Metal etching preparation process

Abstract

The invention relates to a metal etching preparation process, and belongs to the technical field of etching liquid. The metal etching preparation process comprises the following steps of: after coating photoresist on a metal sheet, performing mask exposure and development treatment on a photoresist layer on the surface of the metal sheet; spraying an etching solution on the metal sheet, and etching the part, which is not covered by the photoresist, of the metal sheet; and cleaning and degumming the etched metal sheet, grinding the metal sheet in a grinding machine, and drying the metal sheet after ultrasonic cleaning. By improving the production process and finely etching and grinding the metal sheet, the problem of perforation is effectively avoided, sufficient hardness of the metal sheet is ensured, and deformation is prevented; the metal complexing agent contains an organic heterocyclic compound containing nitrogen, oxygen and sulfur heteroatoms, has a plurality of active adsorption sites, can be effectively adsorbed to the surface layer of metal copper to form a protective film, prevents copper corrosion, ensures that an etching solution keeps an excellent etching speed, and prevents excessive lateral erosion.

Description

Technical Field

[0001] The invention belongs to the technical field of etching liquid, and relates to a metal etching preparation process and a preparation method thereof. Background Art

[0002] In order to meet the heat dissipation challenges of electronic component technology, metal heat dissipation solutions are one of the best choices. In addition to the widely used metal substrate technology, phase change heat spreaders made of metal heat sinks are becoming the trend of current technological development. With the phase change heat transfer mechanism, metal heat spreaders can effectively conduct the heat generated by electronic components, reduce their operating temperature, and extend their service life. As for the metal heat sink, it is an indispensable raw material for manufacturing metal heat spreaders. It uses etching microstructure technology to create sufficient steam channels to improve heat exchange efficiency.

[0003] In the etching process of metal heat sink, the etching solution often needs to add metal complexing agent. The main function of the metal complexing agent is to form a stable complex with metal ions to prevent these metal ions from being re-deposited on the surface of the metal heat sink in the etching solution. This can ensure the uniformity and accuracy of the etching process and avoid the generation of poor surface roughness and uneven etching depth. In addition, the metal complexing agent can also increase the service life of the etching solution, reduce the frequency of frequent replacement of the etching solution due to the accumulation of metal ions, and thus reduce production costs. However, among the existing metal complexing agents, complexing agents containing only a single active functional group are generally used. In order to expand the etching efficiency of metals and broaden the application field, it is necessary to either increase the amount of addition or adopt a method of mixing and matching multiple metal complexing agents, which brings about the problems of high cost and low efficiency. Summary of the invention

[0004] The object of the present invention is to provide a metal etching preparation process and a preparation method thereof. The present invention improves the production process, performs fine etching and grinding on a metal sheet, effectively avoids the perforation problem, and ensures that the metal sheet has sufficient hardness to prevent deformation. The etching process of the present invention improves the quality and service life of the metal sheet, and ensures the stability and reliability of the production process. In addition, the metal complexing agent of the present invention contains an organic heterocyclic compound of nitrogen, oxygen, and sulfur atoms, has multiple active adsorption sites, can be effectively adsorbed to the surface of the metal copper, forms a protective film, prevents copper corrosion, ensures that the etching solution maintains an excellent etching speed, and prevents excessive side etching.

[0005] The purpose of the present invention can be achieved through the following technical solutions:

[0006] A metal etching preparation process comprises the following steps:

[0007] S1, after coating the photoresist on the metal sheet, performing mask exposure and development processing on the photoresist layer on the surface of the metal sheet;

[0008] S2, spraying the etching solution on the metal sheet to etch the parts of the metal sheet not covered by the photoresist;

[0009] S3, cleaning and degumming the etched metal sheet, then grinding it in a grinder, ultrasonic cleaning it and drying it, and the process is complete.

[0010] As a preferred technical solution of the present invention, in step S1, the exposure and development treatment is 40 mJ / cm 2 The exposure is 20s at the exposure power.

[0011] As a preferred technical solution of the present invention, in step S2, the etching temperature is 20-30°C.

[0012] As a preferred technical solution of the present invention, in step S3, the ultrasonic cleaning includes sequentially placing in a dewaxing solution, acetone and isobutanol for cleaning at a temperature of 45° C. for 5 minutes each.

[0013] As a preferred technical solution of the present invention, in step S3, the ultrasonic cleaning is performed by placing the product in deionized water for 10 minutes; and the temperature of the drying treatment is 80-90°C.

