Efficient and high-leveling-capacity electronickelling solution

Abstract

The invention discloses a high-efficiency and high-leveling-capacity electronickelling solution, and relates to the technical field of electroplating. The high-efficiency and high-leveling-capacity electronickelling solution comprises the following components in parts by mass: 60-90 parts of nickel salt; 60-120 parts of a composite brightener; 40-80 parts of a stabilizer; 50 to 100 parts of an anti-pinhole agent; 40-80 parts of a dispersant; and 50-150 parts of a composite leveling agent. The composite brightener provided by the invention improves the tolerance of high current density, and especially has more prominent advantages on the compactness and binding force of a thick nickel coating; the anti-pinhole agent can reduce the porosity of the plating layer possibly caused by gas precipitation in the electroplating process, and less nickel nodule is generated, so that the toughness of the plating layer is enhanced; according to the nickel electroplating solution with the composite leveling agent matched with the composite brightening agent, the roughness Ra value of a base material with the roughness Ra value being 2.0 microns or above can be reduced to 0.4 microns or below, a dendritic crystal structure cannot occur when the leveling agent and the brightening agent are used in cooperation, and the problem of brittleness of a plating layer is avoided.

Description

Technical Field

[0001] The invention relates to the technical field of electroplating, in particular to a high-efficiency and high-leveling nickel electroplating solution. Background Art

[0002] The manufacturing process of power semiconductors involves a variety of high-end electronic chemicals. In recent years, the development of advanced surface treatment technology for electronic components has become a very important research direction; among them, the optical module is a device used for optical communication, which includes a light emitter and a receiver. It can convert electrical signals into optical signals and send them to remote devices, or convert received optical signals into electrical signals and pass them to computers, routers or switches. Optical modules are usually used in data centers, enterprise networks, telecommunications operator networks and other fields to achieve high-speed, long-distance, and high-reliability communications. With the rapid advancement of transmission speeds and entering the 800G era, and the future will usher in higher transmission rates such as 1.6T to 3.2T, power loss and heat dissipation management issues will be the biggest problem. At the same time, chips with lower temperatures will run better and have longer lifespans, thus saving costs in the long run.

[0003] The contact thermal resistance of the die-cast module decreases with the increase of temperature. The surface roughness of the die-cast module will significantly affect the size of the contact thermal resistance. The greater the roughness, the greater the contact thermal resistance and the slower the heat transfer efficiency. Therefore, in the manufacturing process of the radiator, the roughness of the surface of the joint material must be taken seriously.

[0004] The quality of electroplated nickel directly affects the quality of subsequent processing, which in turn affects the power loss and heat dissipation management of power semiconductors. To this end, many companies are committed to developing electroplated nickel layers with low roughness and high density, but the results are not ideal because the brightener cannot achieve satisfactory results.

[0005] Currently, no effective solution has been proposed for the problems in the related technologies. Summary of the invention

[0006] In view of the problems in the related art, the present invention proposes a high-efficiency and high-leveling ability nickel electroplating solution to overcome the above-mentioned technical problems existing in the existing related art.

[0007] To this end, the specific technical solution adopted by the present invention is as follows:

[0008] A high efficiency and high leveling ability nickel electroplating solution, comprising the following components by mass fraction:

[0009] Nickel salt 60-90 parts.

[0010] 60-120 parts of composite brightener.

[0011] Stabilizer 40-80 parts.

[0012] 50-100 parts of anti-pinhole agent.

[0013] Dispersant 40-80 parts.

[0014] 50-150 parts of composite leveling agent.

[0015] The solvent is deionized water.

[0016] Furthermore, the composite brightener includes poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate) and (2-bromoethyl)diphenylsulfonium trifluoromethanesulfonate.

[0017] Among them, poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate) is a multifunctional conductive polymer, and (2-bromoethyl)diphenylsulfonium trifluoromethanesulfonate is an organic compound.

[0018] Furthermore, the mass concentration ratio of poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate) to (2-bromoethyl)diphenylsulfonium trifluoromethanesulfonate is 1:1.

[0019] Furthermore, the composite leveler includes BzATP triethylammonium salt and Z-Lys(Boc)-OH dicyclohexylammonium salt.

[0020] Among them, BzATP triethylammonium salt is a derivative of adenosine triphosphate, and Z-Lys(Boc)-OH dicyclohexylammonium salt is a derivative of lysine.

[0021] Furthermore, the mass concentration ratio of BzATP triethylammonium salt to Z-Lys(Boc)-OH dicyclohexylammonium salt is 4:1.

[0022] Furthermore, the composite leveling agent is used to improve the positioning and leveling effect of the die casting surface and the low current area, so as to reduce the roughness of the substrate.

