Preparation method of solution formula for laser-induced liquid phase deposition copper plating, solution formula and copper plating method

Abstract

The present invention relates to the field of copper plating technology, and specifically to a preparation method, solution formula, and copper plating method for a laser-induced liquid phase deposition copper plating solution. The preparation method comprises S1, dissolving a copper salt and a chelating agent separately in deionized water to obtain a copper salt solution and a chelating agent solution, mixing the copper salt solution and the chelating agent solution to obtain a first mixed solution that is transparent blue; S2, sequentially adding a reducing agent and a stabilizer to the first mixed solution, mixing them evenly, to obtain a second mixed solution; S3, adding an alkaline agent to the second mixed solution, adjusting the pH of the second mixed solution to alkaline, to obtain a third mixed solution as a copper ion solution system; S4, adding a hydroxyl-containing polymer compound to the third mixed solution, mixing evenly, and then adding nano-copper powder, and mixing evenly again to obtain a solution formula for laser-induced liquid phase deposition copper plating. The solution formula for laser-induced liquid phase deposition copper plating has the advantages of being environmentally friendly and having a stable and uniform deposition process.

Description

Technical Field

[0001] The invention relates to the technical field of copper plating, and in particular to a preparation method of a solution formula for laser-induced liquid phase deposition copper plating, a solution formula and a copper plating method. Background Art

[0002] In the modern electronics manufacturing industry, laser-induced copper deposition (LIDC) technology, due to its high precision and high resolution, has become a key process in the manufacture of printed circuit boards (PCBs), semiconductor packaging, and microelectronic devices. This technology uses a laser to generate localized high temperatures on the substrate surface, inducing a reduction reaction of copper ions and depositing copper metal on the substrate. Compared to traditional electroplating and chemical copper plating processes, LIDDC requires no applied current, offers flexible operation, and offers high precision, demonstrating significant potential in the fabrication of complex structures and minute patterns.

[0003] However, despite the many advantages of laser-induced copper deposition technology, the current solution formulation still has many problems in practical application: formaldehyde is used as a reducing agent when preparing the copper ion solution. There are two basic chemical reactions in the reaction process, namely, copper ions obtain electrons and become copper elemental, and formaldehyde reacts with hydroxide ions to produce hydrogen, water, and carboxylic acid ions and donate electrons; in addition to the effective redox reaction of copper ions on the catalytic surface and in addition to being reduced to metallic copper by formaldehyde, there are also many side reactions. This non-side reaction will reduce cuprous oxide particles, and the resulting cuprous oxide, copper and extremely fine powder will be suspended in the plating solution, which is difficult to remove by filtration and easily causes the plating solution to decompose.

[0004] If cuprous oxide co-deposits with copper, the copper deposited layer on the surface of the plated part will be loose and rough, resulting in poor adhesion between the copper deposited layer (i.e., the plated copper layer) and the substrate. Furthermore, some chemical components in the solution are highly corrosive or toxic, posing a potential threat to operator health and environmental safety. Wastewater treatment is complex and costly, increasing the environmental burden of the process and production costs. Summary of the Invention

[0005] One of the purposes of the present invention is to avoid the shortcomings of the prior art and provide a method for preparing a solution formula for laser-induced liquid deposition copper plating. The solution formula for laser-induced liquid deposition copper plating obtained by this preparation method has the advantages of being environmentally friendly, having a stable and uniform deposition process, and the obtained copper plating has the advantages of long service life and high quality.

[0006] A second object of the present invention is to provide a solution formula for laser-induced liquid deposition copper plating.

[0007] A third object of the present invention is to provide a copper plating method using laser-induced liquid deposition.

[0008] To achieve one of the above objectives, the present invention provides the following technical solutions:

[0009] Provided is a method for preparing a solution formula for laser-induced liquid deposition copper plating.