[0014] As a preferred technical solution of the present invention, the etching solution comprises the following components in parts by weight: 30-40 parts by weight of hydrogen peroxide, 5.4-6.2 parts by weight of glutaric acid, 4.6-5.4 parts by weight of pentaerythritol, 5.5-6.0 parts by weight of a metal complexing agent, 2-3 parts by weight of 2-aminobenzoic acid, 5-6 parts by weight of isopropanolamine and 45-52 parts by weight of deionized water.

[0015] As a preferred technical solution of the present invention, the preparation method of the metal complexing agent comprises the following steps:

[0016] Step 1: Add hydroxycinnamaldehyde and anhydrous ethanol into a reaction kettle, mix well, and then preheat. Under an inert atmosphere and stirring conditions, add ethylenediamine solution and glacial acetic acid for heating treatment, cool to room temperature, remove the solvent by rotary evaporation, wash, and then vacuum dry to obtain a preform;

[0017] Step 2: Add the preform and anhydrous ethanol into a reactor and stir to mix, then add thiomalic acid and an initiator in a mass ratio of , perform ultraviolet irradiation treatment, centrifuge to remove the solvent, wash and vacuum dry to obtain a metal complexing agent.

[0018] As a preferred technical solution of the present invention, in step one, the preheating temperature is 40°C; the inert atmosphere is a nitrogen atmosphere; the stirring condition is stirring at a speed of 400-600 rpm; and the heating treatment is heating at a temperature of 50-60°C for 4-5h.

[0019] As a preferred technical solution of the present invention, in step 1, the mass ratio of the hydroxycinnamaldehyde, anhydrous ethanol, ethylenediamine solution and glacial acetic acid is 7-8:30-40:20-25:0.3-0.4; the hydroxycinnamaldehyde is 2-hydroxycinnamaldehyde; and the ethylenediamine solution is prepared by mixing ethylenediamine and anhydrous ethanol in a mass ratio of 0.8-1.0:10.

[0020] As a preferred technical solution of the present invention, in step 2, the stirring and mixing is stirring at a rotation speed of 300-400rpm for 15-20min; the ultraviolet irradiation treatment is ultraviolet irradiation at a wavelength of 365nm for 5-6h; the washing is washing three times with anhydrous ethanol; and the vacuum drying is vacuum drying at a temperature of 60°C to constant weight.

[0021] As a preferred technical solution of the present invention, in step 2, the mass ratio of the preform, anhydrous ethanol, thiomalic acid and initiator is 10-11:40-50:2.4-2.8:0.20-0.23; the initiator is benzoin diethyl ether.

[0022] Beneficial effects of the present invention:

[0023] (1) The present invention improves the production process. Specifically, the metal sheet is finely etched and then the thickness of the metal sheet is further reduced by a grinding process after the etching process is completed, so that the problem of perforation during the etching process can be effectively avoided. At the same time, it can also ensure that the metal sheet will not be deformed due to insufficient hardness during subsequent use. The etching process of the present invention not only improves the quality and service life of the metal sheet, but also ensures the stability and reliability of the entire production process.

[0024] (2) The metal complexing agent obtained by the present invention contains an organic heterocyclic compound of nitrogen, oxygen and sulfur atoms, and has many active adsorption sites. It can be more easily adsorbed to the surface of metal copper, thereby forming a protective film to achieve the effect of inhibiting copper corrosion, showing excellent metal corrosion inhibition performance, ensuring that the etching solution maintains an excellent etching speed, and preventing excessive side corrosion. DETAILED DESCRIPTION

[0025] In order to further illustrate the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the specific implementation methods, structures, features and effects of the present invention are described in detail below in combination with the embodiments.

[0026] A metal etching preparation process comprises the following steps:

[0027] S1. After coating the photoresist on the metal sheet, the photoresist layer on the surface of the metal sheet is subjected to mask exposure and development treatment; the exposure and development treatment is 40 mJ / cm 2 The exposure is 20s at the exposure power;

[0028] S2, spraying the etching liquid on the metal sheet to etch the metal sheet portion not covered by the photoresist; the etching temperature is 20-30°C

[0029] S3, the etched metal sheet is cleaned and debonded, then placed in a grinder for grinding, and dried after ultrasonic cleaning, and the process is completed; wherein, before the ultrasonic cleaning, the process includes sequentially placing the metal sheet in a dewaxing solution, acetone and isobutyl alcohol for cleaning at 45°C for 5 minutes each; the ultrasonic cleaning is placing the metal sheet in deionized water for ultrasonic cleaning for 10 minutes; and the drying temperature is 80-90°C.