[0023] Further, the anti-pinhole agent includes p-amino-N, N-diethylaniline sulfate. P-amino-N, N-diethylaniline sulfate is a chemical substance.

[0024] Furthermore, the dispersant includes 4-aminobenzaldehyde polymer, which is used to promote the continuous generation of crystal nuclei and improve the compactness of the coating. The 4-aminobenzaldehyde polymer is a polymer obtained by polymerization of 4-aminobenzaldehyde.

[0025] Further, the stabilizer includes 4-tert-butoxycarbonylamino-thiophene-3-carboxylic acid. 4-tert-butoxycarbonylamino-thiophene-3-carboxylic acid is an organic compound, which is generally used as a synthetic intermediate in the fields of medicinal chemistry and biochemistry.

[0026] Furthermore, the nickel salt includes nickel sulfamate and nickel chloride with a mass concentration ratio of 3:2.

[0027] The beneficial effects of the present invention are:

[0028] (1) In the nickel electroplating solution provided by the present invention, the composite brightener can improve the tolerance to high current density. Compared with the traditional brightener saccharin, it has more advantages and higher efficiency, especially for the density and bonding strength of thick nickel plating layers.

[0029] (2) The anti-pinhole agent provided by the present invention can reduce the porosity of the coating that may be caused by gas precipitation during the electroplating process, reduce the generation of nickel nodules, and enhance the toughness of the coating.

[0030] (3) The composite leveling agent provided by the present invention can reduce the roughness Ra value of the die-casting with an initial substrate roughness Ra>2.0um to a minimum of 0.2um after nickel electroplating. In addition, the combination of the leveling agent and the brightener will not produce a dendritic crystal structure, thus avoiding the problem of coating brittleness.

[0031] (4) The dispersant is 4-aminobenzaldehyde polymer, which can promote the continuous generation of crystal nuclei, improve the density of the coating, and prevent atomic diffusion from occurring. DETAILED DESCRIPTION

[0032] According to an embodiment of the present invention, a high-efficiency and high-leveling capability nickel electroplating solution is provided.

[0033] The present invention is now further described in conjunction with a specific embodiment. According to an embodiment of the present invention, the high-efficiency and high-leveling nickel electroplating solution includes the following components by mass fraction:

[0034] Nickel salt 60-90 parts.

[0035] 60-120 parts of composite brightener.

[0036] Stabilizer 40-80 parts.

[0037] 50-100 parts of anti-pinhole agent.

[0038] Dispersant 40-80 parts.

[0039] 50-150 parts of composite leveling agent.

[0040] The solvent is deionized water.

[0041] In one embodiment, the composite brightener includes poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate) and (2-bromoethyl)diphenylsulfonium trifluoromethanesulfonate. The composite brightener can improve the tolerance of high current density, and is more efficient than the traditional brightener saccharin, especially for the density and bonding of thick nickel plating.

[0042] In one embodiment, the mass concentration ratio of poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate) to (2-bromoethyl)diphenylsulfonium trifluoromethanesulfonate is 1:1.

[0043] In one embodiment, the composite leveler includes BzATP triethylammonium salt and Z-Lys(Boc)-OH dicyclohexylammonium salt. The pH is controlled by a solution of 5% mass concentration of sodium hydroxide and 5% volume concentration of concentrated hydrochloric acid.

[0044] In one embodiment, the mass concentration ratio of BzATP triethylammonium salt to Z-Lys(Boc)-OH dicyclohexylammonium salt is 4:1.

[0045] In one embodiment, a composite leveling agent is used to improve the positioning and leveling effect of the die-casting surface and low current area, and can reduce the roughness Ra of the die-casting with an initial substrate roughness Ra>2.0um to below 0.4um after electroplating 6-10um pure nickel, and reduce the roughness Ra to below 0.2um after electroplating 15-20um pure nickel. In addition, the composite leveling agent and the composite brightener will not cause columnar crystals when used in combination, resulting in a brittle coating problem.

[0046] In one embodiment, the anti-pinhole agent includes p-amino-N,N-diethylaniline sulfate. The anti-pinhole agent can reduce the porosity of the coating that may be caused by gas evolution during the electroplating process, reduce the generation of nickel nodules, and enhance the toughness of the coating.

[0047] In one embodiment, the dispersant includes 4-aminobenzaldehyde polymer, which is used to promote the continuous generation of crystal nuclei, improve the density of the coating, and prevent atomic diffusion from occurring.

[0048] In one embodiment, the stabilizer includes 4-tert-butoxycarbonylamino-thiophene-3-carboxylic acid.

[0049] In one embodiment, the nickel salt includes nickel sulfamate and nickel chloride, with a mass concentration ratio of 3:2. The pH is 4.6-5.2, the operating temperature is 45-55°C, and the current density is 0.5-10A / dm2.