[0010] The following raw material components are used in the following formula amounts: copper salt, chelating agent, reducing agent, stabilizer, hydroxyl-containing polymer compound, alkaline reagent, and nano copper powder;

[0011] The preparation method comprises the following steps:

[0012] S1. Dissolving a copper salt and a chelating agent separately in deionized water to obtain a copper salt solution and a chelating agent solution, and mixing the copper salt solution and the chelating agent solution to obtain a first mixed solution that is transparent blue;

[0013] S2. Adding a reducing agent and a stabilizing agent to the first mixed solution in sequence and mixing them uniformly to obtain a second mixed solution;

[0014] S3, adding an alkaline agent to the second mixed solution to adjust the pH of the second mixed solution to alkaline, thereby obtaining a third mixed solution as a copper ion solution system;

[0015] S4. Adding a hydroxyl-containing polymer compound to the third mixed solution, mixing evenly, then adding nano copper powder, and mixing evenly again to obtain a solution formula for laser-induced liquid deposition copper plating.

[0016] In some embodiments, the weight ratio of copper salt, chelating agent, reducing agent, stabilizer, hydroxyl-containing polymer compound, and nano copper powder is 1.2-1.5:1.5-2:1.5-2.2:0.3-0.9:0.3-0.8.

[0017] The hydroxyl-containing polymer compound is polyethylene glycol, and the dosage of the hydroxyl-containing polymer compound is 15 g / L to 30 g / L. In S3, the pH is 11 to 13.

[0018] In some embodiments, the copper salt is one or a combination of two or more of copper sulfate pentahydrate, copper chlorate, and copper nitrate.

[0019] In some embodiments, the chelating agent is ethylenediaminetetraacetic acid powder, and when dissolving the ethylenediaminetetraacetic acid powder, sodium hydroxide is added during stirring to dissolve the ethylenediaminetetraacetic acid powder into a transparent solution.

[0020] In some embodiments, the reducing agent is sodium glutamate, glucose, baking soda, or a combination of two or more thereof.

[0021] In some embodiments, the stabilizer is 2-2-bipyridine.

[0022] In some embodiments, the hydroxyl-containing polymer compound is one or a combination of two or more.

[0023] In some embodiments, the alkaline agent is sodium hydroxide or potassium hydroxide.

[0024] The beneficial effects of the method for preparing a solution formula for laser-induced liquid deposition copper plating of the present invention are as follows:

[0025] The preparation method of the laser induced liquid phase deposition copper plating solution of the present invention adds a hydroxyl-containing polymer compound so that the solution formula can form a protective film on the surface of the formed copper plating, effectively inhibit the oxidation reaction of the copper plating, delay the oxidation process of copper, and improve the quality, stability and service life of the copper plating layer. In addition, nano copper powder is also mixed in to promote the uniform deposition of the entire solution formula, help to form a dense and uniform copper plating layer, reduce the generation of holes and cracks, ensure the consistency of the board surface, and improve the quality of the coating. The chelating agent used in the present invention replaces traditional ammonia water, which is more environmentally friendly and has less impact on operators and the environment. It is also more stable in the solution and is not easily affected by external conditions and loses its effectiveness, which helps to maintain the stability and consistency of the solution. The solution formula of the present invention can bring new breakthroughs to laser induced copper deposition technology and promote the further development and application of this technology in the field of electronic manufacturing.

[0026] To achieve the second of the above objectives, the present invention provides the following technical solutions:

[0027] A solution formula for laser-induced liquid phase deposition copper plating is provided, which is prepared by the above-mentioned preparation method of the solution formula for laser-induced liquid phase deposition copper plating.

[0028] To achieve the third of the above objectives, the present invention provides the following technical solutions:

[0029] A copper plating method using laser-induced liquid deposition is provided. The above-mentioned laser-induced liquid deposition copper plating solution formula is spread on the surface of a substrate, and the laser movement route is controlled to act on the solution formula on the surface of the substrate according to a preset copper plating route to obtain a copper-plated circuit. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 The present invention is a flowchart of a method for preparing a solution for laser-induced liquid deposition copper plating according to a specific embodiment of the present invention. DETAILED DESCRIPTION

[0031] The preferred embodiments of the present invention will be described in more detail below with reference to the accompanying drawings. Although preferred embodiments of the present invention are shown in the accompanying drawings, it should be understood that the present invention can be implemented in various forms and should not be limited by the embodiments described herein. Rather, these embodiments are provided to make the present invention more thorough and complete and to fully convey the scope of the present invention to those skilled in the art.

