Metal etching fabrication process

Abstract

The present application 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: after coating photoresist on a metal sheet, performing mask exposure and development treatment on the photoresist layer on the surface of the metal sheet; spraying etching liquid on the metal sheet to etch the part of the metal sheet not covered by the photoresist; cleaning and removing the photoresist of the metal sheet after etching, then placing the metal sheet in a grinding machine for grinding, and performing drying treatment after ultrasonic cleaning, and the process is completed.The present application improves the production process, finely etches and grinds the metal sheet, effectively avoids the problem of perforation, and ensures that the hardness of the metal sheet is sufficient to prevent deformation; the metal complexing agent of the present application contains an organic heterocyclic compound with nitrogen, oxygen and sulfur heteroatoms, has multiple active adsorption sites, can effectively adsorb to the surface layer of copper, form a protective film, prevent copper corrosion, ensure that the etching liquid maintains excellent etching speed, and prevent excessive side etching.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of etching solution and relates to a metal etching preparation process and a preparation method thereof. BACKGROUND

[0002] To cope with the heat dissipation challenge of electronic components, metal heat dissipation scheme is one of the preferred ones. In addition to the widely used metal substrate technology, the phase change heat plate made of metal heat dissipation sheet is becoming the trend of current technology development. With the mechanism of phase change heat transfer, the metal heat plate can effectively conduct the heat generated by electronic components, reduce the working temperature and prolong the service life. As for the metal heat dissipation sheet, it is an indispensable raw material for manufacturing metal heat plate, and through etching microstructure technology, enough vapor channels are created to improve the heat exchange efficiency.

[0003] In the etching process of metal heat dissipation sheet, metal complexing agent is often added to the etching solution. The main function of the metal complexing agent is to form stable complexes with metal ions to prevent these metal ions from re-depositing on the surface of the metal heat dissipation sheet in the etching solution. This can ensure the uniformity and accuracy of the etching process, avoid the generation of undesirable surface roughness and uneven etching depth. In addition, the metal complexing agent can also improve the service life of the etching solution, reduce the frequency of replacing the etching solution due to the accumulation of metal ions, and thus reduce the production cost. However, among the existing metal complexing agents, a complexing agent containing only a single active functional group is generally used. In order to expand the etching efficiency of metal and broaden the application field, either the amount of addition needs to be increased or a mixed method of multiple metal complexing agents needs to be adopted, which brings the problems of high cost and low efficiency. SUMMARY

[0004] The purpose of the present application is to provide a metal etching preparation process and a preparation method thereof. The present application improves the production process, finely etches and grinds the metal sheet, effectively avoids the problem of perforation, and ensures that the hardness of the metal sheet is sufficient to prevent deformation. The etching process of the present application 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 application contains an organic heterocyclic compound with nitrogen, oxygen and sulfur heteroatoms, has multiple active adsorption sites, can effectively adsorb to the surface layer of copper, form a protective film, prevent copper corrosion, ensure that the etching solution maintains excellent etching speed, and prevent excessive side etching.

[0005] The purpose of the present application can be achieved by the following technical solutions:

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

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

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

[0009] S3, cleaning and removing the photoresist of the etched metal sheet, then placing it in a grinding machine for grinding, ultrasonic cleaning and drying treatment, thereby completing the process.

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

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

[0012] As a preferred technical solution of the present application, in step S3, before the ultrasonic cleaning, the metal sheet is sequentially placed in a de-waxing solution, acetone and isobutyl alcohol for cleaning at 45℃ for 5 min.

[0013] As a preferred technical solution of the present application, in step S3, the ultrasonic cleaning is ultrasonic cleaning in deionized water for 10 min; and the drying treatment is at a temperature of 80-90℃.

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

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

[0016] Step one: mix hydroxycinnamaldehyde and anhydrous ethanol in a reaction kettle, preheat, add ethylenediamine solution and glacial acetic acid under inert atmosphere and stirring conditions, heat treatment, cool to room temperature, remove the solvent by rotary evaporation, wash and vacuum dry to obtain a preform;

[0017] Step two: mix the preform and anhydrous ethanol in a reaction kettle, add thiomalic acid and initiator at a mass ratio of 1:1, ultraviolet irradiation treatment, centrifugal removal of the solvent, washing and vacuum drying to obtain the metal complexing agent.

