Copper surface micro-etching liquid and application method thereof
By using copper surface microetching liquid composed of polyethyleneimine and carboxylated nanodiamond, the safety hazards and environmental pollution problems of traditional strong acid etching liquid are solved, the micro-nano etching and purity of copper surface are achieved, and the safety of the process is improved. Sex and efficiency.
Patent Information
- Application Number
- CN202410843991.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-06-27
- Publication Date
- 2024-12-24
- Estimated Expiration
- 2044-06-27
AI Technical Summary
Traditional copper surface microetching liquid uses strong acids to cause equipment damage, environmental pollution and safety risks, and oxides or hydroxides may be generated during the etching process affect surface quality and subsequent process performance.
A copper surface microetching solution composed of polyethyleneimine and carboxylated nanodiamond is used to etch it in contact with the copper surface to avoid the formation of non-copper elemental products, forming a surface structure from micron to nanometer level.
The purity and consistency of the copper surface is achieved, the operational safety and environmental protection are improved, and the etching effect at the micro-nano level is achieved.
Smart Images
Figure CN118581454B_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of metal surface treatment agents, in particular to a copper surface micro-etching liquid and an application method thereof. Background Art
[0002] In the fields of microelectronics manufacturing, precision metal processing, and semiconductor packaging, copper is widely used due to its excellent electrical and thermal conductivity. Copper surface micro-etching liquid can achieve a certain degree of roughness and flatness on the copper surface through chemical reactions without damaging the copper substrate, thereby improving the copper surface performance and providing a good substrate for subsequent processes such as electroplating, printing, and coating. Traditional copper etching liquids mostly use strong acids such as sulfuric acid and nitric acid. Although these acids can achieve the etching effect on the copper surface, they cause serious damage to the equipment and environment due to their strong oxidizing and corrosive properties, and also pose certain safety hazards. In addition, strong oxidants may react with copper to form oxides or hydroxides during the etching process. These non-copper products not only affect the surface quality after etching, but may also affect the performance of subsequent processes such as electroplating and welding.
[0003] Therefore, providing a copper surface micro-etching solution that does not contain strong acid so that copper does not produce oxides or hydroxides during the etching process is of great significance in the technical field of metal surface treatment agents. Summary of the invention
[0004] Based on the above content, the present invention provides a copper surface micro-etching liquid and an application method thereof. The copper surface micro-etching liquid of the present invention does not contain a strong oxidant, and the surface after etching is single copper.
[0005] To achieve the above object, the present invention provides the following solutions:
[0006] One of the technical solutions of the present invention is a copper surface micro-etching solution, the raw materials of which include polyethyleneimine, carboxylated nano-diamond and solvent.
[0007] A second technical solution of the present invention is the application of the above-mentioned copper surface micro-etching liquid in copper surface micro-etching.
[0008] A third technical solution of the present invention is a method for micro-etching a copper surface, wherein the copper surface is brought into contact with the above-mentioned copper surface micro-etching liquid for etching.
[0009] The present invention discloses the following technical effects:
[0010] The present invention adopts carboxylated nano-diamond and polyethyleneimine complexing agent system to etch the copper surface, which can achieve micron or even nanometer etching effect and form a micro-nano surface. In addition, copper will not generate non-copper simple substance products during the etching process, thereby ensuring the purity and consistency of the surface after etching. At the same time, since the copper surface micro-etching liquid of the present invention does not contain a strong oxidant, it also has better operation safety and environmental protection. BRIEF DESCRIPTION OF THE DRAWINGS
[0011] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.
[0012] Figure 1 This is the surface morphology of copper after etching in Example 1.
[0013] Figure 2 This is the surface morphology of copper after etching in Example 2.
[0014] Figure 3 This is the surface morphology of copper after etching in Example 3.
[0015] Figure 4 This is the EDS image of the copper surface after etching in Example 1. DETAILED DESCRIPTION
[0016] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention.
