example 1 a substrate with an aluminum circuit (hereinafter, simply referred to as a substrate) to be plated is pretreated under the conditions shown in Table 1 below (in order from the top of the table), and then no substrate is used. Electroless copper plating was performed by immersing in an electrolytic copper plating solution for 120 minutes to form a copper plating film on the surface of an aluminum circuit pattern.
• Example 1 an electroless copper plating solution having the composition shown below was prepared.
• Complexing agent ethylenediamine tetra (methylenephosphonic acid)
• Reducing agent dimethylamine borane
• Surfactant sodium dodecyl sulfate
• Precipitation stabilizer sodium tellurate
• Example 1 the precipitation rate of the electroless copper plating film, the appearance of the plating, and the out-of-pattern precipitation of the plating film after forming the copper plating film on the surface of the aluminum circuit pattern (hereinafter, also simply referred to as a pattern) on the substrate. It was confirmed whether or not the pattern was present and whether or not the pattern was not deposited. The above-mentioned "presence or absence of unprecipitated pattern” indicates whether or not an unprecipitated portion of the copper plating film is generated on the surface of the aluminum circuit pattern.
• the precipitation rate of the electroless copper plating film was determined by measurement with a fluorescent X-ray film thickness meter. The plating appearance was visually evaluated (a uniform plating appearance is marked with " ⁇ ", and an uneven plating appearance is marked with "x”). The results of these confirmations are also shown in Table 3.
• Example 2 the solution stability of the plating solution, the precipitation rate of the electroless copper plating film, the presence or absence of out-of-pattern precipitation of the plating film, and the presence or absence of non-precipitation of the pattern were confirmed in the same manner as in Example 1. The results of this confirmation are shown in Table 3.
• Example 2 electroless under the same conditions as in Example 1 except that the content of sodium terlate, which is a precipitation stabilizer in the composition of the electroless copper plating solution, was changed to "2 mg / L" in terms of the concentration of tellurium. Copper plating was performed. Therefore, the description of the conditions for performing electroless copper plating in Example 2 will be omitted.
• Example 3 the solution stability of the plating solution, the precipitation rate of the electroless copper plating film, the presence or absence of out-of-pattern precipitation of the plating film, and the presence or absence of non-precipitation of the pattern were confirmed in the same manner as in Example 1. The results of this confirmation are shown in Table 3.
• Example 3 the content of sodium terlate, which is a precipitation stabilizer in the composition of the electroless copper plating solution, was changed to "10 mg / L" in terms of the concentration of tellurium, but the conditions were the same as in Example 1. Copper plating was performed. Therefore, the description of the conditions for performing electroless copper plating in Example 3 will be omitted.
• Example 4 the solution stability of the plating solution, the precipitation rate of the electroless copper plating film, the presence or absence of out-of-pattern precipitation of the plating film, and the presence or absence of non-precipitation of the pattern were confirmed in the same manner as in Example 1. The results of this confirmation are shown in Table 3.
• Example 4 the content of sodium terlate, which is a precipitation stabilizer in the composition of the electroless copper plating solution, was changed to "20 mg / L" in terms of the concentration of tellurium, but the conditions were the same as in Example 1. Copper plating was performed. Therefore, the description of the conditions for performing electroless copper plating in Example 4 will be omitted.
• Example 5 the solution stability of the plating solution, the precipitation rate of the electroless copper plating film, the presence or absence of out-of-pattern precipitation of the plating film, and the presence or absence of non-precipitation of the pattern were confirmed in the same manner as in Example 1. The results of this confirmation are shown in Table 3.
• Example 5 the content of sodium terlate, which is a precipitation stabilizer in the composition of the electroless copper plating solution, was changed to "50 mg / L" in terms of the concentration of tellurium, but the conditions were the same as in Example 1. Copper plating was performed. Therefore, the description of the conditions for performing electroless copper plating in Example 5 will be omitted.
• Example 6 the solution stability of the plating solution, the precipitation rate of the electroless copper plating film, the presence or absence of out-of-pattern precipitation of the plating film, and the presence or absence of non-precipitation of the pattern were confirmed in the same manner as in Example 1. The results of this confirmation are shown in Table 3.
• Example 6 the content of sodium terlate, which is a precipitation stabilizer in the composition of the electroless copper plating solution, was changed to "5 mg / L" in terms of the concentration of tellurium, and the solution pH was changed to "6.5". Electrolytic copper plating was performed under the same conditions as in Example 1 except for the change. Therefore, the description of the conditions for performing electroless copper plating in Example 6 will be omitted.
• Example 7 the solution stability of the plating solution, the precipitation rate of the electroless copper plating film, the presence or absence of out-of-pattern precipitation of the plating film, and the presence or absence of non-precipitation of the pattern were confirmed in the same manner as in Example 1. The results of this confirmation are shown in Table 3.