[0050] In order to more clearly understand the above technical solution of the present invention, the above solution of the present invention is described in detail below through specific comparative examples and embodiments.

[0051] Embodiment 1

[0052] A high-efficiency and high-leveling nickel electroplating solution, the high-efficiency and high-leveling nickel electroplating solution comprising:

[0053] 60g of nickel salt.

[0054] Composite brightener 60g.

[0055] Stabilizer 40g.

[0056] Anti-pinhole agent 50g.

[0057] Dispersant 40g.

[0058] 50g of composite leveling agent.

[0059] The composite brightener comprises poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate) and (2-bromoethyl)diphenylsulfonium trifluoromethanesulfonate, and the mass concentration ratio is 1:1.

[0060] The composite leveler includes BzATP triethylammonium salt and Z-Lys(Boc)-OH dicyclohexylammonium salt, and the mass concentration ratio is 4:1.

[0061] Anti-pinhole agents include p-amino-N,N-diethylaniline sulfate.

[0062] Dispersants include 4-aminobenzaldehyde polymers.

[0063] Stabilizers include 4-tert-butoxycarbonylamino-thiophene-3-carboxylic acid.

[0064] The nickel salt includes nickel sulfamate and nickel chloride, and the mass concentration ratio is 3:2.

[0065] Current density: 0.5ASD.

[0066] Temperature: 55℃.

[0067] pH: 5.2.

[0068] Current time: 60min.

[0069] Embodiment 2

[0070] A high-efficiency and high-leveling nickel electroplating solution, the high-efficiency and high-leveling nickel electroplating solution comprising:

[0071] Nickel salt 90g.

[0072] Composite brightener 120g.

[0073] Stabilizer 80g.

[0074] 100g of anti-pinhole agent.

[0075] Dispersant 80g.

[0076] 150g of composite leveling agent.

[0077] The composite brightener comprises poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate) and (2-bromoethyl)diphenylsulfonium trifluoromethanesulfonate, and the mass concentration ratio is 1:1.

[0078] The composite leveler includes BzATP triethylammonium salt and Z-Lys(Boc)-OH dicyclohexylammonium salt, and the mass concentration ratio is 4:1.

[0079] Anti-pinhole agents include p-amino-N,N-diethylaniline sulfate.

[0080] Dispersants include 4-aminobenzaldehyde polymers.

[0081] Stabilizers include 4-tert-butoxycarbonylamino-thiophene-3-carboxylic acid.

[0082] The nickel salt includes nickel sulfamate and nickel chloride, and the mass concentration ratio is 3:2.

[0083] Current density: 2.5ASD.

[0084] Temperature: 45℃.

[0085] pH: 4.6.

[0086] Current time: 40min.

[0087] Embodiment 3

[0088] A high-efficiency and high-leveling nickel electroplating solution, the high-efficiency and high-leveling nickel electroplating solution comprising:

[0089] Nickel salt 75g.

[0090] Composite brightener 90g.

[0091] Stabilizer 60g.

[0092] Anti-pinhole agent 75g.

[0093] Dispersant 60g.

[0094] 100g of composite leveling agent.

[0095] The composite brightener comprises poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate) and (2-bromoethyl)diphenylsulfonium trifluoromethanesulfonate, and the mass concentration ratio is 1:1.

[0096] The composite leveler includes BzATP triethylammonium salt and Z-Lys(Boc)-OH dicyclohexylammonium salt, and the mass concentration ratio is 4:1.

[0097] Anti-pinhole agents include p-amino-N,N-diethylaniline sulfate.

[0098] Dispersants include 4-aminobenzaldehyde polymers.

[0099] Stabilizers include 4-tert-butoxycarbonylamino-thiophene-3-carboxylic acid.

[0100] The nickel salt includes nickel sulfamate and nickel chloride, and the mass concentration ratio is 3:2.

[0101] Current density: 8ASD.

[0102] Temperature: 45℃.

[0103] pH: 4.6.

[0104] Current time: 15min.

[0105] Comparative Example 1

[0106] The electroplating nickel solution invented in patent number CN116926632A contains 100-150 g / L of nickel sulfate, 20-40 g / L of nickel chloride, 20-45 g / L of phosphorous acid, 20-35 g / L of sodium allyl sulfonate, 20-30 g / L of hydroxymethyl acrylic acid, and 0.1-0.3 g / L of saccharin. The electroplating nickel solution is mainly reduced to improve the stability by reducing the nickel content and thus obtaining a coating with good brightness and corrosion resistance. However, it does not achieve high leveling performance and specific leveling ability.