[0018] As a preferred technical solution of the present application, in step one, the preheating temperature is 40℃; the inert atmosphere is 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℃ for 4-5 h.

[0019] As a preferred technical scheme of the present application, in step one, the mass ratio of the hydroxyl cinnamaldehyde, anhydrous ethanol, ethylenediamine solution and glacial acetic acid is 7-8:30-40:20-25:0.3-0.4; the hydroxyl cinnamaldehyde is 2-hydroxycinnamaldehyde; the ethylenediamine solution is mixed by ethylenediamine and anhydrous ethanol according to the mass ratio of 0.8-1.0:10.

[0020] As a preferred technical scheme of the present application, in step two, the stirring mixing is stirring at the speed of 300-400 rpm for 15-20 min; the ultraviolet irradiation treatment is ultraviolet irradiation at the wavelength of 365 nm for 5-6 h; the washing is washing with anhydrous ethanol for three times; the vacuum drying is vacuum drying at the temperature of 60℃ until constant weight.

[0021] As a preferred technical scheme of the present application, in step two, 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] The beneficial effects of the present application are:

[0023] (1) The present application improves the production process, specifically, through fine etching treatment of the metal sheet, after completing the etching process, further reducing the thickness of the metal sheet through the grinding process, which can effectively avoid the problem of perforation in the etching process, and also ensures that the metal sheet will not deform in the subsequent use process due to insufficient hardness. The etching process of the present application 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 application contains organic heterocyclic compounds containing nitrogen, oxygen and sulfur heteroatoms, which has many active adsorption sites and can be easily adsorbed to the surface layer of copper, thereby forming a protective film to achieve the effect of inhibiting copper corrosion, exhibiting excellent metal corrosion inhibition performance, ensuring that the etching solution maintains excellent etching speed and prevents excessive side etching. DETAILED DESCRIPTION

[0025] In order to further illustrate the technical means and effects adopted by the present application to achieve the predetermined invention purpose, the specific embodiments, structures, features and effects according to the present application are described in detail as follows in combination with examples.

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

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

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

[0029] S3, cleaning and removing the photoresist of the etched metal sheet, then placing it in a grinding machine for grinding, ultrasonic cleaning and drying treatment, i.e. finished; wherein, before the ultrasonic cleaning, it includes being placed in de-waxing liquid, acetone and isobutyl alcohol in turn for 5 min each at 45℃ temperature; the ultrasonic cleaning is ultrasonic cleaning in deionized water for 10 min; the drying treatment temperature is 80-90℃.

[0030] Example 1

[0031] The etching liquid includes the following components by weight ratio:

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

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

[0034] Step one: mix hydroxycinnamaldehyde and anhydrous ethanol in a reaction kettle, preheat, add ethylenediamine solution and glacial acetic acid under inert atmosphere and stirring conditions, heat treatment, cool to room temperature, rotary evaporation to remove the solvent, wash and vacuum dry to obtain a preform; the preheating temperature is 40℃; the inert atmosphere is nitrogen atmosphere; the stirring condition is stirring at a speed of 400 rpm; the heating treatment is heating at 50℃ for 4h; the mass ratio of hydroxycinnamaldehyde, anhydrous ethanol, ethylenediamine solution and glacial acetic acid is 7:30:20:0.3; the hydroxycinnamaldehyde is 2-hydroxycinnamaldehyde; the ethylenediamine solution is mixed by ethylenediamine and anhydrous ethanol in a mass ratio of 0.8:10;

[0035] Step two: the preform and anhydrous ethanol are added into a reaction kettle and stirred and mixed, then thiomalic acid and an initiator are added for ultraviolet irradiation treatment, after centrifugation to remove the solvent, washing and vacuum drying, a metal complexing agent is obtained; the stirring and mixing is stirring at a speed of 300 rpm for 15 min; the ultraviolet irradiation treatment is ultraviolet irradiation at a wavelength of 365 nm for 5 h; the washing is washing with anhydrous ethanol for three times; the vacuum drying is vacuum drying at a temperature of 60℃ until 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 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 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 one: hydroxycinnamaldehyde and anhydrous ethanol are added into a reaction kettle and mixed, then preheating is performed, under the condition of inert atmosphere and stirring, ethylenediamine solution and glacial acetic acid are added for heating treatment, cooled to room temperature, rotary evaporation to remove the solvent, washing and vacuum drying, a preform is obtained; the preheating temperature is 40℃; the inert atmosphere is nitrogen atmosphere; the stirring condition is stirring at a speed of 500 rpm; the heating treatment is heating at a temperature of 55℃ for 4.5 h; the mass ratio of 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 at a mass ratio of 0.9:10;