• Example 7 the content of sodium terlate, which is a precipitation stabilizer in the composition of the electroless copper plating solution, was changed to "5 mg / L" in terms of the concentration of tellurium, and the solution pH was changed to "7.0". Electrolytic copper plating was performed under the same conditions as in Example 1 except for the change. Therefore, the description of the conditions for performing electroless copper plating in Example 7 will be omitted.
• Example 8 the solution stability of the plating solution, the precipitation rate of the electroless copper plating film, the presence or absence of out-of-pattern precipitation of the plating film, and the presence or absence of non-precipitation of the pattern were confirmed in the same manner as in Example 1. The results of this confirmation are shown in Table 3.
• Electrolytic copper plating was performed under the same conditions as in Example 1 except for the change. Therefore, the description of the conditions for performing electroless copper plating in Example 8 will be omitted.
• Example 9 the solution stability of the plating solution, the precipitation rate of the electroless copper plating film, the presence or absence of out-of-pattern precipitation of the plating film, and the presence or absence of non-precipitation of the pattern were confirmed in the same manner as in Example 1. The results of this confirmation are shown in Table 3.
• Example 9 the content of sodium terlate, which is a precipitation stabilizer in the composition of the electroless copper plating solution, was changed to "5 mg / L" in terms of the concentration of tellurium, and the solution pH was changed to "8.5".
• Electrolytic copper plating was performed under the same conditions as in Example 1 except for the change. Therefore, the description of the conditions for performing electroless copper plating in Example 9 will be omitted.
• Comparative Example 1 the solution stability of the plating solution, the precipitation rate of the electroless copper plating film, the presence or absence of out-of-pattern precipitation of the plating film, and the presence or absence of non-precipitation of the pattern were confirmed in the same manner as in Example 1. The results of this confirmation are shown in Table 3.
• Comparative Example 1 in order to make a comparison with Examples 1 to 9, "antimon oxide” was used instead of sodium terlate as a precipitation stabilizer in the electrolytic copper plating solution composition, and the content thereof was set as antimon.
• Electrolytic copper plating was performed under the same conditions as in Example 1 except that the concentration of the reducing agent was 4 mg / L and the concentration of the reducing agent was 0.14 mol / L. Therefore, the description of the conditions for performing electroless copper plating in Comparative Example 1 will be omitted.
• Comparative Example 2 the solution stability of the plating solution, the precipitation rate of the electroless copper plating film, the presence or absence of out-of-pattern precipitation of the plating film, and the presence or absence of non-precipitation of the pattern were confirmed in the same manner as in Example 1. The results of this confirmation are shown in Table 3.
• Comparative Example 2 in order to make a comparison with Examples 1 to 9, the content of sodium tellurium, which is a precipitation stabilizer in the electrolyzed copper plating solution composition, was set to "0 mg / L (that is, that is, the concentration as tellurium). Electrolytic copper plating was performed under the same conditions as in Example 1 except that the mixture was changed to "sodium terlate-free)". Therefore, the description of the conditions for performing electroless copper plating in Comparative Example 2 will be omitted.
• Comparative Example 3 the solution stability of the plating solution, the precipitation rate of the electroless copper plating film, the presence or absence of out-of-pattern precipitation of the plating film, and the presence or absence of non-precipitation of the pattern were confirmed in the same manner as in Example 1. The results of this confirmation are shown in Table 3.
• Comparative Example 3 in order to make a comparison with Examples 1 to 9, the content of sodium terlate, which is a precipitation stabilizer in the electroless copper plating solution composition, was changed to "200 mg / L" in terms of the concentration as tellurium. Electrolytic copper plating was performed under the same conditions as in Example 1. Therefore, the description of the conditions for performing electroless copper plating in Comparative Example 3 will be omitted.
• Table 2 shows the compositions of the electroless copper plating solutions used in Examples and Comparative Examples.
• Table 3 shows the confirmation results in the above-mentioned tests conducted as Examples and Comparative Examples.
• Comparative Example 2 protrusion from the pattern was confirmed.
• the concentration of tellurium in the precipitation stabilizer exceeds 100 mg / L as in Comparative Example 3, the plating hardly precipitates, and the plating film cannot be formed on the surface of the aluminum circuit pattern on the substrate. rice field.
• the conditions of the present application are "a copper salt as a copper ion supply source, a complexing agent for chelating copper ions, a reducing agent, a surfactant, and an aromatic compound containing nitrogen.
• the solution contains a tellurium compound as a precipitation stabilizer and the solution pH is 6 to 9, it is a reduced electrolytic copper plating solution used in the neutral region without containing formaldehyde. Nevertheless, it was found that the composition of the plating solution was less likely to fluctuate during the plating operation, and a stable copper plating film could be formed.
• the electroless copper plating solution according to this application is used in the neutral region and does not damage the object to be plated. Therefore, it is an electroless copper plating solution that can be used for an object to be plated that is easily damaged by an electroless copper plating solution such as an aluminum material or a ceramic material. Moreover, since the electroless copper plating solution has a long life and excellent solution stability, the running cost of the electroless copper plating can be reduced.

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• 2021
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