CN109457238B - High-speed stable chemical copper plating solution and preparation method thereof - Google Patents
High-speed stable chemical copper plating solution and preparation method thereof Download PDFInfo
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- CN109457238B CN109457238B CN201811592325.8A CN201811592325A CN109457238B CN 109457238 B CN109457238 B CN 109457238B CN 201811592325 A CN201811592325 A CN 201811592325A CN 109457238 B CN109457238 B CN 109457238B
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- 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
- C23C18/405—Formaldehyde
Abstract
The invention discloses a high-speed stable chemical copper plating solution and a preparation method thereof, wherein the high-speed stable chemical copper plating solution comprises the following components in volume concentration: 8-25 g/L of copper sulfate pentahydrate, 15-40 g/L of potassium sodium tartrate, 5-20 ml/L of formaldehyde, 5-20 g/L of sodium hydroxide, 10-500 mg/L of stabilizer and the balance of water. The high-speed stable electroless copper plating solution further comprises a combined additive, wherein the combined additive is composed of a thiourea derivative and a hydroxyalkyl-containing aminocarboxylic compound. Dissolving copper sulfate pentahydrate with water, fully stirring until the solution is clear, sequentially adding sodium potassium tartrate, a stabilizer, a combined additive, sodium hydroxide and formaldehyde, fully stirring until the solution is clear, and metering the volume with water to obtain the high-speed stable chemical copper plating solution. The high-speed stable electroless copper plating solution has the deposition speed of more than 10 mu m/h, is stable, and can ensure that the copper plating layer is smooth and uniform, thereby meeting the requirements of functional electroless copper plating.
Description
Technical Field
The invention relates to the technical field of non-metallic surface chemical plating, in particular to a high-speed stable chemical copper plating solution and a preparation method thereof.
Background
Chemical plating is also called autocatalytic plating, and refers to a surface treatment technology in which metal ions and a reducing agent in a solution undergo an autocatalytic redox reaction on the surface of a substrate with catalytic activity under the condition of no external current, and a metal or alloy coating is formed on the surface of the substrate through chemical deposition. Electroless copper plating is one of the important electroless plating techniques, and an electroless copper plating layer has been widely used in various industrial and civil fields such as through-hole conduction of printed wiring boards, electronic packaging connection, electromagnetic wave shielding, decorative plating, and the like, because of its good ductility, thermal conductivity, and electrical conductivity.
The chemical copper plating solution mainly comprises copper salt, a complexing agent, a reducing agent, a stabilizing agent, a pH value regulator and other additives. At present, most of commercial chemical copper plating solutions adopt formaldehyde (formula HCHO) as a reducing agent, in the chemical copper plating solution, HCHO reacts with hydroxide ions to generate hydrogen, water and carboxylic acid ions, and divalent copper ions are reduced into a metal copper simple substance to be deposited on the surface of a substrate with catalytic activity. The general chemical reaction formula of the electroless copper plating is Cu2++2HCHO+4OH-→Cu+H2+2H2O+2HCOO-. The reaction formula only shows the relationship between reactants and final reaction products, the actual reaction process is much more complicated, a plurality of side reactions exist, and unstable cuprous ions are generatedThe stabilizer is added because the electroless plating solution may be decomposed and the electroless copper plating layer is rough.
According to the chemical copper plating reaction mechanism, formaldehyde is used as a reducing agent and needs to be carried out under an alkaline condition, a pH regulator is generally used for regulating the pH value of the plating solution to be 11-12, and under the condition, in order to prevent copper ions from forming copper hydroxide precipitates in the alkaline plating solution, a complexing agent needs to be added to form a complex with the copper ions so as to ensure the normal operation of the reaction. At present, Ethylene Diamine Tetraacetic Acid (EDTA) is a commonly used complexing agent for the chemical copper plating solution, but the EDTA influences the neutralization and precipitation of heavy metals, and increases the difficulty for treating the chemical copper plating waste solution. With the increasing environmental protection requirements of manufacturing industry, the chemical copper plating solution tends to adopt tartrate as a complexing agent of copper ions. Tartrate is also called rochelle salt, is easy to treat waste liquid, but when the tartrate is used as a complexing agent of chemical copper plating solution, the tartrate is generally low in deposition speed and is only suitable for a low-speed chemical copper plating process. For example, the chemical plating solution using tartrate as a complexing agent disclosed in the Chinese patent publication No. CN104372315A has a deposition rate of about 1.2-2.5 μm/h and a plating thickness of about 0.5 μm, and is suitable for chemical plating of thin copper. For functional chemical copper plating, the deposition speed of the chemical copper plating solution at least reaches 4-6 μm/h, and the thickness of the final plating layer can be ensured to meet the functional requirements of the material. The high-speed chemical copper plating solution disclosed in the Chinese patent with the publication number of CN106086836 can ensure high copper plating rate, the deposition speed reaches 5-10 mu m/h, but a mixed complexing agent is adopted, and complexing agents such as EDTA and the like are added besides tartrate, so that the application of the mixed complexing agent increases the difficulty for treating chemical copper waste liquid.