[0017] It should be understood that the terms described in the present invention are only for describing a particular embodiment and are not intended to limit the present invention. In addition, for the numerical range in the present invention, it should be understood that each intermediate value between the upper and lower limits of the scope is also specifically disclosed. The intermediate value in any stated value or stated range, and each smaller range between any other stated value or intermediate value in the described range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.
[0018] Unless otherwise indicated, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art. Although the present invention describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of a conflict with any incorporated document, the content of this specification shall prevail.
[0019] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments of the present invention description without departing from the scope or spirit of the present invention. Other embodiments derived from the present invention description will be apparent to those skilled in the art. The present invention description and examples are exemplary only.
[0020] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.
[0021] The "room temperature" described in the present invention, unless otherwise specified, refers to 20-30°C.
[0022] The first aspect of the present invention provides a copper surface micro-etching solution, the raw materials of which include polyethyleneimine, carboxylated nano-diamond and a solvent.
[0023] In some embodiments of the invention, the solvent is water.
[0024] In some embodiments of the present invention, the concentration of carboxylated nanodiamond in the copper surface micro-etching solution is 50 μg / mL.
[0025] If the concentration of carboxylated nanodiamonds in the copper surface micro-etching solution is too low, micro-nano etching cannot be achieved, so the present invention limits the concentration of carboxylated nanodiamonds to the above parameters.
[0026] In some embodiments of the present invention, the concentration of polyethyleneimine in the copper surface micro-etching solution is 5-20 g / L.
[0027] Too high a concentration of polyethyleneimine in the copper surface micro-etching solution will lead to over-etching, while too low a concentration of polyethyleneimine will affect the etching effect. Therefore, the present invention preferably limits the concentration of polyethyleneimine in the copper surface micro-etching solution to 5-20 g / L.
[0028] In some embodiments of the present invention, the polyethyleneimine is a linear and / or branched polyethyleneimine with a weight average molecular weight of 600 to 10000. More preferably, the polyethyleneimine is a branched polyethyleneimine with a weight average molecular weight of 600.
[0029] The second aspect of the present invention provides the use of the above copper surface micro-etching solution in copper surface micro-etching.
[0030] A third aspect of the present invention provides a method for micro-etching a copper surface, wherein the copper surface is brought into contact with the above-mentioned copper surface micro-etching liquid for etching.
[0031] In some embodiments of the present invention, the step of polishing the copper surface is further included before contacting the copper surface with the copper surface micro-etching solution.
[0032] In some embodiments of the present invention, the contact between the copper surface and the copper surface micro-etching solution is achieved by immersing the copper surface in the copper surface micro-etching solution.
[0033] In some embodiments of the present invention, the contact time is 3-24 hours; more preferably 8-15 hours; and even more preferably 11-13 hours.
[0034] In some embodiments of the present invention, during the etching process, the copper surface micro-etching liquid is stirred at a rotation speed of 200-600 rpm; more preferably, the rotation speed is 300-500 rpm; and even more preferably, 400 rpm.
[0035] As the contact time is prolonged and the stirring speed is increased, the degree of etching will be increased, forming different morphologies. The present invention preferably limits the contact time and the rotation speed to the above parameters.
[0036] In some embodiments of the present invention, the temperature of the copper surface micro-etching solution during the etching process is 20-40°C.
[0037] Unless otherwise specified, the raw materials used in the embodiments of the present invention can be obtained through commercial sources.
[0038] The polyethyleneimine used in the embodiment of the present invention is branched polyethyleneimine with a weight average molecular weight of 600.
[0039] The mass concentration of the carboxylated nano-diamond used in the embodiment of the present invention is 5%, and the solvent is water.
[0040] The present invention is further described below by way of examples.
[0041] Example 1
[0042] Step 1, dilute 0.5g polyethyleneimine with deionized water to 100ml, add 100μL carboxylated nanodiamond (5%) and mix them thoroughly to obtain a copper surface micro-etching solution with a polyethyleneimine content of 5g / L.