[0032] Example

[0033] The preparation method of the laser induced liquid deposition copper plating solution disclosed in this embodiment is as follows: Figure 1 As shown, the following raw material components are used in the following formula amounts: copper salt, chelating agent, reducing agent, stabilizer, hydroxyl-containing polymer compound, alkaline reagent, nano copper powder;

[0034] The preparation method comprises the following steps:

[0035] S1. Dissolving a copper salt and a chelating agent separately in deionized water to obtain a copper salt solution and a chelating agent solution, and mixing the copper salt solution and the chelating agent solution to obtain a first mixed solution that is transparent blue;

[0036] Specifically, the copper salt solution is slowly injected into the chelating agent solvent along an auxiliary tool such as a glass rod to ensure uniform stirring.

[0037] S2. Adding a reducing agent and a stabilizing agent to the first mixed solution in sequence and mixing them uniformly to obtain a second mixed solution;

[0038] S3, adding an alkaline agent to the second mixed solution to adjust the pH of the second mixed solution to alkaline, thereby obtaining a third mixed solution of a copper ion solution system;

[0039] Specifically, the desired copper ion solution system can be obtained by adjusting the solution to alkalinity with an alkaline reagent.

[0040] S4. Adding a hydroxyl-containing polymer compound to the third mixed solution, mixing evenly, then adding nano copper powder, and mixing evenly again to obtain a solution formula for laser-induced liquid deposition copper plating.

[0041] Specifically, the hydroxyl-containing polymer compound forms a protective film on the surface of the final copper plating layer, inhibiting copper oxidation and slowing its oxidation process. Adding nano-copper powder to the mix accelerates copper deposition, helping to form a dense copper plating layer, reducing the occurrence of holes and cracks, and improving the quality of the plating.

[0042] In this embodiment, the ratio of copper salt, chelating agent, reducing agent, stabilizer, hydroxyl-containing polymer compound, and nano copper powder is 1.2-1.5: 1.5-2: 1.5-2.2: 0.3-0.9: 0.3-0.8.

[0043] The weight ratio of the above raw material components can be adjusted according to actual conditions, wherein:

[0044] Copper salt can be 0.01 to 0.5 g / ml;

[0045] The chelating agent can be 0.02 to 0.4 g / ml;

[0046] The reducing agent can be 0.1 to 0.3 g / ml;

[0047] The stabilizer can be 0.01 to 0.2 g / ml;

[0048] The hydroxyl-containing polymer compound is polyethylene glycol, and the dosage of the hydroxyl-containing polymer compound is 15 g / L to 30 g / L. In S3, the pH is 11 to 13.

[0049] In this embodiment, the copper salt is one or a combination of two or more of copper sulfate pentahydrate, copper chlorate, and copper nitrate;

[0050] In this embodiment, the chelating agent is ethylenediaminetetraacetic acid powder. When dissolving the ethylenediaminetetraacetic acid powder, sodium hydroxide is added during stirring to dissolve the ethylenediaminetetraacetic acid powder into a transparent solution.

[0051] In this embodiment, the reducing agent is sodium glutamate, glucose, baking soda, or a combination of two or more thereof;

[0052] The use of the above-mentioned reducing agent is environmentally friendly, conforms to green production and does not harm the health of operators.

[0053] They are readily available on the market and relatively inexpensive, which can reduce production costs. At the same time, sodium glutamate and glucose are relatively stable in solution and are not easily affected by external conditions and become ineffective, helping to maintain the stability and consistency of the copper precipitation solution.