Therefore, how to increase the deposition rate of the electroless copper plating solution using tartrate as a complexing agent to meet the requirement of a high-speed electroless copper plating process becomes a problem to be solved urgently in the industry. For electroless copper plating, the higher the plating rate, the more difficult the stability of the plating solution is to control; the better the stability of the plating solution, the higher the plating rate is. Therefore, the relation between the stability of the chemical copper plating solution (especially the chemical copper plating solution taking tartrate as a complexing agent) and the plating speed is well coordinated, and the high-speed and stable chemical plating solution is obtained, which is always the research direction in the chemical copper plating field.
Disclosure of Invention
The invention aims to provide a high-speed stable chemical copper plating solution and a preparation method thereof aiming at the defects of the prior art, wherein the deposition speed is more than 10 mu m/h, the plating solution is stable, the copper plating layer is smooth and uniform, and the requirements of functional chemical copper plating are met.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect of the present invention, there is provided a high-speed stable electroless copper plating solution, comprising the following components by volume:
8 g/L-25 g/L of copper sulfate pentahydrate,
15-40 g/L of potassium sodium tartrate,
5-20 ml/L of formaldehyde,
5-20 g/L of sodium hydroxide,
10-500 mg/L of a stabilizer,
the balance of water.
Further, the mass concentration of the formaldehyde is 37%.
Further, the stabilizing agent is a derivative of hydantoin, the derivative of hydantoin is non-toxic and has good biodegradability, the stabilizing effect of the chemical plating solution is poor when the concentration of the derivative of hydantoin is less than 10mg/L, and the deposition rate of the chemical plating solution is reduced when the concentration of the derivative of hydantoin is more than 500 mg/L.
Preferably, the stabilizer is one of hydantoin, 5-dimethylhydantoin and 5, 5-diethylhydantoin.
Further, the high-speed stable electroless copper plating solution further comprises a combined additive, wherein the combined additive is composed of a thiourea derivative and a hydroxyalkyl-containing aminocarboxylic compound. The combined additive can be used in chemical plating solution taking potassium sodium tartrate as a complexing agent, so that the deposition rate is improved, and the plating solution is stabilized.
Preferably, the thiourea derivative is one of thiosemicarbazide and thioallylamine, and the hydroxyalkyl-containing aminocarboxylic compound is one of N-hydroxyethylethylenediaminetriacetic acid (HEDTA) and tetrahydroxypropylethylenediamine (EDTP).
Preferably, the volume concentration of the thiourea derivative in the high-speed stable electroless copper plating solution is 0.1-50 mg/L, and the volume concentration of the hydroxyalkyl-containing aminocarboxylic compound in the high-speed stable electroless copper plating solution is 0.1-5 g/L.
In a second aspect of the present invention, there is provided a method for preparing the above-mentioned high-speed and stable electroless copper plating solution, comprising the steps of: dissolving copper sulfate pentahydrate with water, fully stirring until the solution is clear, sequentially adding sodium potassium tartrate, a stabilizer, a combined additive, sodium hydroxide and formaldehyde, fully stirring until the solution is clear, and metering the volume with water to obtain the high-speed stable chemical copper plating solution.
Compared with the prior art, the invention has the following beneficial effects: the high-speed stable electroless copper plating solution has the deposition speed of more than 10 mu m/h, is stable, and can ensure that the copper plating layer is smooth and uniform, thereby meeting the requirements of functional electroless copper plating.
Detailed Description
The present invention will be further described with reference to the following examples, but the scope of the present invention is not limited to these examples. Other variations and modifications which may occur to those skilled in the art without departing from the spirit and scope of the invention are intended to be included within the scope of the invention.