[0043] Step 2, after polishing the surface of the copper substrate, immersing the polished surface of the copper substrate in a copper surface micro-etching solution so that the polished surface of the copper substrate contacts the copper surface micro-etching solution for etching (the temperature of the copper surface micro-etching solution is room temperature at this time), stirring the micro-etching solution at 400 rpm during the etching process, and the immersion time is 12 hours.
[0044] In this embodiment, the surface morphology of copper after etching is as follows Figure 1 As shown. Figure 1 It can be seen that after being etched by the copper surface micro-etching solution with a polyethyleneimine content of 5 g / L, a relatively uniform nanostructure is formed on the copper surface, and the width of the smallest unit is about 200 nm.
[0045] The EDS image of the copper surface after etching in this embodiment is as follows: Figure 4 As shown. Figure 4 It can be seen that the surface of copper is still copper after etching.
[0046] Example 2
[0047] Step 1, dilute 1g of polyethyleneimine with deionized water to 100ml, add 100μL of carboxylated nanodiamond (5%) and mix them thoroughly to obtain a copper surface micro-etching solution with a polyethyleneimine content of 10g / L.
[0048] Step 2 is the same as step 2 of Example 1.
[0049] In this embodiment, the surface morphology of copper after etching is as follows Figure 2 As shown. Figure 2 It can be seen that after being etched by the copper surface micro-etching solution with a polyethyleneimine content of 10 g / L, a uniform micrometer-level rough structure is formed on the copper surface.
[0050] Example 3
[0051] Step 1, dilute 2g of polyethyleneimine with deionized water to 100ml, add 100μL of carboxylated nanodiamond (5%) and mix them thoroughly to obtain a copper surface micro-etching solution with a polyethyleneimine content of 20g / L.
[0052] Step 2 is the same as step 2 of Example 1.
[0053] In this embodiment, the surface morphology of copper after etching is as follows Figure 3 As shown. Figure 3 It can be seen that after being etched by the copper surface micro-etching solution with a polyethyleneimine content of 20 g / L, a uniform micrometer-level rough structure is formed on the copper surface.
[0054] The embodiments described above are only descriptions of the preferred modes of the present invention, and are not intended to limit the scope of the present invention. Without departing from the design spirit of the present invention, various modifications and improvements made to the technical solutions of the present invention by ordinary technicians in this field should all fall within the protection scope determined by the claims of the present invention.
Claims
1. A copper surface micro-etching solution, characterized in that: The raw materials consist of polyethyleneimine, carboxylated nanodiamond and solvent; The solvent is water; The concentration of carboxylated nanodiamond in the copper surface micro-etching solution is 50 μg / mL; The concentration of polyethyleneimine in the copper surface micro-etching solution is 5-20 g / L.
2. The copper surface micro-etching solution according to claim 1, characterized in that: The polyethyleneimine is a linear and / or branched polyethyleneimine with a weight average molecular weight of 600-10000.
3. Application of the copper surface micro-etching solution as claimed in claim 1 or 2 in copper surface micro-etching.
4. A method for micro-etching a copper surface, characterized in that: The copper surface is brought into contact with the copper surface micro-etching solution according to claim 1 or 2 for etching.
5. The method for micro-etching a copper surface according to claim 4, characterized in that: The method also includes a step of polishing the copper surface before contacting the copper surface with the copper surface micro-etching liquid.
6. The method for micro-etching a copper surface according to claim 4, characterized in that: The contact between the copper surface and the copper surface micro-etching liquid is achieved by immersing the copper surface in the copper surface micro-etching liquid.
7. The method for micro-etching a copper surface according to claim 4, characterized in that: The contact time is 3-24 hours; during the etching process, the copper surface micro-etching liquid is stirred at a rotation speed of 200-600 rpm.