[0030] Example 1

[0031] The etching solution comprises the following components in parts by weight:

[0032] 30 parts by weight of hydrogen peroxide, 5.4 parts by weight of glutaric acid, 4.6 parts by weight of pentaerythritol, 5.5 parts by weight of a metal complexing agent, 2 parts by weight of 2-aminobenzoic acid, 5 parts of isopropanolamine and 45 parts by weight of deionized water;

[0033] The preparation method of the metal complexing agent comprises the following steps:

[0034] Step 1: Add hydroxycinnamaldehyde and anhydrous ethanol to a reactor, mix well, and then preheat. Under an inert atmosphere and stirring conditions, add ethylenediamine solution and glacial acetic acid for heating treatment, cool to room temperature, evaporate the solvent, wash, and then vacuum dry to obtain a preform; the preheating temperature is 40°C; the inert atmosphere is a nitrogen atmosphere; the stirring condition is stirring at a speed of 400rpm; the heating treatment is heating at a temperature of 50°C for 4h; the mass ratio of the hydroxycinnamaldehyde, anhydrous ethanol, ethylenediamine solution and glacial acetic acid is 7:30:20:0.3; the hydroxycinnamaldehyde is 2-hydroxycinnamaldehyde; the ethylenediamine solution is prepared by mixing ethylenediamine and anhydrous ethanol in a mass ratio of 0.8:10;

[0035] Step 2: adding the preform and anhydrous ethanol into a reaction kettle and stirring and mixing, adding thiomalic acid and an initiator for ultraviolet irradiation treatment, centrifuging to remove the solvent, washing and vacuum drying to obtain a metal complexing agent; the stirring and mixing is stirring at a speed of 300 rpm for 15 minutes; the ultraviolet irradiation treatment is ultraviolet irradiation at a wavelength of 365 nm for 5 hours; the washing is washing with anhydrous ethanol three times; the vacuum drying is vacuum drying at a temperature of 60°C to constant weight; the mass ratio of the preform, anhydrous ethanol, thiomalic acid and initiator is 10:40:2.4:0.20; the initiator is benzoin diethyl ether.

[0036] Example 2

[0037] The etching solution comprises the following components in parts by weight:

[0038] 35 parts by weight of hydrogen peroxide, 5.8 parts by weight of glutaric acid, 5 parts by weight of pentaerythritol, 5.8 parts by weight of a metal complexing agent, 2.5 parts by weight of 2-aminobenzoic acid, 5.5 parts of isopropanolamine and 48 parts by weight of deionized water;

[0039] The preparation method of the metal complexing agent comprises the following steps:

[0040] Step 1: Add hydroxycinnamaldehyde and anhydrous ethanol to a reactor, mix well, and then preheat. Under an inert atmosphere and stirring conditions, add ethylenediamine solution and glacial acetic acid for heating treatment, cool to room temperature, evaporate the solvent, wash and vacuum dry to obtain a preform; the preheating temperature is 40°C; the inert atmosphere is a nitrogen atmosphere; the stirring condition is stirring at a speed of 500rpm; the heating treatment is heating at a temperature of 55°C for 4.5h; the mass ratio of the hydroxycinnamaldehyde, anhydrous ethanol, ethylenediamine solution and glacial acetic acid is 7.5:35:22:0.35; the hydroxycinnamaldehyde is 2-hydroxycinnamaldehyde; the ethylenediamine solution is prepared by mixing ethylenediamine and anhydrous ethanol in a mass ratio of 0.9:10;

[0041] Step 2: adding the preform and anhydrous ethanol into a reactor and stirring and mixing, adding thiomalic acid and an initiator for ultraviolet irradiation treatment, centrifuging to remove the solvent, washing and vacuum drying to obtain a metal complexing agent; the stirring and mixing is stirring at a speed of 350rpm for 18min; the ultraviolet irradiation treatment is ultraviolet irradiation at a wavelength of 365nm for 5.5h; the washing is washing with anhydrous ethanol three times; the vacuum drying is vacuum drying at a temperature of 60°C to constant weight; the mass ratio of the preform, anhydrous ethanol, thiomalic acid and initiator is 10.5:45:2.6:0.22; the initiator is benzoin diethyl ether.