[0054] In this embodiment, the stabilizer is 2-2-bipyridine;

[0055] In this embodiment, the hydroxyl-containing polymer compound is one or a combination of two or more;

[0056] In this embodiment, the alkaline reagent is sodium hydroxide or potassium hydroxide.

[0057] Experimental example:

[0058] In order to illustrate the effect of the solution formulation of the present invention, the following experimental examples are carried out:

[0059] The present invention method is used to prepare a 25g / L copper sulfate solution with a volume of 50ml for laser-induced copper deposition. Laser induction is performed using a laser machine with an ultraviolet nanosecond laser wavelength of 1064λ / nm, a pulse width of 40ns, and a frequency of 300kHz. The substrate is high borosilicate glass with a silicon content of >80%, dimensions of 40×40×1mm, and a thermal conductivity of 1.2W / m·K. Specifically, the concentrations of the various raw material components are shown in Table 1:

[0060] Table 1

[0061]

[0062] Use a balance to weigh 1.25g copper sulfate pentahydrate, 1.75g ​​EDTA, 1.3g sodium glutamate, and an appropriate amount of sodium hydroxide;

[0063] Dissolve copper sulfate pentahydrate, sodium glutamate, and 25 g of sodium hydroxide in deionized water, respectively, and stir with a glass plate to prepare a 25 g / L copper sulfate solution, a 26 g / L sodium glutamate solution, and a sodium hydroxide solution with a pH of 12.2 to 12.8.

[0064] Put EDTA powder into a beaker, add deionized water to dissolve it, and place the resulting suspension on a magnetic stirrer for stirring. Then, add a certain amount of sodium hydroxide solution and stir until transparent.

[0065] Add EDTA solution to the copper sulfate solution and stir until a transparent blue mixed solution appears;

[0066] adding the sodium glutamate solution to the mixed solution;

[0067] Add 0.4g-0.83g of stabilizer 2-2-bipyridine and stir evenly;

[0068] Pour the prepared sodium hydroxide solution into the above mixed solution until the pH of the solution reaches 12.2-12.8, then add 20 g / L polyethylene glycol;

[0069] Finally, 0.5 g of nano copper powder was added to the mixed solution.

[0070] Experimental results:

[0071] The prepared solution was applied to a glass surface and then laser-treated on the glass plate coated with the copper ion solution. The resulting copper wire was 5% to 10% narrower in width than conventional copper wires, with a 20% to 40% increase in uniformity. Tensile testing showed a 30% to 60% increase in adhesion, a 10% to 30% increase in conductivity, and a 30% to 50% reduction in holes and cracks. This demonstrates that the present invention can produce superior copper wire.

[0072] Unless otherwise specifically stated, the relative arrangement of the parts and steps, numerical expressions and numerical values ​​set forth in these embodiments do not limit the scope of the present application. At the same time, it should be understood that, for ease of description, the sizes of the various parts shown in the drawings are not drawn according to actual proportional relationships. The techniques, methods and equipment known to those of ordinary skill in the relevant art may not be discussed in detail, but where appropriate, the techniques, methods and equipment should be considered as part of the authorization specification. In all examples shown and discussed here, any specific values ​​should be interpreted as being merely exemplary and not as limitations. Therefore, other examples of the exemplary embodiments may have different values. It should be noted that similar numbers and letters represent similar items in the following figures, and therefore, once an item is defined in one figure, it does not need to be further discussed in subsequent figures.

[0073] In the description of this application, it should be understood that the directions or positional relationships indicated by directional words such as "front, back, up, down, left, right", "horizontal, vertical, vertical, horizontal" and "top, bottom" are usually based on the directions or positional relationships shown in the accompanying drawings. They are only for the convenience of describing this application and simplifying the description. Unless otherwise specified, these directional words do not indicate or imply that the device or element referred to must have a specific direction or be constructed and operated in a specific direction. Therefore, they cannot be understood as limiting the scope of protection of this application; the directional words "inside and outside" refer to the inside and outside relative to the outline of each component itself.