[0041] Step two: the preform and anhydrous ethanol are added into a reaction kettle and stirred and mixed, then thiomalic acid and an initiator are added for ultraviolet irradiation treatment, after centrifugation to remove the solvent, washing and vacuum drying, a metal complexing agent is obtained; the stirring and mixing is stirring at a speed of 350 rpm for 18 min; the ultraviolet irradiation treatment is ultraviolet irradiation at a wavelength of 365 nm for 5.5 h; the washing is washing with anhydrous ethanol for three times; the vacuum drying is vacuum drying at a temperature of 60℃ until 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 by weight ratio:

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

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

[0046] Step one: hydroxycinnamaldehyde and anhydrous ethanol are added to the reaction kettle, mixed and preheated, then ethylenediamine solution and glacial acetic acid are added and heated under inert atmosphere and stirring conditions, cooled to room temperature, the solvent is removed by rotary evaporation, washed and vacuum dried to obtain a preform; the preheating temperature is 40℃; the inert atmosphere is nitrogen atmosphere; the stirring condition is stirring at a speed of 600 rpm; the heating treatment is heating at 60℃ for 5h; the mass ratio of hydroxycinnamaldehyde, anhydrous ethanol, ethylenediamine solution and glacial acetic acid is 8:40:25:0.4; the hydroxycinnamaldehyde is 2-hydroxycinnamaldehyde; the ethylenediamine solution is mixed by ethylenediamine and anhydrous ethanol at a mass ratio of 1.0:10;

[0047] Step two: the preform and anhydrous ethanol are added to the reaction kettle and stirred and mixed, then thiomalic acid and initiator are added and subjected to ultraviolet irradiation treatment, the solvent is removed by centrifugation, washed and vacuum dried to obtain a metal complexing agent; the stirring and mixing is stirring at a speed of 400 rpm for 20 min; the ultraviolet irradiation treatment is ultraviolet irradiation at a wavelength of 365 nm for 6h; the washing is washing with anhydrous ethanol three times; the vacuum drying is vacuum drying at a temperature of 60℃ until 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] Comparative Example 1 differs from Example 3 in that cinnamaldehyde is used instead of hydroxycinnamaldehyde, and the other components, preparation steps and parameters are the same.

[0050] Comparative Example 2

[0051] Comparative Example 2 differs from Example 3 in that ethylamine is used instead of ethylenediamine, and the other components, preparation steps and parameters are the same.

[0052] Comparative Example 3

[0053] Comparative Example 3 differs from Example 3 in that anhydrous ethanol is used instead of ethylenediamine, and the other components, preparation steps and parameters are the same.

[0054] Comparative Example 4

[0055] Comparative Example 4 differs from Example 3 in that thiomalic acid is not used, and the remaining components, preparation steps and parameters are consistent.

[0056] Comparative Example 5

[0057] Comparative Example 5 differs from Example 3 in that pentaerythritol is 3 parts by weight, and the remaining components, preparation steps and parameters are consistent.

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

[0059] Copper corrosion resistance test: immerse the substrate material with a copper layer in the etching solution at 50°C for 10 minutes, then blow-dry the surface resistance of the copper layer, and observe the change in resistance value; during this process, the criteria are as follows: resistance change less than 10% is considered to be qualified; resistance change reaching or exceeding 10% is considered to be unqualified.