The deposition rate of the high-speed stable electroless copper plating solution prepared in the following examples was measured as follows: (1) taking a copper-free full-epoxy resin substrate with the size of 69mm multiplied by 69mm, putting the substrate into an oven, and baking the substrate for 1 hour at the temperature of 120 ℃; then putting the mixture into a dryer for cooling for 10-15 minutes; (2) taking out and weighing to be accurate to 0.0001G to obtain an initial weight G1; (3) cleaning, roughening and activating the surface of the sample plate; (4) the electroless copper plating solution prepared in the example was deposited in a 1 liter beaker for 1 hour, the deposition temperature was controlled at 40 ℃; (5) taking out the sample plate, putting the sample plate into an oven, baking the sample plate for 1 hour at the temperature of 120 ℃, taking out the sample plate, and putting the sample plate into a dryer for cooling for 10 to 15 minutes; (6) taking out and weighing the copper alloy to be accurate to 0.0001 gram to obtain the weight G2 after electroless copper plating; (7) calculating the formula: the electroless plating solution deposition rate (μm/h) was (G2-G1)/0.08. And observing the clarification condition of the electroless copper plating solution in the reaction process, and observing the surface condition of the electroless copper plating solution after the reaction is finished.
Example 1
A high-speed stable electroless copper plating solution comprises the following components: 15g/L of copper sulfate pentahydrate, 25g/L of potassium sodium tartrate, 20ml/L of formaldehyde (37%), 10g/L of sodium hydroxide, 30mg/L of hydantoin, 1.5mg/L of thiosemicarbazide, 0.75g/L of tetrahydroxypropylethylenediamine and the balance of water.
The preparation method of the high-speed stable electroless copper plating solution comprises the following steps: dissolving copper sulfate pentahydrate with water, fully stirring until the solution is clear, sequentially adding potassium sodium tartrate, hydantoin, thiosemicarbazide, tetrahydroxypropylethylenediamine, sodium hydroxide and formaldehyde, fully stirring until the solution is clear, and finally adding water to a constant volume of 1 liter.
The deposition speed measured by the high-speed stable electroless copper plating solution is 12 mu m/h, the working solution is stable and does not decompose in the chemical deposition process, no copper particles are generated on the inner wall of the beaker, and the electroless copper plating layer is flat and uniform and has no roughness defect.
Example 2
A high-speed stable electroless copper plating solution comprises the following components: 25g/L of copper sulfate pentahydrate, 40g/L of sodium potassium tartrate, 10ml/L of formaldehyde (37%), 15g/L of sodium hydroxide, 60mg/L of 5, 5-dimethylhydantoin, 5mg/L, N-hydroxyethylethylenediamine triacetic acid, and the balance of water.
The preparation method of the high-speed stable electroless copper plating solution comprises the following steps: firstly, copper sulfate pentahydrate and water are mutually dissolved, the mixture is fully stirred until the solution is clear, potassium sodium tartrate, 5,5 dimethyl hydantoin, allylthiourea, N-hydroxyethyl ethylene diamine triacetic acid, sodium hydroxide and formaldehyde are sequentially added, the mixture is fully stirred until the solution is clear, and finally, the water is used for fixing the volume to 1 liter.
The deposition speed measured by the high-speed stable electroless copper plating solution is 15 mu m/h, the working solution is stable and does not decompose in the chemical deposition process, no copper particles are generated on the inner wall of the beaker, and the electroless copper plating layer is flat and uniform and has no roughness defect.
Example 3
A high-speed stable electroless copper plating solution comprises the following components: 20g/L of copper sulfate pentahydrate, 30g/L of sodium potassium tartrate, 5ml/L of formaldehyde (37%), 10g/L of sodium hydroxide, 40mg/L of 5, 5-diethylhydantoin, 10mg/L, N-hydroxyethylethylenediamine triacetic acid, and the balance of water.
The preparation method of the high-speed stable electroless copper plating solution comprises the following steps: firstly, copper sulfate pentahydrate and water are mutually dissolved, the mixture is fully stirred until the solution is clear, potassium sodium tartrate, 5,5 diethyl hydantoin, thiosemicarbazide, N-hydroxyethyl ethylenediamine triacetic acid, sodium hydroxide and formaldehyde are sequentially added, the mixture is fully stirred until the solution is clear, and finally, the water is used for fixing the volume to 1 liter.
The deposition speed measured by the high-speed stable electroless copper plating solution is 18 mu m/h, the working solution is stable and does not decompose in the chemical deposition process, no copper particles are generated on the inner wall of the beaker, and the electroless copper plating layer is flat and uniform and has no roughness defect.