[0042] Example 3

[0043] The etching solution comprises the following components in parts by weight:

[0044] 40 parts by weight of hydrogen peroxide, 6.2 parts by weight of glutaric acid, 5.4 parts by weight of pentaerythritol, 6.0 parts by weight of a metal complexing agent, 3 parts by weight of 2-aminobenzoic acid, 6 parts of isopropanolamine and 52 parts by weight of deionized water;

[0045] The preparation method of the metal complexing agent comprises the following steps:

[0046] Step 1: Add hydroxycinnamaldehyde and anhydrous ethanol to a reactor, mix well, and then preheat. Under an inert atmosphere and stirring conditions, add ethylenediamine solution and glacial acetic acid for heating treatment, cool to room temperature, evaporate the solvent, wash, and then vacuum dry to obtain a preform; the preheating temperature is 40°C; the inert atmosphere is a nitrogen atmosphere; the stirring condition is stirring at a speed of 600rpm; the heating treatment is heating at a temperature of 60°C for 5h; the mass ratio of the hydroxycinnamaldehyde, anhydrous ethanol, ethylenediamine solution and glacial acetic acid is 8:40:25:0.4; the hydroxycinnamaldehyde is 2-hydroxycinnamaldehyde; the ethylenediamine solution is prepared by mixing ethylenediamine and anhydrous ethanol in a mass ratio of 1.0:10;

[0047] Step 2: adding the preform and anhydrous ethanol into a reaction kettle and stirring and mixing, adding thiomalic acid and an initiator for ultraviolet irradiation treatment, centrifuging to remove the solvent, washing and vacuum drying to obtain a metal complexing agent; the stirring and mixing is stirring at a speed of 400 rpm for 20 minutes; the ultraviolet irradiation treatment is ultraviolet irradiation at a wavelength of 365 nm for 6 hours; the washing is washing with anhydrous ethanol three times; the vacuum drying is vacuum drying at a temperature of 60°C to constant weight; the mass ratio of the preform, anhydrous ethanol, thiomalic acid and initiator is 11:50:2.8:0.23; the initiator is benzoin diethyl ether.

[0048] Comparative Example 1

[0049] Compared with Example 3, the difference in Comparative Example 1 is that cinnamaldehyde replaces hydroxycinnamaldehyde, and the other components, preparation steps and parameters are the same.

[0050] Comparative Example 2

[0051] Compared with Example 3, the difference in Comparative Example 2 is that ethylamine replaces ethylenediamine, and the other components, preparation steps and parameters are the same.

[0052] Comparative Example 3

[0053] Compared with Example 3, the difference in Comparative Example 3 is that anhydrous ethanol replaces ethylenediamine, and the other components, preparation steps and parameters are the same.

[0054] Comparative Example 4

[0055] Compared with Example 3, Comparative Example 4 is different in that thiomalic acid is not used, and the other components, preparation steps and parameters are the same.

[0056] Comparative Example 5

[0057] Compared with Example 3, the difference in Comparative Example 5 is that pentaerythritol is 3 parts by weight, and the other components, preparation steps and parameters are the same.

[0058] The etching solutions prepared in Examples 1-3 and Comparative Examples 1-5 were subjected to the following performance tests, respectively. The test results are shown in Table 1.

[0059] Copper corrosion resistance test: Immerse the base material with copper layer in 50℃ etching solution for 10 minutes, then blow dry the surface resistance of the copper layer and observe the change of resistance value. In this process, the judgment criteria are as follows: if the resistance change is less than 10%, it is considered qualified; if the resistance change reaches or exceeds 10%, it is considered unqualified.

[0060] Side etching effect test: After etching and stripping, the substrate is dried and its pattern line width is observed;

[0061] Table 1

[0062] Copper corrosion test Side etch line width (μm) Example 1 qualified 1.1 Example 2 qualified 1.2 Example 3 qualified 1.0 Comparative Example 1 Failure 1.6 Comparative Example 2 Failure 1.8 Comparative Example 3 Failure 2.5 Comparative Example 4 Failure 2.2 Comparative Example 5 Failure 1.9

[0063] From the test results in Table 1, it can be seen that compared with Comparative Examples 1-5, the etching effect of the etching solution prepared in Examples 1-3 is significantly better than that in Comparative Examples 1-5.