[0060] Side etching effect test: observe the pattern line width after etching and film removal treatment of the substrate and drying;

[0061] Table 1

[0062] Copper corrosion resistance test Side etch line width (pm) Example 1 Pass 1.1 Example 2 Pass 1.2 Example 3 Pass 1.0 Comparative Example 1 Fail 1.6 Comparative Example 2 Fail 1.8 Comparative Example 3 Fail 2.5 Comparative Example 4 Fail 2.2 Comparative Example 5 Fail 1.9

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

[0064] As can be seen from the comparative analysis, the metal complexing agent prepared in the present application contains a double-hydroxyl, double-imine structure and a double-carboxyl structure, forming an organic heterocyclic compound containing nitrogen, oxygen and sulfur heteroatoms, with numerous active adsorption sites, which can more easily adsorb to the surface layer of copper, and then form a protective film to achieve the effect of blocking copper corrosion, showing excellent metal corrosion inhibition performance, ensuring that the etching solution maintains excellent etching speed and prevents excessive side etching. In Comparative Examples 1-5, there is no sulfur element and carboxyl group, and the number of hydroxyl or imine structures is reduced, resulting in a difference in line width after etching and a tendency for the line to deteriorate. Pentaerythritol has a solubilizing effect, which makes the metal complexing agent better dissolve in the etching solution, fully exerting its function of inhibiting copper corrosion.

[0065] The above merely describes the preferred embodiments of the present application, and is not intended to limit the present application in any form. Although the present application has been disclosed with the preferred embodiments as above, it is not intended to limit the present application. Any person skilled in the art can make some changes or modifications to the above disclosed technical content to obtain equivalent embodiments with equivalent changes, as long as the changes or modifications do not deviate from the technical solution of the present application. Any indirect modifications, equivalent changes and modifications made to the above embodiments according to the technical essence of the present application still belong to the scope of the technical solution of the present application.

Claims

1. A metal etch preparation process, characterized by, The metal etching preparation process comprises the following steps: S1. After coating photoresist on the metal sheet, perform mask exposure and development treatment on the photoresist layer on the surface of the metal sheet; S2. Spray etching liquid on the metal sheet to etch the part of the metal sheet not covered by the photoresist; S3. Clean and remove the photoresist of the metal sheet after etching, then place it in a grinding machine for grinding, ultrasonic cleaning and drying treatment, and the process is completed; The etching liquid comprises the following components by weight: 30-40 parts of hydrogen peroxide, 5.4-6.2 parts of glutaric acid, 4.6-5.4 parts of pentaerythritol, 5.5-6.0 parts of metal complexing agent, 2-3 parts of 2-aminobenzoic acid, 5-6 parts of isopropyl alcohol amine and 45-52 parts of deionized water; The preparation method of the metal complexing agent comprises the following steps: Step one: mix hydroxycinnamaldehyde and anhydrous ethanol in a reaction kettle, preheat, add ethylenediamine solution and glacial acetic acid under inert atmosphere and stirring conditions, heat treatment, cool to room temperature, remove the solvent by rotary evaporation, wash and vacuum dry to obtain a preform; Step two: mix the preform and anhydrous ethanol in a reaction kettle, add thiomalic acid and initiator, and perform ultraviolet irradiation treatment, remove the solvent by centrifugation, wash and vacuum dry to obtain the metal complexing agent.

2. The metal etch preparation process of claim 1, wherein: In step S1, the exposure development treatment is 40 mJ / cm 2 Exposure power under exposure is 20 s.

3. The metal etch preparation process of claim 1, wherein: In step S2, the etching temperature is 20-30℃.

4. The metal etch preparation process of claim 1, wherein: In step S3, before ultrasonic cleaning, the metal sheet is sequentially placed in a de-waxing liquid, acetone and isobutyl alcohol for cleaning at 45℃ for 5 minutes each.

5. The metal etch preparation process of claim 1, wherein: In step S3, the ultrasonic cleaning is performed by placing the metal sheet in deionized water for 10 minutes, and the drying treatment is performed at a temperature of 80-90℃.

6. The metal etch preparation process of claim 1, wherein: In step one, the preheating temperature is 40℃; the inert atmosphere is nitrogen atmosphere; the stirring condition is stirring at a speed of 400-600 rpm; the heating treatment is heating at a temperature of 50-60℃ for 4-5 hours; the mass ratio of 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 mixed by ethylenediamine and anhydrous ethanol at a mass ratio of 0.8-1.0:

10.

7. The metal etch preparation process of claim 1, wherein: In step two, the stirring and mixing is performed at a speed of 300-400 rpm for 15-20 minutes; the ultraviolet irradiation treatment is performed at a wavelength of 365 nm for 5-6 hours; the washing is performed by cleaning with anhydrous ethanol three times; the vacuum drying is performed at a temperature of 60℃ until the weight is constant; 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.