Example 4
A high-speed stable electroless copper plating solution comprises the following components: 25g/L of copper sulfate pentahydrate, 30g/L of sodium potassium tartrate, 15ml/L of formaldehyde (37%), 5g/L of sodium hydroxide, 50mg/L of 5, 5-diethylhydantoin, 20mg/L of allylthiourea, 4g/L of tetrahydroxypropylethylenediamine and the balance of water.
The preparation method of the high-speed stable electroless copper plating solution comprises the following steps: firstly, copper sulfate pentahydrate and water are mutually dissolved, the mixture is fully stirred until the solution is clear, potassium sodium tartrate, 5, 5-diethylhydantoin, allylthiourea, tetrahydroxypropylethylenediamine, sodium hydroxide and formaldehyde are sequentially added, the mixture is fully stirred until the solution is clear, and finally, the volume is fixed to 1 liter by using water.
The deposition speed measured by the high-speed stable electroless copper plating solution is 14 mu m/h, the working solution is stable and does not decompose in the chemical deposition process, no copper particles are generated on the inner wall of the beaker, and the electroless copper plating layer is flat and uniform and has no roughness defect.
Example 5
A high-speed stable electroless copper plating solution comprises the following components: 20g/L of copper sulfate pentahydrate, 40g/L of sodium potassium tartrate, 15ml/L of formaldehyde (37%), 20g/L of sodium hydroxide, 20mg/L of 5, 5-diethylhydantoin, 10mg/L of thiosemicarbazide, 2g/L of tetrahydroxypropylethylenediamine and the balance of water.
The preparation method of the high-speed stable electroless copper plating solution comprises the following steps: firstly, dissolving copper sulfate pentahydrate with water, fully stirring until the solution is clear, sequentially adding potassium sodium tartrate, 5, 5-diethylhydantoin, thiosemicarbazide, tetrahydroxypropylethylenediamine, sodium hydroxide and formaldehyde, fully stirring until the solution is clear, and finally adding water to a constant volume of 1 liter.
The deposition speed measured by the high-speed stable electroless copper plating solution is 18 mu m/h, the working solution is stable and does not decompose in the chemical deposition process, no copper particles are generated on the inner wall of the beaker, and the electroless copper plating layer is flat and uniform and has no roughness defect.
The foregoing detailed description is given by way of example only, to better enable one of ordinary skill in the art to understand the patent, and is not to be construed as limiting the scope of what is encompassed by the patent; any equivalent alterations or modifications made according to the spirit of the disclosure of this patent are intended to be included in the scope of this patent.
Claims (3)
1. The high-speed stable electroless copper plating solution is characterized by comprising the following components in volume concentration:
8-25 g/L of copper sulfate pentahydrate,
15-40 g/L of potassium sodium tartrate,
5-20 ml/L of formaldehyde,
5-20 g/L of sodium hydroxide,
10-500 mg/L of a stabilizer,
the balance of water;
wherein the stabilizer is one of hydantoin, 5-dimethylhydantoin and 5, 5-diethylhydantoin;
the high-speed stable electroless copper plating solution also comprises a combined additive, wherein the combined additive consists of a thiourea derivative and a hydroxyalkyl-containing aminocarboxylic compound, the volume concentration of the thiourea derivative in the high-speed stable electroless copper plating solution is 0.1-50 mg/L, and the volume concentration of the hydroxyalkyl-containing aminocarboxylic compound in the high-speed stable electroless copper plating solution is 0.1-5 g/L;
wherein the thiourea derivative is one of thiosemicarbazide and thioallylamine, and the hydroxyalkyl-containing aminocarboxylic compound is one of N-hydroxyethyl ethylenediamine triacetic acid (HEDTA) and tetrahydroxypropyl Ethylenediamine (EDTP).
2. A high-speed stable electroless copper plating solution according to claim 1, wherein the mass concentration of formaldehyde is 37%.
3. A method of preparing a high speed stable electroless copper plating solution according to any of claims 1-2, comprising the steps of: dissolving copper sulfate pentahydrate with water, fully stirring until the solution is clear, sequentially adding sodium potassium tartrate, a stabilizer, a combined additive, sodium hydroxide and formaldehyde, fully stirring until the solution is clear, and metering the volume with water to obtain the high-speed stable chemical copper plating solution.
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