[0074] For ease of description, spatially relative terms such as "above", "above", "on the upper surface of", "above", etc. may be used herein to describe the spatial positional relationship of a device or feature to other devices or features as shown in the figures. It should be understood that spatially relative terms are intended to include different orientations of the device in use or operation in addition to the orientation described in the figures. For example, if the device in the drawings is inverted, the device described as "above other devices or structures" or "above other devices or structures" will be positioned as "below other devices or structures" or "below other devices or structures". Thus, the exemplary term "above" can include both "above" and "below". The device can also be positioned in other different ways (rotated 90 degrees or in other orientations), and the spatially relative descriptions used here are interpreted accordingly.

[0075] In addition, it should be noted that the use of terms such as "first" and "second" to limit components is only for the convenience of distinguishing the corresponding components. Unless otherwise stated, the above terms have no special meaning and therefore cannot be understood as limiting the scope of protection of this application.

[0076] The foregoing description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Those skilled in the art will readily appreciate that various modifications and variations of the present invention are possible. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention are intended to be within the scope of protection of the present invention.

Claims

1. A method for preparing a solution formula for laser-induced liquid deposition copper plating, characterized in that: The following raw material components are used in the following formula amounts: copper salt, chelating agent, reducing agent, stabilizer, hydroxyl-containing polymer compound, alkaline reagent, and nano copper powder; The preparation method comprises the following steps: S1. Dissolving a copper salt and a chelating agent separately in deionized water to obtain a copper salt solution and a chelating agent solution, and mixing the copper salt solution and the chelating agent solution to obtain a first mixed solution that is transparent blue; S2. Adding a reducing agent and a stabilizing agent to the first mixed solution in sequence and mixing them uniformly to obtain a second mixed solution; S3, adding an alkaline agent to the second mixed solution to adjust the pH of the second mixed solution to alkaline, thereby obtaining a third mixed solution as a copper ion solution system; S4, adding a hydroxyl-containing polymer compound to the third mixed solution, mixing evenly, adding nano copper powder, and mixing evenly again to obtain a solution formula for laser-induced liquid deposition copper plating; the weight ratio of copper salt, chelating agent, reducing agent, stabilizer, and nano copper powder is 1.25:1.75:1.3:0.4-0.83:0.5; The hydroxyl-containing polymer compound is polyethylene glycol, and the amount of the hydroxyl-containing polymer compound is 15g / L to 30g / L. In S3, the pH is 11-13; and the reducing agent is sodium glutamate.

2. The method for preparing a solution formula for laser-induced liquid deposition copper plating according to claim 1, characterized in that: The copper salt is one or a combination of two or more of copper sulfate pentahydrate, copper chlorate, and copper nitrate.

3. The method for preparing a solution formula for laser-induced liquid deposition copper plating according to claim 1, characterized in that: The chelating agent is ethylenediaminetetraacetic acid powder. When dissolving the ethylenediaminetetraacetic acid powder, sodium hydroxide is added during stirring to dissolve the ethylenediaminetetraacetic acid powder into a transparent solution.

4. The method for preparing a solution formula for laser-induced liquid deposition copper plating according to claim 1, characterized in that: The stabilizer is 2-2-bipyridine.

5. The method for preparing a solution formula for laser-induced liquid deposition copper plating according to claim 1, characterized in that: The alkaline reagent is sodium hydroxide or potassium hydroxide.

6. A solution formula for laser-induced liquid deposition copper plating, characterized in that: The copper plating solution is prepared by the method for preparing the laser-induced liquid deposition copper plating solution according to any one of claims 1 to 5.

7. A copper plating method using laser-induced liquid deposition, characterized in that: The laser-induced liquid deposition copper plating solution formula of claim 6 is spread on the surface of the substrate, and the laser movement route is controlled to act on the solution formula on the surface of the substrate according to a preset copper plating route to obtain a copper-plated circuit.

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