[0064] Through comparative analysis, it can be known that the metal complexing agent prepared by the present invention contains a dihydroxyl, a diimine structure and a dicarboxyl structure, forming an organic heterocyclic compound containing nitrogen, oxygen and sulfur atoms, and has many active adsorption sites, which can be more easily adsorbed to the surface of metal copper, thereby forming a protective film to achieve the effect of inhibiting copper corrosion, showing excellent metal corrosion inhibition performance, ensuring that the etching solution maintains an excellent etching speed, and preventing excessive side etching; when the comparative examples 1-5 do not contain sulfur elements and carboxyl groups, lack hydroxyl groups or the number of imine structures decreases, the line width after etching is poor, and the line shape is easy to deteriorate; pentaerythritol has a solubilizing effect, so that the metal complexing agent is better soluble in the etching solution, and its function of inhibiting copper corrosion is fully exerted.

[0065] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Although the present invention has been disclosed as a preferred embodiment as above, it is not used to limit the present invention. Any technical personnel in this field can make some changes or modify the technical contents disclosed above into equivalent embodiments without departing from the scope of the technical solution of the present invention. However, any indirect modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention without departing from the content of the technical solution of the present invention still fall within the scope of the technical solution of the present invention.

Claims

1. A metal etching preparation process, characterized in that: The metal etching preparation process comprises the following steps: S1, after coating the photoresist on the metal sheet, performing mask exposure and development processing on the photoresist layer on the surface of the metal sheet; S2, spraying the etching solution on the metal sheet to etch the parts of the metal sheet not covered by the photoresist; S3, cleaning and degumming the etched metal sheet, then grinding it in a grinder, ultrasonic cleaning it and drying it, and the process is complete.

2. The metal etching preparation process according to claim 1, characterized in that: In step S1, the exposure and development process is 40 mJ / cm 2 The exposure is 20s at the exposure power.

3. The metal etching preparation process according to claim 1, characterized in that: In step S2, the etching temperature is 20-30°C.

4. The metal etching preparation process according to claim 1, characterized in that: In step S3, the ultrasonic cleaning includes sequentially placing in a dewaxing solution, acetone and isobutanol for cleaning at 45°C for 5 minutes each.

5. The metal etching preparation process according to claim 1, characterized in that: In step S3, the ultrasonic cleaning is performed in deionized water for 10 minutes; the temperature of the drying treatment is 80-90°C.

6. The metal etching preparation process according to claim 1, characterized in that: The etching solution comprises the following components in parts by weight: 30-40 parts by weight of hydrogen peroxide, 5.4-6.2 parts by weight of glutaric acid, 4.6-5.4 parts by weight of pentaerythritol, 5.5-6.0 parts by weight of a metal complexing agent, 2-3 parts by weight of 2-aminobenzoic acid, 5-6 parts by weight of isopropanolamine and 45-52 parts by weight of deionized water.

7. The metal etching preparation process according to claim 6, characterized in that: The preparation method of the metal complexing agent comprises the following steps: Step 1: Add hydroxycinnamaldehyde and anhydrous ethanol into a reaction kettle, mix well, and then preheat. Under an inert atmosphere and stirring conditions, add ethylenediamine solution and glacial acetic acid for heating treatment, cool to room temperature, remove the solvent by rotary evaporation, wash, and then vacuum dry to obtain a preform; Step 2: Add the preform and anhydrous ethanol into a reactor and stir to mix, then add thiomalic acid and an initiator in a mass ratio of , perform ultraviolet irradiation treatment, centrifuge to remove the solvent, wash and vacuum dry to obtain a metal complexing agent.

8. The metal etching preparation process according to claim 7, characterized in that: In step one, the preheating temperature is 40°C; the inert atmosphere is a nitrogen atmosphere; the stirring condition is stirring at a rotation speed of 400-600 rpm; the heating treatment is heating at a temperature of 50-60°C for 4-5h; the mass ratio of the hydroxycinnamaldehyde, anhydrous ethanol, ethylenediamine solution and glacial acetic acid is 7-8:30-40:20-25:0.3-0.4; the hydroxycinnamaldehyde is 2-hydroxycinnamaldehyde; the ethylenediamine solution is prepared by mixing ethylenediamine and anhydrous ethanol in a mass ratio of 0.8-1.0:

10.

9. The metal etching preparation process according to claim 7, characterized in that: In step 2, the stirring and mixing is stirring at a speed of 300-400 rpm for 15-20 minutes; the ultraviolet irradiation treatment is ultraviolet irradiation at a wavelength of 365 nm for 5-6 hours; the washing is washing three times with anhydrous ethanol; the vacuum drying is vacuum drying at a temperature of 60°C to constant weight; the mass ratio of the preform, anhydrous ethanol, thiomalic acid and initiator is 10-11:40-50:2.4-2.8:0.20-0.23; and the initiator is benzoin diethyl ether.