[0107] Comparative Example 2

[0108] The nickel electroplating solution invented in patent number CN116926632A includes 400g / L to 900g / L of nickel sulfamate, 1g / L to 20g / L of nickel sulfate, conductive salt, buffer and solvent, and the pH of the nickel electroplating solution is 3.5 to 4.5, and the solvent is pure water. It is a nickel electroplating solution dominated by the nickel sulfamate system. Without affecting the stress of the nickel layer, an appropriate amount of nickel sulfate is added to the nickel sulfamate system, which can promote the reduction and deposition of metal ions, so that the surface crystal particles of the electroplated product increase, and the crystal grain sense is more obvious, thereby increasing the intercalation force between the nickel layer and other metals, so that the nickel layer and the binding force of other metals are enhanced. At the same time, nickel sulfate can react with other chemical substances that constitute the nickel electroplating solution, such as chloride and other coordination ions to form complexes to improve the stability of the nickel electroplating solution. However, it is mainly through formula optimization to obtain a high-stability plating solution, and does not involve leveling ability related performance.

[0109] Electroplating experiments were conducted on substrates using the electroplating nickel solution products based on Examples 1 to 3. The experimental results show that the product provided in Example 1 makes the roughness Ra value of the substrate after nickel electroplating to be 0.113 μm; the product provided in Example 2 makes the roughness Ra value of the substrate after nickel electroplating to be 0.204 μm; and the product provided in Example 3 makes the roughness Ra value of the substrate after nickel electroplating to be 0.388 μm.

[0110] In summary, in the nickel electroplating solution provided by the present invention, the composite brightener can improve the tolerance to large current density, and compared with the traditional brightener saccharin, it has more advantages and higher efficiency, especially for the compactness and bonding strength of thick nickel coatings. The anti-pinhole agent provided by the present invention can reduce the porosity of the coating that may be caused by gas precipitation during the electroplating process, and reduce the generation of nickel nodules, thereby enhancing the toughness of the coating. The composite leveling agent provided by the present invention can reduce the roughness Ra value of the die-casting with an initial roughness Ra>2.0um of the substrate after nickel electroplating to a minimum of 0.2um, and the use of the leveling agent and the brightener in combination will not produce a dendritic crystal structure, thereby avoiding the problem of coating brittleness. The dispersant is a 4-aminobenzaldehyde polymer, and the dispersant can promote the continuous generation of crystal nuclei, improve the compactness of the coating, and is not prone to atomic diffusion.

[0111] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A high-efficiency and high-leveling nickel electroplating solution, the solvent is deionized water, characterized in that: The following components are included in mass fraction: 60-90 parts of nickel salt; Composite brightener 60-120 parts; 40-80 parts of stabilizer; 50-100 parts of anti-pinhole agent; Dispersant 40-80 parts; 50-150 parts of composite leveling agent.

2. The high-efficiency and high-leveling nickel electroplating solution according to claim 1, characterized in that: The composite brightener comprises poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate) and (2-bromoethyl)diphenylsulfonium trifluoromethanesulfonate.

3. The high-efficiency and high-leveling nickel electroplating solution according to claim 2, characterized in that: The mass concentration ratio of the poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate) to (2-bromoethyl)diphenylsulfonium trifluoromethanesulfonate is 1:

1.

4. The high-efficiency and high-leveling nickel electroplating solution according to claim 1, characterized in that: The composite leveler includes BzATP triethylammonium salt and Z-Lys(Boc)-OH dicyclohexylammonium salt.

5. The high-efficiency and high-leveling nickel electroplating solution according to claim 4, characterized in that: The mass concentration ratio of the BzATP triethylammonium salt to the Z-Lys(Boc)-OH dicyclohexylammonium salt is 4:

1.

6. The high-efficiency and high-leveling nickel electroplating solution according to claim 1, characterized in that: The composite leveling agent is used to improve the positioning and leveling effect of the die casting surface and the low current area, so as to reduce the roughness of the base material.

7. The high-efficiency and high-leveling nickel electroplating solution according to claim 1, characterized in that: The anti-pinhole agent includes p-amino-N,N-diethylaniline sulfate.

8. The high-efficiency and high-leveling nickel electroplating solution according to claim 1, characterized in that: The dispersant includes 4-aminobenzaldehyde polymer, which is used to promote the continuous generation of crystal nuclei and improve the compactness of the coating.

9. The high-efficiency and high-leveling nickel electroplating solution according to claim 1, characterized in that: The stabilizer includes 4-tert-butoxycarbonylamino-thiophene-3-carboxylic acid.

10. The high-efficiency and high-leveling nickel electroplating solution according to claim 1, characterized in that: The nickel salt includes nickel sulfamate and nickel chloride, and the mass concentration ratio is 3:2.